table of contents - the clay minerals society · 2009-05-31 · 4 clays of the big sky 46th annual...

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TABLE OF CONTENTS CLAYS OF THE BIG SKY ................................................................................................................ 4

THE CLAY MINERALS SOCIETY ................................................................................................. 6

SOCIETY HISTORY .......................................................................................................................... 7

AWARDS ............................................................................................................................................. 9

Marilyn and Sturges W. Bailey Distinguished Member Award ...................................................... 9

Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Award .......................................... 9

George W. Brindley Lecture Award .............................................................................................. 10

Pioneer in Clay Science Award ...................................................................................................... 10

Citation of Special Recognition ...................................................................................................... 10

Editors of Clays and Clay Minerals ................................................................................................ 11

Past Presidents of the Society ......................................................................................................... 12

BILLINGS, MONTANA .................................................................................................................. 13

CROWNE PLAZA ............................................................................................................................ 19

MEETING SCHEDULE AT A GLANCE ...................................................................................... 21

TECHNICAL PROGRAM ............................................................................................................... 22

THURSDAY, JUNE 4, 2009 ......................................................................................................... 22

REGISTRATION ...................................................................................................................... 22

FRIDAY, JUNE 5, 2009 ................................................................................................................ 22

REGISTRATION ...................................................................................................................... 22

FIELD TRIP #1 - BENTONITES OF THE BIG HORN BASIN ....................................... 22

EXECUTIVE COMMITTEE MEETING .............................................................................. 22

SATURDAY, JUNE 6, 2009 ......................................................................................................... 23

REGISTRATION ...................................................................................................................... 23

FIELD TRIP #2 - BENTONITES OF THE BIG HORN BASIN ....................................... 23

CMS COUNCIL MEETING .................................................................................................... 23

WELCOMING RECEPTION ................................................................................................ 23

SUNDAY MORNING, JUNE 7, 2009 ......................................................................................... 24

REGISTRATION ...................................................................................................................... 24

PLENARY SESSION (Ballroom A, 3rd Floor) ......................................................................... 24

Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Lecture ............................................. 24

George W. Brindley Lecture ................................................................................................................. 24

TECHNICAL SESSIONS ........................................................................................................ 24

Bentonite - The Most Versatile Clay? (Session 1) ................................................................................ 24

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Practical Applications of Quantitative Analysis (Session 1) ................................................................. 25

Reactions of Iron in Clays and Clay Minerals (Session 1) ................................................................... 26

SUNDAY AFTERNOON, JUNE 7, 2009 ................................................................................... 26


Bentonite - The Most Versatile Clay? (Session 2) ................................................................................ 26

Microscopic and Spectroscopic Studies of Clay Mineral Reactions .................................................... 27

Reactions of Iron in Clays and Clay Minerals (Session 2) ................................................................... 28

MONDAY MORNING, JUNE 8, 2009 ....................................................................................... 30

REGISTRATION ...................................................................................................................... 30

PLENARY SESSION (Ballroom A, 3rd Floor) ......................................................................... 30

Welcome ........................................................................................................................................... 30

Pioneer in Clay Science Lecture............................................................................................................ 30

Marilyn and Sturges W. Bailey Award Lecture ..................................................................................... 30


Practical Applications of Quantitative Analysis (Session 2) ................................................................. 30

Industrial Clay Mineralogy: Mining, Processing, Utilization ............................................................... 31

MONDAY AFTERNOON, JUNE 8, 2009 ................................................................................. 32


Isotopes and Clays ................................................................................................................................. 32

From Discovery to Dollars: the Challenges of Innovation and Commercialization ........................... 33

POSTER SESSION ................................................................................................................... 34

Bentonite - The Most Versatile Clay? .................................................................................................... 34

Clay Interactions With Environmental Contaminants In Soils And Sediments ............................... 34

Practical Applications of Quantitative Analysis ................................................................................... 34

Clays and Energy ................................................................................................................................... 35

Isotopes and Clays ................................................................................................................................. 35

General Session ..................................................................................................................................... 35

TUESDAY MORNING, JUNE 9, 2009 ...................................................................................... 36

REGISTRATION ...................................................................................................................... 36

SUSTAINING MEMBERS BREAKFAST ............................................................................. 36


Clays and Energy ................................................................................................................................... 36

Clay Interactions With Environmental Contaminants In Soils And Sediments ............................... 37

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TUESDAY AFTERNOON, JUNE 9, 2009 ................................................................................. 38


A Drugstore In The Dirt: Medicinal Clays And Clay Minerals ........................................................... 38

General Session ..................................................................................................................................... 39

CMS BUSINESS MEETING ................................................................................................... 39

FEATS OF CLAY SESSION .................................................................................................... 39

BANQUET ................................................................................................................................ 40

WEDNESDAY, JUNE 10, 2009 ................................................................................................... 40

CLAYS OF YELLOWSTONE NATIONAL PARK ............................................................. 40

THURSDAY, JUNE 11, 2009 ....................................................................................................... 40

Workshop returns from Yellowstone National Park ................................................................ 40

SOCIETY AWARD LECTURE ABSTRACTS ............................................................................. 41

TECHNICAL SESSIONS ABSTRACTS ........................................................................................ 46

Author Index ..................................................................................................................................... 156

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CLAYS OF THE BIG SKY

46th Annual Meeting of

The Clay Minerals Society Billings, Montana, USA

June 5 – 11, 2009 Organizing Committee: Richard K. Brown, Chair, Wyo-Ben, Inc. Don D. Eisenhour, Amcol International Jessica Elzea-Kogel, Imerys Douglas K. McCarty, Chevron Energy Technology Corp. Andrew R. Thomas, Chevron Energy Technology Corp. Field Trips: Don D. Eisenhour, Amcol International Rick Magstadt, Wyo-Ben, Inc. G. Dale Nuttall, Wyo-Ben, Inc. Jason Schneider, American Colloid Company Workshop: Paul A. Schroeder, University of Georgia Abstracts: Joanne Lamb, Wyo-Ben, Inc. Mary Gray, The Clay Minerals Society Registration: Mary Gray, The Clay Minerals Society Web Site and Publications Design: Joanne Lamb, Wyo-Ben, Inc. Society Administration: Mary Gray, The Clay Minerals Society J. Alexander Speer, Mineralogical Society of America

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Session Chairs: Derek C. Bain, The Macauley Institute Gary W. Beall, Texas State University Steve J. Chipera, Chesapeake Energy Corporation Hailiang Dong, Miami University Dennis D. Eberl, U.S. Geological Survey W. Crawford Elliott, Georgia State University Will P. Gates, SmecTech Research Consulting Mark A. Herpfer, Oil-Dri Corp. of America Warren D. Huff, University of Cincinnati Cliff T. Johnston, Purdue University Jin-Wook Kim, Yonsei University Peter Komadel, Slovak Academy of Sciences David A. Laird, USDA National Soil Tilth Laboratory Douglas K. McCarty, Chevron Energy Technology Corp. Oladipo Omotoso, Natural Resources Canada Robert J. Pruett, Imerys Peter C. Ryan, Middlebury College Paul A. Schroeder, University of Georgia Lynda B. Williams, Arizona State University Andrew R. Thomas, Chevron Energy Technology Corp. Sponsors: Platinum Chevron Energy Technology Company Wyo-Ben, Inc. Gold AMCOL International Corp. Silver Sorptive Minerals Institute Bronze H. H. Murray and Associates M-I Swaco Thiele Kaolin Company

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THE CLAY MINERALS SOCIETY

President: Andrew R. Thomas, Chevron Energy Technology Vice President: Derek C. Bain, The Macaulay Institute Secretary: Warren Huff, University of Cincinnati Treasurer: J. Reed Glasmann, Willamette Geological Service Past President: Ray E. Ferrell, Jr., Louisiana State University

Editor-In-Chief, Clays and Clay Minerals: Joseph W. Stucki, University of Illinois Council: James E. Amonette, Pacific Northwest National Laboratory Christopher Breen, Sheffield Hallam University Victoria C. Hover, University of Louisiana at Lafayette Sridhar Komareni, Pennsylvania State University Kathleen Carrado, Argonne National Laboratory Hailiang Dong, Miami University Bruno Lanson, University J Fourier Sabine Petit, Universite de Poiters Steve J. Chipera, Chesapeake Energy Corporation Eric J Daniels, Chevron Energy Technology Co. Georg H Grathoff, Universitaet Greifswald Anja Maria Schleicher, University of Michigan Society Manager: Mary Gray The Clay Minerals Society 3635 Concorde Parkway, Suite 500 Chantilly, Virginia 20151-1125, USA Phone: 703-652-9960 Fax: 703-652-9951 Email: [email protected]

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SOCIETY HISTORY The Clay Minerals Society began as the Clay Mineral Committee of the National Academy of Sciences-National Research Council in 1952, in response to the need for a formal way to hold national clay conferences. By 1962, the Clay Minerals Committee had become strong enough to stand on its own, and The Clay Minerals Society was incorporated. From 1952 to 1964, proceedings of the annual conference were published. The journal Clays and Clay Minerals was first published in 1964. The primary purpose of The Clay Minerals Society is to stimulate research and to disseminate information relating to all aspects of clay science and technology. Through its conferences and publications, the Society offers individuals a means of following the many-sided growth of the clay sciences and of meeting fellow scientists with widely different backgrounds and interests. The primary activities of The Clay Minerals Society consist of publication of the bimonthly journal Clays and Clay Minerals, organization of the annual meeting, workshop, and field trips, awarding student research and travel grants, publication of a workshop lecture series, slide sets, and special publications, the providing of clays for research purposes through the Source Clays Repository, and publication of the society newsletter in the bimonthly Elements. Various committees within the Society deal also with such matters as regulatory issues, Eastern European liaison, and nomenclature. The Society also maintains a list server dedicated to increasing world-wide communications pertaining to clay minerals. The membership of The Clay Minerals Society is a diverse group because the study of clay touches upon so many fields. Members include clay mineralogists, crystallographers, physicists, chemists, geochemists, soil scientists, agronomists, ceramic scientists, civil engineers, petroleum geologists and engineers, and industrial scientists in fields involving products ranging from catalysts to cat litter. The Society has about one thousand members, a third of whom represent countries outside the United States. Awards given by the Society include the Marilyn and Sturges W. Bailey Award, the George W. Brindley Lecture, the Pioneer in Clay Science Lecture, and the Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Award. Awards are also presented for student papers and posters at the annual conference. Student research grants totaling $10,000 per year are awarded. The CMS Workshop Lectures Series includes Quantitative Mineral Analysis of Clays, Electron-Optical Methods in Clay Science, Thermal Analysis in Clay Science, Clay-Water Interface and its Rheological Implications, Computer Applications to X-Ray Powder Diffraction Analysis of Clay Minerals, Layer Charge Characteristics of 2:1 Silicate Clay Minerals, Scanning Probe Microscopy of Clay Minerals, Organic Pollutants in the Environment, Synchrotron X-Ray Methods in Clay Science, Teaching Clay Science, Electrochemical Properties of Clays, Molecular Modeling of Clays and Mineral Surfaces, The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides, Methods for Study of Microbe-Mineral Interactions, and Clay-Based Polymer Nano-Composites(CPN). The Society also publishes various conference proceedings, annual abstract volumes, and other research and educational publications.

www.clays.org

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Sustaining Contributors Sustaining Benefactors Chevron ETC Exxon Sorptive Minerals Institute Southern Clay Products, Inc. Wyo - Ben, Inc. Patrons: IMERYS M-I Swaco Thiele Kaolin Company H.H. Murray & Associates Individual Sustaining Members David L. Bish John D. Bloch Carl J. Bowser Richard K. Brown Wen-An Chiou Michael L. Cummings Randall T. Cygan Joe B. Dixon

Will P. Gates J. Reed Glassman Stephen Guggenheim Necip Guven Wayne Hudnall William D. Johns Blair Jones George H. Kacandes

Christine Bender Koch Robert H. Lander Duane M. Moore Haydn H. Murray Joseph W. Stucki James P. Talbot Kenneth M. Towe

Funders of the Marilyn and Sturges W. Bailey Distinguished Member Award Linda Bailey and David Bailey Funders of the Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Award Marion L. and Chrystie M. Jackson

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AWARDS

MARILYN AND STURGES W. BAILEY DISTINGUISHED MEMBER AWARD The Marilyn and Sturges W. Bailey Award, the highest honor of The Clay Minerals Society, is awarded solely for scientific eminence in clay mineralogy (in its broadest sense) as evidenced by the publication of outstanding original scientific research and by the impact of this research on the clay sciences. This Award replaces the Society's Distinguished Member Award and is not restricted to members of the Society.

Distinguished Members 1968 - Ralph E. Grim 1990 - John Hower 1969 - C. S. Ross 1991 - Joe B. Dixon 1970 - Paul F. Kerr 1992 - Philip F. Low 1971 - Walter D. Keller 1993 - Thomas J. Pinnavaia 1972 - G. W. Brindley 1995 - W. D. Johns 1975 - William F. Bradley 1996 - Victor A. Drits 1975 - Sturges W. Bailey 1997 - Udo Schwertmann 1975 - Jose J. Fripiat 1998 - Brij L. Sawhney 1977 - M. L. Jackson Bailey Distinguished Members 1979 - Toshio Sudo 2000 - Boris Zvyagin 1980 - Haydn H. Murray 2001 - Keith Norrish 1984 - C. Edmund Marshall 2002 - Gerhard Lagaly 1985 - Charles E. Weaver 2004 - Benny K. G. Theng 1988 - Max M. Mortland 2005 - M. Jeff Wilson 1989 - R. C. Reynolds, Jr. 2006 - Frederick J. Wicks 1990 - Joe L. White 2008 - Norbert Clauer

MARION L. AND CHRYSTIE M. JACKSON MID-CAREER CLAY SCIENTIST AWARD The Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Award recognizes a mid-career scientist for excellence in the contribution of new knowledge to clay minerals science through original and scholarly research. The honoree must be within the ages of 39 and 60.

Jackson Awardees 1992 - Joseph W. Stucki 2001 - Cliff T. Johnston 1993 - Jan Srodon 2002 - Sridhar Komarneni 1994 - Stephen Guggenheim 2003 - Peter Komadel 1995 - David L. Bish 2004 - Fred J. Longstaffe 1996 - Darrell G. Schulze 2005 - Samuel J. Traina 1997 - Jerry M. Bigham 2006 - J. Theo Kloprogge 1998 - Murray McBride 2007 - Paul A. Schroeder 1999 - Stephen Boyd 2008 - Hailiang Dong 2000 - Jillian Banfield

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GEORGE W. BRINDLEY LECTURE AWARD The G. W. Brindley Lecture Award recognizes an outstanding clay scientist, someone who is both a dynamic speaker and involved in innovative research, and charges the recipient to deliver a lecture that will infuse The Clay Minerals Society with new ideas. The speaker is challenged to deliver a lecture that Brindley himself would applaud. Brindley Lecturers

1984 - Walter Keller 1995 - Gerhard Lagaly 1985 - J. J. Fripiat 1996 - Samuel M. Savin 1986 - Ralph E. Grim 1997 - Paul H. Nadeau 1987 - S. W. Bailey 1998 - Bruce Velde 1988 - M. L. Jackson 1999 - Richard Eggleton 1989 - W. D. Johns 2000 - D. M. Moore 1990 - Alain Baronnet 2001 - Robert Schoonheydt 1991 - Thomas J. Pinnavaia 2002 - David L. Bish 1992 - Philip Low 2003 - Alain Manceau 1993 - Dennis D. Eberl 2005 - Maria F. Brigatti 1994 - R. C. Reynolds, Jr. 2008 - Robert Gilkes

PIONEER IN CLAY SCIENCE AWARD The lecture award recognizes research contributions that have led to important new directions in clay mineral science and technology. The recipient is responsible for delivering a plenary lecture supporting symposia organized for the national meeting. Pioneer Lecturers

1987 - Marion L. Jackson 1998 - Robert C. Reynolds 1988 - R. M. Barrer 1999 - V. Colin Farmer 1989 - H. van Olphen 2000 - William F. Moll 1990 - John W. Jordan 2001 - Don Scafe 1991 - Charles E. Weaver 2002 - Victor Drits 1992 - Udo Schwertmann 2003 - Vernon J. Hurst 1993 - Linus Pauling 2004 - Hideomi Kodama 1994 - Joe L. White 2005 - Jillian Banfield 1995 - Rustum Roy 2006 - Jean-Maurice Cases 1996 - Max M. Mortland 2007 - Spencer G. Lucas 1997 - Koji Wada 2008 - Emilio Galan

CITATION OF SPECIAL RECOGNITION

1984 - Richards A. Rowland 1984 - Ada Swineford 1991 - Frederick A Mumpton 1994 - Kenneth M. Towe 1996 - Don Scafe 2003 - William D. Johns

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EDITORS OF CLAYS AND CLAY MINERALS

1952 J. A. Pash and M. D. Turner 1953 Ada Swineford and Norman Plummer 1954 W. O. Milligan 1955 – 1961 Ada Swineford 1962 – 1964 William F. Bradley 1964 – 1969 Sturges W. Bailey 1970 – 1972 Max M. Mortland 1973 – 1974 William T. Granquist 1975 – 1978 Richards A. Rowland 1979 – 1990 Frederick A. Mumpton 1990 – 1991 Kenneth M. Towe 1991 – 1995 Ray E. Ferrell, Jr. 1995 – 1998 Wayne H. Hudnall 1999 – 2000 Stephen Guggenheim 2000 – 2007 Derek C. Bain 2008 – Present Joseph W. Stucki

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PAST PRESIDENTS OF THE SOCIETY Chairman, Interdivisional Committee on Clay Minerals of the National Academy of Sciences – National Research Council

1952 – 1956 Ralph E. Grim 1957 – 1959 Walter D. Keller 1960 – 1962 A. F. Frederickson 1963 Richards A. Rowland

Presidents

1963 - 1964 Richards A. Rowland 1985 – 1986 Marion G. Reed 1964 - 1965 James W. Earley 1986 – 1987 Sam H. Patterson 1965 - 1966 Haydn H. Murray 1987 – 1988 Necip Guven 1966 - 1967 Marion L. Jackson 1988 – 1989 William F. Moll 1967 - 1968 Charles E. Weaver 1989 – 1990 Brij L. Sawhney 1968 - 1969 Paul G. Nahin 1990 – 1991 Thomas J. Pinnavaia 1969 - 1970 George W. Brindley, 1991 – 1992 Robert C. Reynolds, Jr. Katherine Mather 1992 – 1993 David R. Pevear 1970 - 1971 John F. Burst 1993 – 1994 Dennis D. Eberl 1971 - 1972 Sturges W. Bailey 1994 – 1995 Rossman F. Giese, Jr. 1972 - 1973 William F. Bradley 1995 – 1996 Kenneth M. Towe 1973 - 1974 John W. Jordan 1996 – 1997 Stephen Guggenheim 1974 - 1975 John C. Hathaway 1997 – 1998 Joseph W. Stucki 1975 - 1976 Stanley B. McCaleb 1998 – 1999 David L. Bish 1976 - 1977 John Hower 1999 – 2000 Patricia M. Costanzo 1977 - 1978 John B. Hayes 2000 – 2001 Darrell G. Schultze 1978 – 1979 Max M. Mortland 2001 – 2002 Blair F. Jones 1979 – 1980 Finis Turner 2002 – 2003 Jessica Elzea Kogel 1980 – 1981 R. Torrence Martin 2003 – 2004 Kathryn L. Nagy 1981 – 1982 Joe B. Dixon 2004 – 2005 Duane M. Moore 1982 – 1983 William D. Johns 2005 – 2006 Cliff T. Johnston 1983 – 1984 Wayne Hower 2006 – 2007 Richard K. Brown 1984 – 1985 Wayne M Bundy 2007 – 2008 Ray E. Ferrell, Jr.

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BILLINGS, MONTANA

A Brief History of Billings

Most of Billings is located in the Yellowstone Valley, carved out of the surrounding area by the Yellowstone River. Over 65 million years ago, this valley was underwater with the tops of the "Rims," the sandstone cliffs bordering the city, being a prehistoric beach. It is not unusual to find fossilized fish in the area. Pictographs found in the Pictograph Cave, 6 miles (9.7 km) south of Billings, show that people began inhabiting the area as much as 2,100 years ago. The Crow Indians frequented this area from about the year 1700. However, archeological evidence places the Cheyenne in this area first, ahead of the Crow and then the Sioux.

In 1806, William Clark traveled through the region on the Lewis and Clark Expedition. He inscribed his name on a sandstone pillar about 25 miles (40 km) east of Billings, on July 25, 1806. Clark named the place "Pompys Tower" in honor of the infant son of Sacajawea, who helped guide the Lewis and Clark expedition and acted as an interpreter. The name of the formation was changed by 1814 to the current title of Pompey's Pillar. Clark's inscription is the only remaining physical evidence found along the route that was followed by the expedition.

Billings was founded in 1877, and formally established in 1882, in the then Montana Territory near the already-existing town of Coulson. Coulson was situated at the terminus of the Steamboat route on the Yellowstone River making it an ideal location for commerce. When the Montana & Minnesota Land Company saw the development potential of railroad in the valley they ignored Coulson and platted a new town, named for Frederick H. Billings the railroad’s president, several miles to the west. After the Northern Pacific Railroad was built, Coulson died as Billings flourished. On March 15, 1882, Frederick Billings and other Northern Pacific officials formed the Montana & Minnesota Land & Improvement Co., which platted and promoted the sale of land in what would become Billings. Two main commercial streets were built along the railroad tracks and were named Montana and Minnesota avenues after the land company. After the company was formed, the city grew quickly and earned the nickname, "The Magic City" because the city appeared to grow like magic. By mid-June that year, Billings had grown to 79 tent shelters and 81 houses. 75 more homes were being built as well. The buildings were hastily built along the south of the tracks. By the end of 1883, Billings had 400 buildings, 1,500 people and a nine-block commercial district. After World War II, Billings boomed into the major financial, medical and cultural center in the region. In the 1960s, Billings surpassed Great Falls as Montana's largest city. The 2007 census estimate listed the city's population at 101,876. It is the 60th fastest growing city out of the 259 cities in the U.S. with populations over 100,000. Billings is the county seat of Yellowstone County and is the largest city between Denver and Calgary, and between Minneapolis and Spokane, thereby being the cultural and economic hub of a vast area. BestLife Magazine, from the editors of Men's Health, recently ranked Billings the 3rd best place in the U.S. to raise a family.

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Things to do in the Billings Area Dining

Billings Petroleum Club (Lunch and Dinner) – Crowne Plaza Hotel 22nd floor Phone: 252-6702. www.billingspetroleumclub.org The Petroleum Club is a private club. CMS meeting attendees are welcome for lunch without reservations or dinner with reservations. Tell the maître d’ you are with The Clay Minerals Society when making reservations and checking in.

Bin 119 (Lunch and Dinner) – 119 N. Broadway Phone: 294-9119 Dinner reservations suggested.

Burger King – 520 N. 27th St. Café Jones – 2712 2nd Avenue N.

Denny’s (Breakfast, Lunch and Dinner) – 501 N. 27th St. Don Luis (Mexican) Restaurant (Lunch and Dinner) – 15 N 26th St.

Phone: 256-3355

The Dude Rancher Café (Lunch and Dinner) – 415 29th St. Phone: 259-5561

George Henry’s Restaurant (Lunch and Dinner) – 404 N. 30th St. Phone: 245-4570 Dinner reservations suggested.

Guadalajara Mexican Restaurant (Lunch and Dinner) – 17 N. 29th St.

Hardees – 608 N. 27th St.

Jakes (Lunch and Dinner) – 2701 1st Avenue N. Phone: 259-9375 Dinner reservations suggested.

Log Cabin Bakery (Breakfast and Lunch) – 2519 Montana Avenue Phone: 294-5555 McCormick Cafe (Breakfast and Lunch) - 2419 Montana Avenue

Phone: 255-9555 www.mccormickcafe.com

Montana Brewing Company (Lunch, Dinner and Beer) – 113 N. Broadway Phone: 252-9200 montanabrewingco.net

Montana Sky Restaurant (Breakfast, Lunch, and Dinner) – Crowne Plaza Hotel 20th floor Dinner reservations recommended

Pug Mahon’s Irish Pub (Lunch and Dinner) - 3011 1st Avenue N. Phone: 259-4190 www.pugmahons.com

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Q Cuisine (Dinner) - 2503 Montana Avenue Phone: 245.2503 www.qcuisine.com Reservations suggested.

The Rex (Lunch and Dinner) – 2401 Montana Avenue Phone: 245-7477 www.therexbillings.com Dinner reservations recommended.

The Soup Place (Lunch) – 106 N. Broadway Phone: 294-7687

Stella’s Kitchen & Bakery (Lunch and Dinner) – 2525 1st Avenue N. Phone: 248-3060

Traxx Bar and Grill (Dinner) – 2314 Montana Avenue Phone: 896-9200

Walkers Grill (Dinner) - 2700 1st Ave North

Phone: 245-9291 www.walkersgrill.com Dinner reservations suggested.

Wendy’s – 2906 2nd Avenue N. Museums

Chief Plenty Coups Museum at Chief Plenty Coups State Park Pryor, Montana (35 miles S. of Billings) Phone: 252-1289 http://fwp.mt.gov/lands/site_283264.aspx http://www.nezperce.com/pcmain.html

Little Big Horn Battlefield National Monument

Crow Agency, Montana (65 miles SW of Billings) Phone: 406-638-2621 http://www.nps.gov/libi/ web cams http://www.nps.gov/libi/photosmultimedia/webcams.htm

Moss Mansion Museum - 917 Division Street Phone: 256-5100 http://www.mossmansion.com Museum of Woman’s History - 2822 3rd Avenue North Phone: 248-2015

http://www.museumofwomenshistory.org/ Peter Yegen Jr. Yellowstone County Museum - Logan Int’l. Airport Phone: 256-6811

http://www.yellowstonecountymuseum.org/ Western Heritage Center - 2822 Montana Avenue Phone: 256-6809

http://www.ywhc.org/ Echoes of Eastern Montana: Stories from an Open Country A Place Called Thorofare: People, Wilderness and Wildlife Management Parading Through History: The Apsaalooke Nation The Real West: Farming and Ranching Families of the Yellowstone River Valley Coming Home: The Northern Cheyenne Odyssey The American History Tribal Histories Project J.K. Ralston Studio Cabin

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Yellowstone Art Museum - 401 North 27th Street Phone: 256-6804

http://www.artmuseum.org Ifs, Ands, and Butts: New Acquisitions by Freeman Butts and Other Regional

Artists Theater Billings Studio Theater - 1500 Rimrock Drive Reservations: 248-1141 http://www.billingsstudiotheatre.com/ One Flew Over the Cuckoo’s Nest June 5, 6, 7 11, 12 and 13th Venture Theater - 2317 Montana Avenue Reservations: 591-9535 http://www.venturetheatre.org/ Watering Holes

Angry Hanks Brewing (Great beer) – 2405 1st Avenue N. Phone: 252-3370

Montana Brewing Company (Lunch, Dinner and Beer) – 113 N. Broadway

Phone: 252-9200 montanabrewingco.net

Pug Mahon’s Irish Pub (Lunch and Dinner) - 3011 1st Avenue N. Phone: 259-4190 www.pugmahons.com

Yellowstone Valley Brewing Company (Great beer) – 2123-B 1st Avenue N.

Phone: 245-0918 www.yellowstonevalleybrew.com Monday-Saturday 4-8pm Zoos Zoo Montana – Zoo Drive and Shiloh Road W. of Billings Phone: 652-8100 http://www.zoomontana.org/

http://www.artmuseum.org/index.php/current-exhibitions/78-freeman-butts?f936e45de371569e7c870c0c95a279b9=cb672f098b796c577cbe2871962f83d2�



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Map of the Billings Area

1. Crowne Plaza Hotel 5. Billings Studio Theater 2. Chief Plenty Coup Museum 6. Zoo Montana 3. Little Big Horn Battlefield Zoo Montana 4. Peter Yegen Jr. Yellowstone County Museum

To Chief Plenty Coups State Park and Museum

To Little Big Horn Battlefield

N N N

To Yellowstone National Park

1

2

3

5 4

6

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Map of Downtown Billings To Airport

1. Crowne Plaza Hotel 16. Jakes Restaurant 28. Moss Mansion Museum Montana Sky Restaurant 17. Log Cabin Bakery 29. Museum of Woman’s History

Billings Petroleum Club 18. McCormick Café 30. Western Heritage Center 7. Bin 119 19. Montana Brewing Company 31. Yellowstone Art Museum 8. Burger King 20. Pug Mahon’s Irish Pub 32. Venture Theater 9. Café Jones 21. Q Cuisine 33. Angry Hanks Brewery 10. Denny’s 22. The Rex Restaurant 34. Yellowstone Valley Brewing Co. 11. Don Luis Mexican Restaurant 23. The Soup Place 12. The Dude Rancher Café 24. Stella’s Kitchen and Bakery 13. George Henry’s Restaurant 25. Traxx Bar and Grill 14. Guadalajara Mexican Restaurant 26. Walker’s Grill 15. Hardee’s 27. Wendy’s

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CROWNE PLAZA

Floor Plan: Second Floor Meeting Rooms

Technical Sessions

Business Center

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Floor Plan: Third Floor Meeting Rooms

CMS Meeting Office

Plenary Sessions

Banquet Poster Session

Technical Sessions

Technical Sessions

Registration

North Lobby

Hospitality Room

Banquet

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MEETING SCHEDULE AT A GLANCE

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TECHNICAL PROGRAM

THURSDAY, JUNE 4, 2009 5:30 PM- REGISTRATION 6:30 PM Crowne Plaza 3rd Floor North Lobby

FRIDAY, JUNE 5, 2009 7:00 AM- REGISTRATION 8:00 AM Crowne Plaza 3rd Floor, North Lobby 7:30 AM- FIELD TRIP #1 - BENTONITES OF THE BIG HORN BASIN 5:30 PM Meet on North side of Crowne Plaza, facing parking garage 5:30 PM- REGISTRATION 6:30 PM Crowne Plaza 3rd Floor, North Lobby 6:30 PM EXECUTIVE COMMITTEE MEETING AND DINNER Billings Petroleum Club, Presidents Room, Crowne Plaza Building, 22nd floor

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SATURDAY, JUNE 6, 2009 7:00 AM- REGISTRATION 8:00 AM Crowne Plaza 3rd Floor, North Lobby 7:30 AM- FIELD TRIP #2 - BENTONITES OF THE BIG HORN BASIN 5:30 PM Meet on North side of Crowne Plaza, facing parking garage 7:30 AM- CMS COUNCIL MEETING BREAKFAST 8:00 AM Conference Room 1, 3rd Floor 8:00 AM- CMS COUNCIL MEETING MORNING SESSION 12:00 PM Conference Room 1, 3rd Floor 12:00 PM- CMS COUNCIL MEETING LUNCH 12:30 PM Conference Room 1, 3rd Floor 12:30 PM- CMS COUNCIL MEETING AFTERNOON SESSION 5:30 PM Conference Room 1, 3rd Floor

5:30 PM- REGISTRATION 6:30 PM Crowne Plaza 3rd Floor North Lobby 6:00 PM- WELCOMING RECEPTION 8:00 PM Billings Petroleum Club, Crowne Plaza building 22nd floor

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SUNDAY MORNING, JUNE 7, 2009 7:00 AM- REGISTRATION 8:00 AM Crowne Plaza 3rd Floor North Lobby

PLENARY SESSION (Ballroom A, 3rd Floor) 8:00 AM Welcome and Introductory Remarks, Richard Brown 8:05 AM CMS Presidential Welcome, Andrew Thomas 8:20 AM Introduction of the Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist

Lecturer by Ray Ferrell 8:25 AM Marion L. and Chrystie M. Jackson Mid-Career Clay Scientist Lecture

STABLE ISOTOPES OF CLAY MINERALS ARCHIVE ORGANIC SOURCES

Lynda B. Williams 9:10 AM Introduction of the George W. Brindley Lecturer by Andrew Quicksall 9:15 AM George W. Brindley Lecture NANOMINERALS, MINERAL NANOPARTICLES AND EARTH SYSTEMS Michael F. Hochella, Jr. 10:00 AM- BREAK 10:30 AM Crowne Plaza 3rd Floor North Lobby

TECHNICAL SESSIONS Bentonite - The Most Versatile Clay? (Session 1) Conference Room 5, 3rd Floor Derek Bain and Warren Huff, Co-Chairs 10:30 AM- BENTONITE AND ITS IMPACT ON MODERN LIFE 10:50 AM Don D. Eisenhour and Richard K. Brown 10:50 AM- BENTONITE RESOURCES IN JAPAN, SUPPLY AND FUTURE DEMAND 11:10 AM Tetsuichi Takagi 11:10 AM- EFFECTS OF USA & WORLD RECESSION ON BENTONITE MARKETS 11:30 AM William J. Miles

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11:30 AM- BENTONITES OVER TIME: GEOLOGICAL SIGNIFICANCE AND 11:50 AM IMPORTANT CHARACTERISTICS George E. Christidis and Warren D. Huff 11:50 AM- A ZONED K-BENTONITE FROM THE MONTANA DISTURBED BELT 12:10 PM REVISITED: NEW IMPLICATIONS FOR SMECTITE ILLITIZATION Douglas K. McCarty, Boris A. Sakharov and Victor A. Drits 12:10 PM- DETERMINATION OF LAYER CHARGE OF SMECTITES IN 12:30 PM ASSESSMENT OF THE K-SATURATION METHOD George E. Christidis and D. D. Eberl Practical Applications of Quantitative Analysis (Session 1) Skybridge 3, 2nd Floor Denny Eberl and Oladipo Omotoso, Co-Chairs 10:30 AM- CURRENT LEVEL AND TRENDS IN QUANTITATIVE PHASE ANALYSIS 10:50 AM OF GEOLOGICAL MATERIALS Reinhard Kleeberg 10:50 AM- QUANTITATIVE XRD ANALYSIS OF CLAY-BEARING SAMPLES USING 11:10 AM FULL XRD PATTERNS Steve J. Chipera and David L. Bish 11:10 AM- CALCULATION OF THE CHEMISTRY OF MINERALS IN MIXTURES: 11:30 AM VERIFICATION AND APPLICATION OF THE HANDLENS PROGRAM Dennis D. Eberl 11:30 AM- CHOICE OF STANDARDS: A MAJOR VARIABLE IN QUANTITATIVE X- 11:50 AM RAY DIFFRACTION (QXD) WITH ROCKJOCK Christine L. Thomas and Ray E. Ferrell, Jr. 11:50 AM- SAMPLE PREPARATION AND DATA COLLECTION STRATEGIES FOR 12:10 PM X-RAY DIFFRACTION QUANTITATIVE PHASE ANALYSIS OF CLAY BEARING ROCKS Oladipo Omotoso and Dennis Eberl 12:10 PM- BEHAVIOR OF WATER MOLECULES IN MORDENITE SOLID 12:30 PM SOLUTIONS Jie Wang and Philip S. Neuhoff

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Reactions of Iron in Clays and Clay Minerals (Session 1) Conference Room 1, 3rd Floor Will Gates and Peter Komadel, Co-Chairs 10:30 AM- INTRODUCTION 10:50 AM Will Gates and Peter Komadel 10:50 AM- MEASUREMENT OF THE OXIDATION STATE OF IRON IN MINERALS 11:10 AM AND SOILS James E. Amonette 11:10 AM- REDUCTION AND REOXIDATION OF NONTRONITE: HOW WAS 11:30AM MAXIMAL REDUCTION ACHIEVED IN 1986-87 Peter Komadel, Paul R. Lear and Joseph W. Stucki 11:30 AM- KAOLIN MINING AND BENEFICIATION: THE ROLE OF IRON 11:50 AM E. Murad and J.D. Fabris 11:50 AM- LIPID PEROXIDATION INDUCED BY EXPANDABLE CLAY MINERALS 12:10 PM Daria Kibanova, Antonio Nieto-Camacho and Javiera Cervini-Silva 12:10 PM- MICROBIAL REDUCTION OF IRON IN SMECTITE (NONTRONITE), 12:30 PM MIXED-LAYER SMECTITE/ILLITE, AND ILLITE: CORRELATING THE RATE AND EXTENT OF BIOREDUCTION WITH LAYER CHARGE AND EXPANDIBILITY Hailiang Dong, Shanshan Ji, Junjie Yang, Michael Bishop and Jing Zhang

SUNDAY AFTERNOON, JUNE 7, 2009

TECHNICAL SESSIONS Bentonite - The Most Versatile Clay? (Session 2) Conference Room 5, 3rd Floor Derek Bain and Warren Huff, Co-Chairs 2:00 PM- BARRIER PERFORMANCE OF BENTONITE TO HYPER-ALKALINE 2:20 PM CONDITIONS Will P. Gates, Craig H. Benson and Peter Hines 2:20 PM- CONVERSION OF ANIONIC CLAYS TO CATIONIC CLAYS 2:40 PM Necip Guven 2:40 PM- LAYER-BY-LAYER ASSEMBLY OF MULTIFUNCTIONAL CLAY- 3:00 PM POLYMER THIN FILMS Jaime C. Grunlan, Daniel Gamboa, Woo-Sik Jang, Yu-Chin Li, Morgan A. Priolo, Ian Rawson and Jessica Schulz

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3:00 PM- FACTORS INFLUENCING MONTMORILLONITE INTERCALATION BY 3:20 PM POLYACRYLAMIDE Sungho Kim and Angelica M. Palomino 3:20 PM- STRUCTURE OF POLYVINYLPYRROLIDONE (PVP) ON SMECTITE 3:40 PM BASED ON COMPUTER SIMULATIONS Marek S. Szczerba, Jan Środoń and Michał Skiba 3:40 PM- BREAK 4:10 PM Crowne Plaza 3rd Floor North Lobby 4:10 PM- ACID DISSOLUTION OF BENTONITES 4:30 PM Peter Komadel, Martin Pentrák and Jana Madejová Microscopic and Spectroscopic Studies of Clay Mineral Reactions Skybridge 3, 2nd Floor Hailiang Dong and Jin-Wook Kim, Co-Chairs 2:00 PM- SPECIAL MICROSTRUCTURES OF AUTHIGENIC ILLITE IN 2:20 PM DIAGENETIC ENVIRONMENT: A STUDY BY TRANSMISSION ELECTRON MICROSCOPY (TEM) Tao Chen, Hejing Wang and Xialin Zhang 2:20 PM- BIOAVAILABILITY OF Fe(III) IN LOESS SEDIMENTS: AN IMPORTANT 2:40 PM SOURCE OF ELECTRON ACCEPTORS Michael E. Bishop, Deb P. Jaisi, Hailiang Dong, Ravi K. Kukkadapu and Junfeng Ji 2:40 PM- NANO CONFINED WATER IN CLAY MINERALS 3:00 PM Marika Santagata, Gnasiri Premachandra and Cliff T. Johnston 3:00 PM- BEHAVIOR OF NANOCONFINED WATER IN PALYGORSKITE AND 3:20 PM SEPIOLITE Randall T. Cygan, Nathan W. Ockwig, Jeffery A. Greathouse and Tina M. Nenoff 3:20 PM- APPLICATION AS ELECTRODE MODIFIERS OF NANOHYBRID 3:40 PM MATERIALS OBTAINED FROM THE GRAFTING OF ORGANIC UNITS ON THE INTERLAYER SURFACES OF KAOLINITE Ignas K. Tonle, Emmanuel Ngameni, Thomas Diaco, Sadok Letaief and Christian Detellier 3:40 PM- BREAK 4:10 PM Crowne Plaza 3rd Floor North Lobby 4:10 PM- MORPHOLOGICAL PROPERTIES OF SMECTITE ADSORBENTS OF 4:30 PM AFLATOXIN AS REVEALED BY LATTICE FRINGES J.B. Dixon, A.L. Barrientos Velázquez, Z. Luo and Y. Deng

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4:30 PM- SODIUM PYROPHOSPHATE – BENTONITE SUSPENSIONS FOR USE IN 4:50 PM LIQUEFACTION MITIGATION Julia P. Clarke, A. Bobet, V.P. Drnevich, Chadi El Mohtar, Cliff T. Johnston and Marika Santagata 4:50 PM- NEAR INFRARED SPECTRA OF ILLITE AND MUSCOVITE IN VERY 5:10 PM LOW-GRADE METAMORPHIC ROCKS OF THE BELT SUPERGROUP, MONTANA AND IDAHO Edward F. Duke and Reed S. Lewis Reactions of Iron in Clays and Clay Minerals (Session 2) Conference Room 1, 3rd Floor Will Gates and Peter Komadel, Co-Chairs 2:00 PM- IRON-BEARING CLAY-COATED SAND FOR WATER REMEDIATION 2:20 PM Claire I. Fialips, Yan-Feng Zhuang, Maggie L. White and Dulce Perez Ferrandez 2:20 PM- GEOPOLYMERIZATION OF ORGANIC MATTER VIA REDUCTION OF 2:40 PM STRUCTURAL IRON (III) IN 2:1 EXPANDABLE CLAY MINERLAS Keith D. Morrison, Martin J. Kennedy and Thomas F. Bristow 2:40 PM- ABIOTIC NITRATE REDUCTION BY REDOX ACTIVATED FE-BEARING 3:00 PM SMECTITES Zachary B. Day and Joseph W. Stucki 3:00 PM- MINERALOGICAL CHARACTERISATION OF NONTRONITE 3:20 PM FOLLOWING INTERACTION WITH BACTERIA AND NITROBENZENE Maggie L. White, Claire I. Fialips and Dulce Perez Ferrandez 3:20 PM- COMPARATIVE STUDY OF SOIL CLAY MINERALS DERIVED FROM 3:40 PM ULTRAMAFIC ROCKS OF THE GREAT DYKE, ZIMBABWE Courage Bangira, Youjun Deng, Richard H. Loeppert, C.Thomas Hallmark, Zachary B Day, and Joseph.W. Stucki 3:40 PM- BREAK 4:10 PM Crowne Plaza 3rd Floor North Lobby 4:10 PM- CURRENT STATE OF SITE OCCUPANCY BY IRON IN SMECTITES 4:30 PM Will P. Gates 4:30 PM- STRUCTURAL INCORPORATION OF MULTIPLE METALS IN 4:50 PM GOETHITE AND ITS CONSEQUENCES ON THE MINERAL PROPERTIES Balwant Singh, Navdeep Kaur, Markus Gräfe and Brendan J. Kennedy

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4:50 PM- SIZE DEPENDENT PHYSICAL PROPERTIES AND CHEMICAL 5:10 PM REACTIVITY OF HEMATITE NANOPARTICLES Andrew N. Quicksall, Lauren Barton, Tom Kosel and Patricia Maurice 5:30 PM- REGISTRATION 6:30 PM Crowne Plaza 3rd Floor North Lobby 6:00 PM- STUDENT AND NEW MEMBER RECEPTION 8:00 PM Skyview 1 and 2, 20th Floor

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MONDAY MORNING, JUNE 8, 2009 7:00 AM- REGISTRATION 8:00 AM Crowne Plaza 3rd Floor North Lobby

PLENARY SESSION (Ballroom A, 3rd Floor) 8:00 AM Welcome and Introductory Remarks, Richard Brown 8:10 AM Introduction of the Pioneer in Clay Science Lecturer by Jessica Kogel 8:15 AM Pioneer in Clay Science Lecture 60 YEARS AS A CLAY MINERALOGIST Hayden H. Murray 9:10 AM Introduction of the Marilyn and Sturges W. Bailey Award Lecturer by Peter Komadel 9:15 AM Marilyn and Sturges W. Bailey Award Lecture IRON REDOX REACTIONS IN SMECTITES Joseph W. Stucki 10:00 AM BREAK 10:30 AM Crowne Plaza 3rd Floor North Lobby

TECHNICAL SESSIONS Practical Applications of Quantitative Analysis (Session 2) Conference 5, 3rd Floor Dennis D. Eberl and Oladipo Omotoso, Co-Chairs 10:30 AM- QUANTITATIVE MINERALOGY OF FINE-GRAINED SEDIMENTARY 10:50 AM ROCKS: AN EXAMPLE FROM THE MANCOS SHALE AND A PRELIMINARY LOOK AT QEMSCAN® Richard I. Grauch and D. D. Eberl 10:50 AM- QUANTIFYING CARBON FIXATION IN TRACE MINERALS FROM 11:10 AM KIMBERLITE MINE TAILINGS Siobhan A. Wilson, Mati Raudsepp and Gregory M. Dipple 11:10 AM- QUANTIFICATION OF ETTRINGITE FORMATION IN STABILIZED 11:30 AM CLAYS Maria Chrysochoou and Dennis G. Grubb

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11:30 AM- SMECTITE CONTENT OF CRUSHED BASALTIC AGGREGATE: ROCK 11:50 AM RESPONSE TO DMSO ACCELERATED WEATHERING TEST J. Reed Glasmann 11:50 AM- MEAN THICKNESS DISTRIBUTION AND EVOLUTION OF GROWTH 12:10 PM MECHANISMS FOR TOBELITE - SMECTITE MIXED LAYERS, NEAR END-MEMBER TOBELITE, AND TOBELITE – K-ILLITE FROM THE FOSSIL HYDROTHERMAL SYSTEM OF HARGHITA BÃI, EASTERN CARPATHIANS Iuliu Bobos and Dennis Eberl Industrial Clay Mineralogy: Mining, Processing, Utilization Conference Room 1, 3rd Floor Mark A. Herpfer and Robert J. Pruett, Co-Chairs 10:30 AM- APPLICATION OF QUANTITATIVE CLAY MINERALOGY IN 10:50 AM DEVELOPING PREDICTIVE NIR MODELS FOR ANALYSIS OF GANGUE MINERALS ON CONVEYORS Alexander F. H. Goetz, Brian Curtiss and Daniel A. Shiley 10:50 AM- THE CARBON FOOTPRINT AND LIFECYCLE ANALYSIS OF KAOLIN 11:10 AM AND CALCIUM CARBONATE PIGMENTS IN PAPER. Robert J. Pruett 11:10 AM- BENEFITS OF MICROPOROUS CERAMIC MEDIA IN BRICKS 11:30 AM Marc A. Herpfer 11:30 AM- HYDROTHERMAL ALTERATION AND ORIGIN OF THE KAOLIN- 11:50 AM ALUNITE DEPOSITS: DUVERTEPE DISTRICT, SIMAV GRABEN, TURKEY Ömer I. Ece, Bala Ekinci and Fahri Esenli 11:50 AM- MODIFICATION OF ANION RETENTION BEHAVIOR OF CLAY 12:10 PM MATERIAL Sudhakar M.Rao and Sadasivam Sivachidambaram 12:30 PM- PAST PRESIDENT’S LUNCH (by invitation) 2:00 PM Billings Petroleum Club, Crowne Plaza 22nd Floor

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MONDAY AFTERNOON, JUNE 8, 2009 TECHNICAL SESSIONS Isotopes and Clays Conference Room 5, 3rd Floor W. Crawford Elliott, Chair 2:00 PM- A MODEL FOR POTASSIUM GAIN AND RADIOGENIC ARGON LOSS 2:20 PM DURING BURIAL ILLITIZATION BASED ON ANALYTICAL DATA Norbert Clauer and Abraham Lerman 2:20 PM- LI AND B ISOTOPIC TRACING OF ILLITE NUCLEATION AND 2:40 PM GROWTH IN BENTONITE UNITS OF THE EAST SLOVAK BASIN Norbert Clauer, Lynda Williams, Miroslav Honty and Vladimir Sucha 2:40 PM- DIAGENESIS OF THE CRETACEOUS MARIAS SHALE, DISTURBED 3:00 PM BELT, MONTANA W. Crawford Elliott, R. Douglas Elmore and Michael H. Engel 3:00 PM- DATING THE PROGRESSIVE BURIAL OF THE SOURCE ROCKS OF 3:20 PM THE ALBERTA TAR SANDS DEPOSITS Edward Meyer, James Aronson, Paul Nadeau, Cindy Riediger, Steve Hillier, Barry Richards and Michele Asgar-Deen 3:20 PM- K-Ar DATING OF THE Fe-ILLITE FROM LE PUY (FRANCE) APPLYING 3:40 PM SEQUENTIAL ACID DISSOLUTION Arkadiusz Derkowski, Jan Środoń, Marc Amouric and Michał Banaś 3:40P M- BREAK 4:10 PM Crowne Plaza 3rd Floor Lobby 4:10 PM- SOURCE AND ORIGINS OF SEDIMENTARY KAOLIN DEPOSITS IN 4:30 PM EGYPT H. Baioumy, H. A. Gilg, E. Hegner, S. Hölzl, H. Taubald and L. N. Warr 4:30 PM- RADIOGENIC ARGON AS AN INDICATOR OF MICA REMNANTS IN 4:50 PM HYDROXY-INTERLAYERED VERMICULITE J. M. Wampler and W. Crawford Elliott 4:50 PM- BORON BEHAVIOR DURING SEAWATER PALAGONITIZATION 5:10 PM REVEALED USING SIMS MICROANALYSIS: IMPLICATIONS FOR ENVIRONMENTAL CONTROL Bruce D. Pauly, Lynda B. Williams, Richard L. Hervig and Peter Schiffman

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From Discovery to Dollars: the Challenges of Innovation and Commercialization Conference Room 1, 3rd Floor Gary W. Beall, Chair 2:00 PM- INVENTIONS TO BENEFIT MANKIND AND MAKE MONEY 2:40 PM Richard W. Helfrich 2:40 PM- A PERSPECTIVE OF COMMERCIALIZATION IN ACADEMIA, 3:00 PM GOVERNMENT LABS AND INDUSTRY Gary W. Beall 3:00 PM- IMPLEMENTING INNOVATION 3:20 PM Chris DeArmitt 3:20 PM- Panel Discussion 3:40 PM 3:40 PM- BREAK 4:10 PM Crowne Plaza 3rd Floor Lobby 4:10 PM- ANTI-FLAMMABLE AND FOIL REPLACEMENT TECHNOLOGIES 4:30 PM BASED UPON CLAY-CONTAINING THIN FILMS: EFFORTS TO OBTAIN SPONSORSHIP AND/OR PARTNERSHIPS FOR COMMERCIAL DEVELOPMENT Jaime C. Grunlan 4:30 PM- A CASE STUDY OF THE ROAD TO COMMERCIALIZATION OF 4:50 PM ORGANOCLAYS FOR WASTEWATER TREATMENT Gary W. Beall 4:50 PM- SAFETY OF CLAY MINERALS AND CLAY MINERAL PRODUCTS 5:10 PM William F. Moll 5:10 PM- DEVELOPMENT OF NANOCLAY FOR PLASTIC ADDITIVE 5:30 PM APPLICATIONS Tie Lan 5:30 PM- Panel Discussion 5:40 PM

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POSTER SESSION Ballroom C, 3rd Floor 5:30 PM to 7:30 PM Bentonite - The Most Versatile Clay?

CARBON BLACK HALOING OF CLAY AND ITS INFLUENCE ON ELECTRICAL AND MECHANICAL PROPERTIES OF EPOXY COMPOSITES Jaime C. Grunlan, Krishna Etika, Lance Hess and Lei Liu THE SYNTHESIS OF AL-MCM-41 FROM VOLCLAY -A LOW-COST AL AND SI SOURCE M. Adjdir, T. Ali-Dahmane, F. Friedrich, T. Scherer and P.G. Weidler

Clay Interactions With Environmental Contaminants In Soils And Sediments

SIDEROPHORE-LEAD MUTUAL SORPTION IN THE INTERLAYER OF Na-SATURATED MONTMORILLONITE Erin Hunter, Andrew N. Quicksall, Elizabeth Haack, Ashok Patra and Patricia Maurice

Practical Applications of Quantitative Analysis RELATION BETWEEN MINERAL SURFACE AREA AND TOTAL ORGANIC CARBON CONTENTS FOR THE NORTH SEA JURASSIC KIMMERIDGE CLAY FORMATION Alex Blum, Neil Fishman, D. D. Eberl, and Ronald Hill CYCLICAL TRENDS IN CLAY MINERALOGY OF THE GREEN RIVER FORMATION Thomas F. Bristow and Keith Morrison RIETVELD REFINEMENT OF ALUMINUM-SUBSTITUTED GOETHITE AND HEMATITE IN SOME BRAZILIAN OXISOLS Oladipo Omotoso, Douglas, G. Ivey and Marcelo, E. Ives THE MINERALOGY AND GEOCHEMISTRY OF BEDLOAD SEDIMENTS, TAIERI RIVER, SOUTH ISLAND, NEW ZEALAND N.J. Reid and C.E. Martin MINERALOGICAL STUDY OF ISTANBUL SILE-UVEZLI CLAYS Yildiz Yildirim and Gulseher Coban

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Clays and Energy

SEQUENCE STRATIGRAPHIC DISTRIBUTION OF THE CLAY MINERAL CORRENSITE IN MISSISSIPPIAN AGED LIMESTONE: EVIDENCE FROM TUSCUMBIA-MONTEAGLE FORMATIONS, NORTHWEST GEORGIA Daniel E. Bulger

Isotopes and Clays

THE BENTONITE PUZZLE: A STABLE ISOTOPE AND GEOCHEMICAL PERSPECTIVE H. Albert Gilg and Alexander Rocholl

General Session

ESTIMATION OF ORIGINAL POTTERY FIRING TEMPERATURE THROUGH X-RAY DIFFRACTION Connie I. Constan ELASTIC MODULI AND NANOHARDNESS OF TALC AND PYROPHYLLITE Zhongxin Wei, Guoping Zhang, Ray E. Ferrell and Stephen J. Guggenheim

7:00 PM- EDITOR’S DINNER (by invitation) 9:30 PM Billings Petroleum Club, Crowne Plaza building 22nd floor

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TUESDAY MORNING, JUNE 9, 2009 7:00 AM- REGISTRATION 7:00 AM- SUSTAINING MEMBERS BREAKFAST (by invitation) 8:00 AM McCormicks Café, 2419 Montana Avenue (1/2 block south, 1½ blocks east)

TECHNICAL SESSIONS Clays and Energy Conference Room 5, 3rd Floor Steve Chipera, Chair 8:00 AM- BENTONITE CLAY FOR NUCLEAR WASTE DISPOSAL 8:20 AM Patrik Sellin 8:20 AM- SORPTION OF IODIDE AND SODIUM IONS ON MODIFIED CLAY 8:40 AM MATERIALS Sadasivam Sivachidambaram and Sudhakar M.Rao 8:40 AM- THE USE OF CLAY MINERALS FOR TREATMENT OF COAL FLY ASH 9:00 AM AND FLY ASH LEACHATE Rona J. Donahoe, Sidhartha Bhattacharyya and Ghanashyam Neupane 9:00 AM- CO2 TRAPPING IN CLAYEY MATERIALS 9:20 AM Vyacheslav N. Romanov, Yee Soong, Bret H. Howard, Elizabeth A. Frommell, Robert L. Kleinmann and George D. Guthrie 9:20 AM- Break 9:50 AM Crowne Plaza 3rd Floor North Lobby 9:50 AM- EARTH'S ENERGY "GOLDEN ZONE": A TRIUMPH OF 10:10 AM MINERALOGICAL RESEARCH Paul H. Nadeau 10:10 AM- CHARACTERIZATION OF CLAY MINERALS IN THE ALBERTA OIL 10:30 AM SANDS Peter Uhlík, Ali Hooshiar, Oladipo Omotoso, Thomas H. Etsell, Qi Liu and Douglas G. Ivey 10:30 AM- A COMPREHENSIVE ANALYSIS OF ORGANIC MATTER REMOVAL 10:50 AM FROM CLAY-SIZED MINERALS EXTRACTED FROM OIL SANDS USING LOW TEMPERATURE ASHING AND HYDROGEN PEROXIDE Adebukola Y. Adegoroye, Peter Uhlik, Oladipo Omotoso, Zhenghe Xu and Jacob Masliyah

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10:50 AM- RESERVOIR QUALITY OF LOUISIANA MIOCENE SHELF 11:10 AM SANDSTONES, GULF OF MEXICO: CLAYS ARE THE KEY Andrew Thomas, Doug McCarty, Mark Filewicz, Matt Johnson, Tom Dunn and Marek Kacewicz 11:10 AM- BACKSCATTERED ELECTRON MICROFABRIC OF BLACK SHALES 11:30 AM Nchekwube Mbamalu, Logan Kirst and Ray E. Ferrell, Jr. 11:30 AM- CLAY IN ENGINEERING AND ENVIRONMENT: APPLICATION AND 11:50 PM TREATMENT IN ABADAN REFINERY S.R. Shadizadeh and Mansoor Zoveidavianpoor Clay Interactions With Environmental Contaminants In Soils And Sediments Conference Room 1, 3rd Floor David Laird and Peter Ryan, Co-Chairs 8:00 AM- A COMPREHENSIVE ANALYSIS OF ORGANIC CONTAMINANT 8:20 AM ADSORPTION BY CLAYS Stephen A. Boyd, Cliff T. Johnston, David A. Laird, Brian J. Teppen and Hui Li 8:20 AM- ADSORPTION OF ISOXAFLUTOLE DEGRADATES TO HYDROUS 8:40 AM METAL OXIDES Keith W. Goyne, Si-Hyun Wu, Robert N. Lerch and Chung-Ho Lin 8:40 AM- PROBING THE MICROSCOPIC HYDROPHOBICITY OF SMECTITE 9:00 AM SURFACES Cliff. T. Johnston, Kiran Rana, Stephen A. Boyd, Brian J. Teppen and Thomas J. Pinnavaia 9:00 AM- LINCOMYCIN SORPTION BY SMECTITE CLAYS 9:20 AM Hui Li, Cuiping Wang, Yunjie Ding, Brian J. Teppen and Stephen A. Boyd 9:20 AM- Break 9:50 AM Crowne Plaza 3rd Floor North Lobby 9:50 AM- CARBOXYLATE FUNCTIONAL GROUPS MEDIATE ADHESION OF 10:10 AM Cryptosproidium Parvum ÖOCYSTS AT THE HEMATITE/WATER INTERFACE Xiaodong Gao and Jon Chorover 10:10 AM- HEAVY METAL UPTAKE AT THE MUSCOVITE-SOLUTION 10:30 AM INTERFACE OBSERVED USING IN-SITU X-RAY REFLECTIVITY Sang Soo Lee, Paul Fenter, Changyong Park, Neil C. Sturchio and Kathryn L. Nagy

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10:30 AM- EFFECTS OF MINERAL TRANSFORMATION, CONTAMINANT 10:50 AM CONCENTRATION AND CO2 PRESSURE ON CONTAMINANT SPECIATION AND MOBILITY IN SIMULATED HANFORD SEDIMENTS. Nicolas Perdrial, Aaron Thompson and Jon Chorover 10:50 AM- AN ADDITIVE MODEL OF AGGREGATE SURFACE ENERGY BASED 11:10 AM ON THE SURFACE ENERGIES OF MINERAL COMPONENTS Clint Miller, Bruce Herbert, Nathan Gardiner and Dallas Little 11:10 AM- REDUCING THE UNCERTAINTY OF THE PALEOSOL PALEOCLIMATE 11:30 AM PROXY USING NUMERICAL MODELING Jason C. Austin, Paul A. Schroeder and John F. Dowd

TUESDAY AFTERNOON, JUNE 9, 2009 TECHNICAL SESSIONS A Drugstore In The Dirt: Medicinal Clays And Clay Minerals Conference Room 5, 3rd Floor Lynda B. Williams, Chair 1:30 PM- MINERALOGICAL AND CHEMICAL COMPARISON OF 1:50 PM ANTIBACTERIAL CLAYS L. B. Williams, D. D. Eberl, D. M. Metge and R. W. Harvey 1:50 PM- THE VARIABLE TOXICITY OF QUARTZ: A COUPLED 2:10 PM TOXICOLOGICAL AND MINERALOGICAL STUDY William F. Moll 2:10 PM- COMPLEX GENETIC EVOLUTION OF SURFACE COATINGS ON 2:30 PM RESPIRABLE QUARTZ GRAINS CONTROLS CYTOTOXICITY IN THE LUNG Richard F. Wendlandt, Millicent P. Schmidt and Wendy J. Harrison 2:30 PM- AFLATOXIN B1 ADSORPTION TO CLAYS: pH, UV, AND IR SPECTRA 2:50 PM William F. Jaynes and Richard E Zartman 2:50 PM- AFLATOXIN ADSORPTION INFLUENCED BY ADSORBENT 3:10 PM MINERALOGY Ana L. Barrientos Velazquez, Youjun Deng and Joe B. Dixon 3:10 PM- PROBE ADSORBED AFLATOXIN B1 MOLECULES IN SMECTITE 3:30 PM Youjun Deng, Ana Luisa Barrientos Velzquez and Joe B. Dixon 3:10 PM- Break 3:45 PM Crowne Plaza 3rd Floor North Lobby

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General Session Conference Room 1, 3rd Floor Douglas K. McCarty and Andrew Thomas, Co-Chairs 1:30 PM- CRYSTAL GROWTH HISTORY OF QUARTZ IN THE ORDOVICIAN 1:50 PM MILLBRIG K-BENTONITE Warren D. Huff and Funda O. Inanli 1:50 PM- SMECTITE AND SILICEOUS SINTER FORMATION IN OCTAPUS 2:10 PM SPRING, YELLOWSTONE NATIONAL PARK, WYOMING, USA Paul A. Schroeder and Jennifer E. Kyle 2:10 PM- USE OF MINERALS TO ASSIST DETECTION OF BIO/ORGANIC 2:30 PM SIGNATURES IN THE SEARCH FOR LIFE Jill R. Scott, C. Doc Richardson, J. Michelle Kotler, and Nancy W. Hinman 2:30 PM- CLAY AS RIGID SURFACTANT FOR DISPERSION OF CARBON 2:50 PM NANOTUBES IN POLYMER Jaime C. Grunlan, Krishna Etika, Lance Hess and Lei Liu 2:50 PM- GEOLOGY AND MINERALOGY OF SEPIOLITE-PALIGORSKITE 3:10 PM DEPOSIT FROM SW ESKIŞEHIR (TURKEY) Mefail Yeniyol

3:10 PM- Break 3:45 PM Crowne Plaza 3rd Floor North Lobby CMS BUSINESS MEETING Billings Petroleum Club, Crowne Plaza 22nd Floor 3:30 PM- Andrew R. Thomas, President 4:30 PM FEATS OF CLAY SESSION Billings Petroleum Club, Crowne Plaza 22nd Floor 4:30 PM- MINERAL SAFETY: WHERE ARE THE MINERALOGISTS? 5:00 PM William F. Moll 5:00 PM- DOES CLAY RESEARCH IMPROVE THE EFFICIENCY AND 5:30 PM ENVIRONMENTAL PERFORMANCE OF ENERGY PRODUCTION?

Paul H. Nadeau

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5:30 PM- BLACK CARBON, THE PYROGENIC CLAY MINERAL? 6:00 PM David Laird BANQUET Ballroom A and B, 3rd Floor 6:45 PM Opening Remarks 7:00 PM Buffet Dinner 8:00 PM CAUSING A DINOSAUR EXTINCTION

Jack Horner, Curator of Paleontology, Museum of the Rockies 8:45 PM Award Presentations 9:15 PM Dancing to the Buster Sparks Band

WEDNESDAY, JUNE 10, 2009 7:30 AM CLAYS OF YELLOWSTONE NATIONAL PARK WORKSHOP departs Meet on North side of Crowne Plaza, facing parking garage

THURSDAY, JUNE 11, 2009 9:00 PM Workshop returns from Yellowstone National Park

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SOCIETY AWARD LECTURE

ABSTRACTS

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NANOMINERALS, MINERAL NANOPARTICLES, AND EARTH SYSTEMS Michael F. Hochella, Jr. Department of Geosciences, Virginia Tech, Blacksburg, VA 24061-0420 USA [email protected]

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller than a few to perhaps as much as several tens of nanometers in at least one dimension. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere. With approximately 4,500 mineral species presently described – not many relative to millions of prokaryotic and eukaryotic species combined – their diversity and range of influence may seem, by comparison, relatively modest. Minerals exert their influence by constituting the bulk of this rocky planet and having a wide range of composition and structure that is expressed in a remarkable diversity of physical and chemical properties. Now we are gaining a much better appreciation for another aspect of mineral diversity, that expressed in the nanoscale size range. Here, atomic and electronic structure of nanoparticles may vary with size even without a phase transformation, and surface to volume ratios change dramatically. Such particles are minerals that are as small as approximately one nanometer and as large as several tens of nanometers in at least one dimension. Limiting size in one, two, or three dimensions results in a nanofilm (or nanosheet), a nanorod, or a nanoparticle, respectively. Minerals can be found in all of these shapes. Nanominerals are defined as minerals that only exist in this size range; that is, one will not find their equivalent at sizes larger than this. Well-known examples include certain clays and iron and manganese (oxyhydr)oxides, with ferrihydrite, an iron oxyhydroxide, as a type example. Mineral nanoparticles are minerals that can also exist in larger sizes, and these probably include most of all known minerals. Elemental distribution and bioavailability, reaction pathways and catalysis, and mineral growth/solubility/weathering are all influenced by phenomena relevant to the nanoscale with no equivalent phenomena at scales larger or smaller. Dissolved ions in aqueous solution, versus that same ion in a 1 nm mineral, versus that ion in a 5 nm or larger mineral, all behave differently. Aqueous and gas-based reactions that occur on (or in conjunction with) a molecular cluster, versus on a small mineral nanoparticle of the same composition, versus on a 50 nm or larger mineral grain, again with the same composition are predicted to most often show significantly different reaction pathways and kinetics.

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60 YEARS AS A CLAY MINERALOGIST Haydn H. Murray Professor Emeritus, Department of Geological Sciences, Indiana University, Bloomington, IN 47405 [email protected] I have had the good fortune of being in academia, industry, state government, and working as a consultant. I have had the opportunity to do research and development on kaolins, smectites, and palygorskites, as will be noted in my presentation. I have had the opportunity to travel and visit clay deposits in many areas of the world. I will discuss chronologically the highlights of my career along with a review of my academic and applied research and development interests. Professor Ralph Grim, my graduate school research advisor at the University of Illinois had the most influence on my career until his death in 1989. I will discuss the physical and chemical properties of the clay minerals and relate them to their primary applications. Also, I will discuss future trends and predict which world class clay deposits will be most utilitized. I will review the history of the Clay Minerals Society and its formation in 1962. I have thoroughly enjoyed being a clay mineralogist and would do it all over again without any major changes.

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IRON REDOX REACTIONS IN SMECTITES Joseph W. Stucki University of Illinois, Urbana IL 61801-4798 [email protected] Iron in the crystal structure of smectite clay minerals plays a significant role in determining the chemical and physical properties of these ubiquitous phyllosilicate minerals. The importance of Fe is attributed largely to its redox activity, which may be invoked either synthetically under controlled conditions or in situ in soils and sediments in response to bacterial respiration or other environmental redox processes. Many studies have examined cause and effect relationships between changes in Fe oxidation state and changes in clay properties and behavior. Effects on the surrounding chemical and physical environments of the clay have also been investigated. The purpose of this presentation is to provide an overview and analysis of these studies in order to give the listener an appreciation for the state of the science in this area and to plant seeds of curiosity that will lead others to delve further into this intriguing aspect of clay science.

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STABLE ISOTOPES OF CLAY MINERALS ARCHIVE ORGANIC SOURCES Lynda B. Williams Earth & Space, Arizona State University, Tempe, AZ 85287-1404; [email protected] The stable isotope geochemistry of clay minerals has proven useful in determining the paleo-fluid compositions recorded by illite and other diagenetic minerals precipitated during burial. Variations in trace element concentrations and isotope compositions, as a function of clay crystal size, record paleo-fluid chemical changes over time as crystals grow and incorporate those elements. By studying fundamental illite particles separated by size, we gain insights to fluid changes during crystal growth. Ideally, this information can be correlated with crystal age to determine the timing of a fluid migration (e.g., hydrocarbon migration). Complications will arise if the system has multiple generations of illite nucleation and growth. This may occur in systems that are supersaturated with illite components. However, our studies of natural samples indicate that most illite crystals stop nucleating after earliest growth and continue to grow by surface controlled growth. This allows for reasonable interpretation of stable isotopes to evaluate the geologic history of a sedimentary unit from a single core sample. A variety of stable isotopic systems of major elements (C, H, O, N, S) have been applied to derive important information about how rocks exchange components with aqueous fluids and hydrocarbons during burial diagenesis; approaching equilibrium under constantly changing physical conditions (increasing T and P). More recently B and Li isotope systematics have been investigated for application to geologic problems in the sedimentary environment. New analytical instruments, such as the secondary ion mass spectrometer (SIMS) allow us to examine stable isotopic systems of trace elements in clay minerals that were not possible in the past. The analytical technique for solid-state mass spectrometry of clay minerals by SIMS will be presented, highlighting important precautions specific to clays. The influence of organic matter (kerogen, coal) on the geochemistry of the fluids that precipitate clay minerals will be demonstrated. Some examples will be shown from hydrocarbon bearing sediments undergoing slow burial diagenesis, and more rapid contact metamorphism. These examples document a correlation between the stable isotope geochemistry of maturing organic matter and clay minerals that archive the migration of hydrocarbon-related fluids through a sedimentary basin.

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TECHNICAL SESSIONS ABSTRACTS

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A COMPREHENSIVE ANALYSIS OF ORGANIC MATTER REMOVAL FROM CLAY – SIZED MINERALS EXTRACTED FROM OIL SANDS USING LOW TEMPERATURE ASHING AND HYDROGEN PEROXIDE Adebukola Y Adegoroye 1, Peter Uhlik 1,2, Oladipo Omotoso 3, Zhenghe Xu 1 and Jacob Masliyah1

1Department of Chemical and Materials Engineering, University of Alberta, Edmonton, T6G 2G6, Canada; [email protected] 2Department of Geology of Mineral Deposits, Comenius University in Bratislava, 842 15, Slovakia 3Natural Resources Canada, CANMET Energy Technology Centre – Devon, Devon, T9G 1A8, Canada

Oil sands in Alberta, Canada comprise of silica sand and other minerals impregnated with bitumen. Bitumen is produced from oil sands by either in-situ techniques or by hot water – based extraction of surface - mined oil sands. The main challenge posed by the water based process is the management of the large quantities of water required for bitumen extraction. Over 70% of the water is re-used but the remaining 30% is trapped in slow - settling tailings ponds+ containing mostly clay-sized minerals (CSM). An understanding of the CSMs is therefore necessary to develop better tailings reclamation technologies. CSM in oil sands are often contaminated by tightly adsorbed organics during hydrocarbon removal thereby increasing surface hydrophobicity and making characterization of CSM problematic. This study evaluates the use of hydrogen peroxide (H2O2) and low temperature ashing (LTA) for the removal of adsorbed organic matter (OM) without changing the bulk mineralogy. In this study, CSM isolated from tailings and bitumen froth of a Denver flotation cell after oil sands extraction were treated by H2O2 and LTA. Both techniques were found to be effective in removing OM from the CSM as shown by the infrared spectra of the samples. Elemental analysis showed a lower percentage of carbon, hydrogen and nitrogen in the treated CSM when compared with those left untreated. Infrared band for siderite at 864 cm-1 was observed for the isolated and LTA treated CSM but was absent for those treated by H2O2. The absence of siderite in the X–ray diffraction patterns of the H2O2 treated CSM further substantiates the oxidation of iron in siderite by H2O2. Calculated cation exchange capacity was found to be unaffected by treatment for LTA treated model clays and samples unlike those treated with H2O2. Overall, LTA appears to be a more suitable method than H2O2 for cleaning isolated CSM because of its selectivity for organics.

MacKinnon, M.D. (1989). Development of the Tailings Pond at Syncrude Oil Sands Plant: 1978–1987. AOSTRA J.Res., 5, 109-133.

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MEASUREMENT OF THE OXIDATION STATE OF IRON IN MINERALS AND SOILS James E. Amonette Geochemistry/Chemical and Materials Sciences Department, Pacific Northwest National Laboratory, PO Box 999, K8-96, Richland, WA 99354, USA; [email protected] The reactivity of iron-bearing clays, and the soils or sediments in which they reside, depends in large part on the oxidation state of the iron (Fe) in their structures. In addition to its direct impact on electron-transfer chemistry, the oxidation state of structural Fe can affect physical-chemical properties such as surface area, layer charge, cation fixation, and swelling pressure of Fe-bearing smectites, and the rate of weathering of Fe-bearing micas and chlorites. It is no wonder then that the development of accurate methods of measuring the Fe oxidation state in these minerals has been essential to understanding their chemistry and related properties. Prof. Joseph W. Stucki, whom we honor in this symposium, recognized the need for a robust method of Fe oxidation state analysis of smectites early in his career, and authored a series of papers during the 1970s and 80s in which 1,10-phenanthroline (phen) was used as the chromophore for Fe(II) and total Fe analysis. Joe also developed expertise in Mössbauer spectroscopy. My advisor, Prof. A. Duncan Scott, across the river in Iowa, recognized the same need for his work on the weathering of micas and had adopted an oxidimetric technique using vanadate. After joining his group in 1979, I spent some time improving this method. A friendly rivalry developed between our two groups, both in terms of the type of mineral being studied and the “proper” way to determine Fe oxidation states in these minerals. The rivalry culminated in a couple of direct comparison studies during the 1990s in which the phenanthroline, vanadate, and Mössbauer spectroscopic methods were used to quantify the oxidation state of Fe in non-refractory minerals as well as soils. Ultimately, I adopted the phenanthroline approach for my work, after making some improvements in the method that Stucki and his co-workers had developed. In this presentation I will review the principles behind each of these three common approaches to measurement of Fe oxidation state, discuss their strengths as well as some of the more spectacular pitfalls associated with each, and summarize the results of the direct comparison studies. I will conclude with a look at some of the newer spectroscopic methods involving synchrotron radiation and provide some perspective on when a given approach is best employed.

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REDUCING THE UNCERTAINTY OF THE PALEOSOL PALEOCLIMATE PROXY USING NUMERICAL MODELING Jason C. Austin, Paul A. Schroeder and John F. Dowd

University of Georgia Department of Geology, 210 Field St., Athens GA, 30602 USA; [email protected] Numerical methods are used to assess new solutions of the model that allows for more complex descriptions of physical processes simultaneously taking into account changes in soil properties with depth and soil processes associated with climatic variations (i.e. soil moisture and temperature). Disagreement between field measured and modeled soil respiration rates determined from carbon isotope concentrations in modern gibbsite indicates that the formulation or assumptions of the analytical solution of the Fickian diffusion model do not adequately describe the process by which soil carbon is incorporated into the gibbsite structure. Testing the sensitivity of the analytical model against the natural variability of the assumed factors indicates that the model solution is most sensitive to the soil respiration rate, which has previously been assigned a value representing the average annual soil respiration rate. A finite difference solution allows for a more accurate representation of model factors such as soil CO2 concentration and CO2 diffusion coefficient and their variation with depth. The uncertainty of modeled paleo-pCO2 using these new methods coupled with determination of the soil respiration rate that is likely associated with pedogenic gibbsite growth is assessed using Monte Carlo analysis.

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COMPARATIVE STUDY OF SOIL CLAY MINERALS DERIVED FROM ULTRAMAFIC ROCKS OF THE GREAT DYKE, ZIMBABWE

Courage Bangira 1, Youjun Deng 1, Richard H. Loeppert 1, C.Thomas Hallmark 1, Zachary B. Day 2 and Joseph.W. Stucki 2 1Soil & Crop Sciences Department, Texas A&M University, College Station, TX 77840 2Department of Natural Resources & Environmental Sciences, University of Illinois, Urbana, IL 61801 [email protected]

Regional and local variations in geology, climate, and landscape have a significant impact on the occurrence of certain soil minerals. The specific minerals in soil greatly impact the bio-geochemical reactions and largely determine necessary environmental management strategies. This study was conducted on soils derived from the Great Dyke of Zimbabwe, one of the world’s largest ultramafic and mafic intrusions. The objective of the study was to determine the occurrence and spatial variability of clay minerals in soil on the landscape. Soil samples were taken across a transect located at Mpinga (mean annual rainfall ~ 800 mm) and at Bannockburn (mean annual rainfall ~ 500 mm) on the northern and southern parts of the Great Dyke, respectively. Mineralogical characterization was performed using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy, and scanning electron microscopy (SEM). The results showed the predominant occurrence of talc, Fe oxides, kaolinite, and Fe-smectites in soils at both locations. Fe-smectite occurred in clay at all spatial locations, although large quantities were associated with poorly drained landscapes at Mpinga. At Bannockburn, however, Fe-smectite was associated with well drained landscapes and the quantity increased with soil depth. Chlorite and vermiculite were also detected in soils at both locations. Significant amounts of serpentine were detected only at Mpinga while palygorskite only was detected at Bannockburn. Irrespective of landscape position, palygorskite was identified only in soils lacking Fe-smectite. The formation and spatial occurrences of clay minerals on the landscape are discussed in relation to parent material, climate, pH, Fe, and Mg.

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AFLATOXIN ADSORPTION INFLUENCED BY ADSORBENT MINERALOGY Ana L. Barrientos Velazquez 1, Alicia Marroquin-Cardona 2, Youjun Deng 1 and Joe B. Dixon 1

1Soil & Crop Sciences Department, 2College of Veterinary Medicine, Texas A&M University, 370 Olsen Blvd, College Station, TX, USA; [email protected] Aflatoxins are chemical compounds produced by fungi Aspergillus flavus and A. parasitcus. Aflatoxin contamination of food and feed has worldwide impact causing substantial economical losses and may cause liver cancer in humans and animals. Aflatoxins can be metabolized, forming derivatives like AfM1 that are found in milk and urine. Various natural and modified minerals, yeast cells, polyphenols, and chlorophyllin have been tested to reduce the bioavailability of aflatoxin. In a parallel study, eight commercial products marketed as mycotoxin binders have been added to aflatoxin-contaminated corn to test the detoxification efficiency of the products on dairy cows. The effectiveness of the adsorbents was evaluated based on the reduction of the concentration of AfM1 in milk. The dairy experiment showed that four effective adsorbents reduced the concentration of AfM1 in milk up to 49% and the in vivo results correlate well with measured adsorption capacities of the marketed products from batch adsorption isotherms. The objective of this study is to characterize the mineralogical compositions of these products and to compare their properties against our published selection criteria for good adsorbents. Chemical analyses of pH, CEC and organic C were obtained for the eight samples. Mineralogical characterization was determined using XRD and FTIR. Laser diffraction was employed for particle size distribution of the samples dispersed in Na-hexametaphosphate solution and with ultrasonic treatment. The XRD analysis of this set of samples shows that the four effective adsorbents contain abundant smectite. Infrared analysis further indicates that these good adsorbents contain Fe in their octahedral sheets. Quartz, calcite and feldspars are present as diluents in seven products. The poorest adsorbent is a non-crystalline material that has an adsorption capacity of 0.0059 mol/kg. The pH of these eight samples range from 4.0 to 8.8, and pH of the four good adsorbents are in the range of 6.2 to 8.8. Three good adsorbents have organic carbon less than 0.5 % while the poorest adsorbent contains 48 % of organic carbon. The good adsorbents have CEC values in the range of 52 to 100 cmol(+)/kg, which correlates well with the contents of smectite observed in XRD patterns. Greater than 22 % of <2µm clay was found in the good adsorbents. These observations suggest that good adsorbents meet those criteria that we have established: near neutral pH, less than 0.27% organic carbon, and structural Fe in the octahedral sheet. This study confirmed that the presence of abundant smectite is important for a product to be considered an aflatoxin binder. Smectite crystallites composed of thin structural layers containing ions and adsorbed water accessible to the relatively planar aflatoxin molecules provide a unique setting for the binding of these carcinogenic molecules. The mineralogical and chemical properties of the four good adsorbents are in agreement with the published selection criteria, and were supported by the dairy experiment.

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A PERSPECTIVE OF COMMERCIALIZATION IN ACADEMIA, GOVERNMENT LABS AND INDUSTRY Gary W. Beall Texas State University, San Marcos, TX 78666, [email protected]

I have been involved in innovation and commercialization since 1975, first at a national lab, then in industry and finally in academia. The approach to innovation and commercialization in each of these sectors is quite different. This talk will give a perspective of the motivations in each sector for innovation and for commercialization of resulting inventions. Particular attention will be given to the process of innovation in each sector as well as the approaches used in commercialization. The perceived hurdles to innovation and commercialization will also be discussed. A few models that have shown great success, especially at universities, will be presented.

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A CASE STUDY OF THE ROAD TO COMMERCIALIZATION OF ORGANOCLAYS FOR WASTEWATER TREATMENT Gary W. Beall Texas State University, San Marcos, TX 78666; [email protected] The use of organoclays for wastewater treatment has now become a standard method of treatment in some industrial sectors. This is particularly true in the petroleum industry on offshore platforms. The path to this successful commercialization was long and meandering. The story behind this commercialization will be given in detail. Particular attention will be given to the multiple false starts that were experienced along the path to success. In many of these cases classic mistakes were made that stalled the efforts to successfully commercialize the technology. One of the critical factors in successful commercialization is having a champion that spends the time to push the technology to fruition. This factor will be discussed in detail.

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BIOAVAILABILITY OF FE(III) IN LOESS SEDIMENTS: AN IMPORTANT SOURCE OF ELECTRON ACCEPTORS Michael E. Bishop 1, Hailiang Dong 1*, Deb P. Jaisi 1,2, Ravi K. Kukkadapu 3 and Junfeng Ji 4 1Department of Geology, Miami University, Oxford, OH 45056 [email protected] 2Department of Geology and Geophysics, Yale University, PO Box 20820, New Haven, CT 06520 3Pacific Northwest National Laboratory, Richland, Washington 99352 4Department of Earth Sciences, Nanjing University, Nanjing China 210093 A quantitative study was performed to understand if Fe (III) in loess soil is available for respiration by using a common metal reducing bacterium, Shewanella putrefaciens, CN32. The loess samples were collected from three different sites I-270, Missouri, USA; Huanxia and Yanchang, Shanxi Province of China. Mineralogy of each loess sample was determined by analyzing the X-ray diffraction (XRD) peaks using the Jade 7 program. Ethylene glycol treatment was used to differentiate smectite and illite. Bioreduction experiments were performed at loess concentration of 20 mg/ml using lactate as the electron donor, Fe (III) in loess as sole electron acceptor in the presence and absence of anthraquinone-2, 6-disulfonate (AQDS). Experiments were performed in both non-growth (bicarbonate buffer) and growth (M1) media with initial cell concentration of ~2.75 x 107 and 2.06 x 107 cells/mL, respectively. The unreduced and bioreduced samples were analyzed using SEM/EDS methods. The chemical analyses revealed that only a small amount of Fe(III) (0.48% to 1.27 wt%) was present in these sediments. The XRD results suggest that all loess sediments contain smectite, illite, quartz, feldspar, plagioclase, and calcite but in different percentages. The ethylene glycol treatment of the sediments showed original d-spacing (~10Å) expanded to ~17Å suggesting the presence of smectite. The diffuse reflectance spectroscopy (DRS) and Mössbauer results suggest that the samples contained both hematite and goethite. Despite many similarities among the three loess samples, the extent and rate of Fe (III) reduction varied significantly. For example, the extent of reduction in the non-growth cell culture in presence of AQDS was 25% in HX, 34% in I-270, and 38% in YCH. Similarly, the extent of reduction in presence of AQDS in the growth experiment was 72% in HX, 94% in I-270, and 56% in YCH. Despite this extent of Fe (III) reduction, no significant change in mineralogy and morphology was detected, probably due to the small proportion of iron containing minerals in the loess sediments. The XRD, DRS and Mössbauer results suggest that iron oxides (goethite, hematite) and phyllosilicates were all bioreducible. In summary, the results of this study suggest that Fe (III) in loess sediments can be used by bacteria for respiration.

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RELATION BETWEEN MINERAL SURFACE AREA AND TOTAL ORGANIC CARBON CONTENTS FOR THE NORTH SEA JURASSIC KIMMERIDGE CLAY FORMATION Alex Blum 1, Neil Fishman 2, D. D. Eberl 1 and Ronald Hill 3

1Water Resources Discipline, U.S. Geological Survey, 3215 Marine St., Boulder, CO 80303, USA; [email protected] 2Geologic Discipline, U.S. Geological Survey, Box 25046 Denver Federal Center, Mail Stop 939, Denver, CO 80225, USA 3Marathon Oil Company, 5555 San Felipe, Houston, TX 77056 The relation between mineralogy, elemental chemistry, mineral surface area, and organic carbon preservation are examined in three cores having increasing degrees of maturation from the Jurassic Kimmeridge Clay Formation (KCF), a major petroleum source rock in the North Sea basin, offshore United Kingdom. Quantitative XRD mineralogy was determined using the RockJock program, and elemental chemistry was determined by XRF and ICP-MS. Mineral surface areas were determined by the adsorption of polyvinylpyrrolidone (PVP), using FTIR (infrared spectroscopy) to determine PVP concentrations (PVP can be adsorbed on clay surfaces) remaining in solution (Blum and Eberl, 1994).

The dominant clay mineral in the KCF samples is illite (plus minor chlorite and kaolinite), with MudMaster analysis showing a consistent mean illite crystallite thickness of 3.4 nm in the low (vitrinite reflectance (VR) <0.6%) and medium (VR ~0.7%) maturity cores, increasing slightly to 4.4 nm in the high (VR >1.0%) maturity core. Illite surface areas were calculated by combining the abundance of illite with the crystallite thickness measurements, and were in agreement with the PVP determined surface areas. This indicates that thin illites are the major contributor to mineral surface area in these rocks, and that there is little or no true smectite (1 nm-thick particles) present. The absence of smectite was confirmed with XRD.

Kennedy et al. (2002) suggested that adsorption of organic matter on clay mineral surfaces may be an important factor in the accumulation, preservation, and sequestration of organic carbon in the geologic record. However, comparison of mineral surface areas and total organic carbon in KCF samples determined by combustion and CO2 detection, and by low-temperature ashing (LTA) at 65oC in an oxygenated atmosphere, revealed no correlation between organic carbon content and mineral surface area in this system.

There is an excellent correlation between mineral surface areas measured on untreated samples and on samples with organics removed by LTA, indicating that the organic matter does not contribute significantly to mineral surface area measurements determined by PVP adsorption.

Blum, A. E., & Eberl, D. D. (2004). Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance. Clays and Clay Minerals, 52(5), 589-602.

Kennedy, M.J., Pevear, D.R. and Hill, R.J. (2002) Mineral surface control of organic carbon in black shale. Science, 95, 657-60.

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MEAN THICKNESS DISTRIBUTION AND EVOLUTION OF GROWTH MECHANISMS FOR TOBELITE - SMECTITE MIXED LAYERS, NEAR END-MEMBER TOBELITE, AND TOBELITE – K-ILLITE FROM THE FOSSIL HYDROTHERMAL SYSTEM OF HARGHITA BÃI, EASTERN CARPATHIANS

Iuliu Bobos 1 and D.D. Eberl 2 1Department of Geology, Faculty of Sciences, University of Porto, Portugal; [email protected] 2U.S.Geological Survey, 3215 Marine Street, Boulder, Colorado, 80303-1066, USA The <2 µm and <0.2 µm fractions of selected samples of a continuous smectite (S) to tobelite (T) end-member series (R1, R2, R3), and T - K-illite (I) interstratified structures with aqueous solutions of PVP-10 to remove swelling (Eberl et al., 1998a) were analyzed by X-ray diffraction (XRD). Tobelite crystallite thickness was measured using the computer program MudMaster (Eberl et al., 1996). Thickness distributions of ordered mixed layers T – S and end-member T show a lognormal shape. Mean thickness distribution of the <2µm fractions of T-S crystallites ranges from 3.5 to 6.1 nm, whereas the <0.2 µm fractions corresponding to end-member T ranges from 4.1 nm to 5.7 nm. Crystal thickness distribution are characterized by α and β2, where the values obtained of both parameters were plotted in the α - β2 diagram (Eberl et al., 1998b), in order to simulate the crystal growth mechanism and the reaction pathways of the samples studied. Ordered interstratified structures of T-S exhibit a theoretical pathway corresponding to two crystal-growth mechanisms: samples with high smectite content (R1) show a constant-rate nucleation followed by surface-controlled growth without simultaneous nucleation. Nucleation started at 2 nm and it continued to 3.3 to 3.5 nm for 30%S (R1) and to 4 nm for R1 to R2 structures. Nucleation ceased at about 15%S (R2), and then the reaction pathways follow one trend above and parallel to path A – C, where the tobelite crystallites continue to growth until nearing the end-member composition (5%S). The T – K-I crystallites show an asymptotic distribution related to a mixture of lognormal-like shapes caused by two distinct populations, which give an X-ray peak at 10.10 Å as a T and K-I mixture. The two lognormal distributions were found mixed in proportions 0.74 and 0.26 or 0.89 and 0.11. Mean thickness distribution measured on each phase ranges from 23.2 nm to 17.3 nm (T) and 11.1 to 6.5 nm (K-I). Otherwise, the mean thickness distribution of the mixed phase corresponding to T - K-I crystallites ranges from 5.7 to 9.6 nm. Both α and β2 parameters for each phase were calculated. The lack of a similar trend indicates the heterogeneous origin of the T - K-I samples, generated by superposition of lognormal distributions that suggests a model of mixing clays of different absolute ages. Eberl, D. D., Drits, V., Srodon, J. and Nüesch, R. (1996) MudMaster: A program for

calculating crystallite size distributions and strain from the shapes of X-ray diffraction peaks: U.S. Geological Survey Open-File Report 96-171, 46 pp.

Eberl, D. D., Nüesch, R., Sucha, V. and Tsipursky, S. (1998a) Measurement of fundamental illite particle thicknesses by X-ray diffraction using PVP-10 intercalation. Clays and Clay Minerals, 46, 89-97.

Eberl, D. D., Drits, V.A. and Srodon J. (1998b) Deducing crystal growth mechanisms for minerals from the shapes of crystal size distributions. American Journal of Science, 298, p. 499-533.

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A COMPREHENSIVE ANALYSIS OF ORGANIC CONTAMINANT ADSORPTION BY CLAYS Stephen A. Boyd 1, Cliff T. Johnston 2, David A. Laird 3, Brian J. Teppen 1 and Hui Li 1

1Department of Crop and Soil Sciences, Michigan State University, East Lansing, MI 48824, USA; [email protected] 2Department of Agronomy, Purdue University, West Lafayette, IN 47907, USA 3National Soil Tilth Laboratory, Ames, IA 50011, USA Macroscopic studies of nonionic organic contaminant (NOC) sorption by clays have revealed many important clues regarding factors that influence sorption affinity, and enabled the development of structural hypotheses for operative adsorption mechanisms. Integrating this understanding with knowledge gained from complementary molecular scale methodologies including X-ray diffraction, vibrational spectroscopies and molecular/quantum mechanical simulations has provided a comprehensive view of the central structural factors, forces and mechanisms responsible for NOC sorption by smectite clays. Based on these studies, we conclude: (1) Sorption of NOCs by smectites can take values along a continuum from zero up to 100 g NOC per kg clay. The critical factors that control sorption are a complex interplay among the functional groups of the NOC, the layer charge of the clay mineral, and the hydration of interlayer cations. (2) An optimal inorganic sorbent for NOCs should be a Cs+-saturated smectite with a low layer charge resulting from tetrahedral substitution. These criteria maximize the size and hydrophobicity of adsorption domains parallel to the clay surfaces while optimizing (near 12.5 Å) the adsorption domains perpendicular to the clay surfaces to promote solute dehydration and interaction with opposing siloxane sheets. Such clays may adsorb 10% of their weight for NOCs with multiple, strongly complexing functional groups (for such solutes, K-smectites are nearly as effective). In contrast, such clays adsorb only 1% by weight of more hydrophobic NOCs with lesser ability to form complexes with interlayer cations.

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CYCLIC TRENDS IN CLAY MINERALOGY OF THE GREEN RIVER FORMATION Thomas F. Bristow 1, Keith Morrison 2

1Division of Geological and Planetary Sciences, Caltech, MC170-25, 1200 E. California Blvd, Pasadena, CA 91125, USA; [email protected] 2Department of Earth Sciences, University of California Riverside, 900 University Ave, Riverside, CA 92521, USA. Sediments of the Eocene Green River Formation represent a complex, long-lived (~8 m.y.) lacustrine system, deposited in a series of continental basins found in parts of Utah, Wyoming and Colorado. At times, these basins were hydrologically closed, resulting in the formation of unusual assemblages of authigenic minerals (including clay minerals) and the development of m-scale cyclicity in sediments as a response to climatically induced changes in lake-level. As in other closed lake systems, a systematic change in the mineral assemblage in a margin-to-depocenter transect of the Green River Formation in the Uinta basin has been observed and is attributed to lateral gradients in redox conditions, pH and salinity. We present a detailed quantitative mineralogical record and analysis of clay minerals through meter-scale cycles of marginal lacustrine deposits of the Parachute Creek Member in the Uinta Basin, Utah. The aim of the study is to use clay minerals as indicators of changing lake chemistry and depositional processes at a sub-meter scale (temporal resolution of ~10,000yrs). Systematic changes in the proportions of dioctahedral and trioctahedral 2:1 clays correspond with sedimentary cycles. Trioctahedral smectite is the dominant clay mineral in organically enriched intervals of oil shale, whereas organic lean, silty, argillaceous carbonates contain greater proportions of 2:1 dioctahedral clays. The 2:1 dioctahedral group includes two phases; illite, which mainly occurs in the >2 µm size fraction, and dioctahedral smectite, identified from orientated and random preparations of clay aggregates. It is not possible to quantify the proportions of these two dioctahedral phases. However, a qualitative look at basal reflections indicates that illite is more abundant in organic lean intervals. The trioctahedral smectite in this part of the Green River is regarded as an early diagenetic mineral that formed in response to saline/alkaline conditions. However, sedimentary evidence, as well as C and O isotope data from carbonates, show that oil shales were deposited during periods of lake expansion (fresher water conditions). It therefore seems counterintuitive to find that trioctahedral smectite is most abundant in oil shale. This trend can be explained in terms of changing proximity of deposition to the lake margin. During lake contraction (organic-lean sediments), this part of the basin received greater inputs of coarser silicilclastics, including illite, and was probably subject to faster burial rates. Examination of the proportions of tri/dioctahedral smectite in sediments deposited during periods of high and low lake level, using compositional information, provides weak evidence that Mg-rich trioctahedral smectite is most abundant during high-stands, possibly resulting from longer periods of exposure to alkaline conditions. However, 060 reflections from clay aggregates do not support this conclusion.

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SEQUENCE STRATIGRAPHIC DISTRIBUTION OF THE CLAY MINERAL CORRENSITE IN MISSISSIPPIAN AGED LIMESTONE: EVIDENCE FROM TUSCUMBIA-MONTEAGLE FORMATIONS, NORTHWEST GEORGIA Daniel E. Bulger Department of Geology, University of Georgia, 210 Field Street, Athens, GA 30602-2501, USA; [email protected] The distribution of clay minerals within a high resolution sequence stratigraphic framework of a single Mississippian aged sequence in Northwest Georgia highlights the potential for corrensite to serve as a sequence boundary proxy for carbonates deposited during semiarid-arid conditions. Corrensite is a regularly ordered (50:50) interstratified chlorite-smectite clay mineral shown to be an intermediate phase in the Mg-smectite to Mg-chlorite transition with increasing temperature and pressure. Studies of a modern restricted marine environment suggest precursor minerals to corrensite form authigenically when pore water Mg/Ca level becomes high during the onset of calcite and gypsum precipitation (Hover et al., 1999, Martini et al., 2002). X-ray diffraction analysis of clay minerals separated from limestones within a single sequence of the Tuscumbia and Monteagle Formations reveal the presence of corrensite in close association with sequence boundaries, its absence within the deepening phase of the transgressive systems tract (TST) and early shallowing phase of the high stand systems tract (HST). During the late HST, corrensite appears progressively deeper within each succeeding parasequence cycle. This pattern suggests marine water became increasingly restricted during each succeeding phase of parasequence development within the HST prior to subaerial exposure. These data illustrate how linking clay mineral diagenesis within a high resolution sequence stratigraphic framework can provide valuable information concerning spacio-temporal distribution of eodiagenetic alterations in sediment, which may help to improve our ability to predict the distribution of porous and permeable rocks in carbonates deposited in semiarid-arid settings. Hover, V. C., L. M. Walter, D. R. Peacor, and A. M. Martini, 1999, Mg-smectite

authigenesis in a marine evaporative environment, Salina Ometepec, Baja California: Clays and Clay Minerals, v. 47, p. 252-268.

Martini, A.M., Walter, L.M., Lyons, T.W., Hover, V.C., and Hansen, J., 2002, Significance of early-diagenetic water-rock interactions in a modern marine siliciclastic/evaporite environment: Salina Ometepec, Baja California: GSA Bulletin, v. 114, p. 1055-1069.

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LIPID PEROXIDATION INDUCED BY EXPANDABLE CLAY MINERALS Daria Kibanova1,2, Antonio Nieto-Camacho 3, and Javiera Cervini-Silva 2,4,5,6 1 Facultad de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacán, C.P. 04150, México City, México 2 Instituto de Geografía, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacán, C.P. 04150, México City, México, +52 (55) 5622-4336, [email protected] 3Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacán, C.P. 04150, México City, México 4 NASA Astrobiology Institute, Department of Astronomy, University of California, 601 Campbell Hall, Berkeley, CA 94720-3411 5 Earth Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd., MS 90-1116, Berkeley, CA 94720 6 Universidad Autonoma Metropolitana, Unidad Cuajimalpa, Mexico, D.F.

Environmental nanoparticles such as 2:1 phyllosilicates induce oxidative stress. This paper reports that the content and distribution of structural Fe influence the ability of expandable clay minerals to induce lipid peroxidation (LP), a major indicator of oxidative stress, in biological matrices. Three smectite clays, hectorite (SHCa-1) and two nontronites (NAu-1) and (NAu-2) containing varying total content and distribution of structural total Fe, Fe(II), and Fe(III) were selected. Screening and monitoring LP was conducted using a Thiobarbituric Acid Reactive Substances (TBARS) essay. The higher content of TBARS present in nontronites compared to SHCa-1 suspensions was explained because structural Fe contributes to LP. The observed lack of correlation between TBARS content and extent of Fe dissolution indicated that the formation of TBARS is surface controlled. Results showing a higher TBARS content in SHCa-1 compared to nontronite (NAu-1 or NAu-2) supernatant solutions was explained because the former contain distinct, soluble chemical component(s) that could i) induce LP by its (their) own right and ii) whose chemical affinity for organic ligands used as inhibitors is weak. Clays serve as stronger inductors than 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH), but are much weaker than FeSO4. The outcome of this work shows that LP is clay-surface controlled and dependent on clay structural composition.

http://www.lbl.gov/visitor-info.html�

http://www.lbl.gov/visitor-info.html�

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SPECIAL MICROSTRUCTURES OF AUTHIGENIC ILLITE IN DIAGENETIC ENVIRONMENT: A STUDY BY TRANSMISSION ELECTRON MICROSCOPY (TEM) Tao Chen 1, Hejing Wang 2 and Xialin Zhang 3 1Institute of Gemology, China University of Geosciences, Wuhan 430074, China; [email protected] 2School of Earth and Space Sciences, Peking University, Beijing 100871, China 3The Faculty of Resources, China University of Geosciences, Wuhan 430074, China Some special microstructures of authigenic illite, which is collected in the northern part of Jixian County, Tianjin City in China, are observed by TEM. A plesiotwinning texture of Fe-rich illite has been found by selected area electron diffraction (SAED) pattern. The lattice of the SAED pattern can be described as a compound tessellation of {3,6}[79{3,6}], which is based on a large coincidence-site lattice (CLS) with the oriented crystal associations rotated at a non-crystallographic angle of 26°. Structure defect is found by one-dimensional structure imaging. In HRTEM study of illite, three continuous dark lines often represent a TOT (T: tetrahedral, O: octahedral) layer and the brightest line represents the interlayer region. While in this study, the continuous dark line on one dimensional structure image does not represent unchangeable T or O sheet, but represent a transformation from T sheet to O sheet or O sheet to T sheet. Such special structure may be caused by reversion of the T sheet. Near-atomic images of 1Mr-n(120), 1M and 2M1 polytypes of illite are observed by high-resolution TEM. Newly formed 2M1 domains are surrounded by packets of 1M r-n(120) or 1M illite. Such intergrowth of different illite-polytypic domains on a scale of several layers suggests that they are metastable. The lateral-coherent 1M and 2M1 illite domains are aligned along the same orientation and crystallographically continuous normal to [001]*. This is a new phenomenon to the polytypic intergrowth and transition.

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QUANTITATIVE XRD ANALYSIS OF CLAY-BEARING SAMPLES USING FULL XRD PATTERNS Steve J. Chipera 1 and David L. Bish 2

1Chesapeake Energy Corp., 6100 N. Western Ave, Oklahoma City, OK 73118, USA; [email protected] 2Indiana University, Dept. Geol. Sciences, 1001 E 10th St., Bloomington, IN 47405, USA Clay minerals are some of the most common minerals on the Earth’s surface, but they are also some of the most difficult materials to quantify accurately via X-ray powder diffraction. Traditional Reference Intensity Ratio (RIR) methods suffer from use of only a limited amount of data, and Rietveld refinement methods often have difficulties due to the disordered nature of many clay minerals. Rietveld refinement, in most current implementations, requires three-dimensional (3-D) diffraction effects and knowledge of the 3-D crystal structure for all phases in the analysis. Unfortunately, many clay minerals exhibit 2-dimensional diffraction effects due to turbostratic layer stacking. The traditional RIR method suffers because it requires one or more “standard” peaks with invariant intensity, which is particularly problematic for minerals such as smectite whose structures expand and contract with changes in relative humidity (RH). The smectite 001 reflection, the strongest, most diagnostic reflection, also suffers from significant intensity variations in response to steep Lorentz-polarization effects in the low-2-theta region. An effective method for analyzing samples containing clay minerals is to fit complete standard patterns to an observed pattern, pioneered by Smith et al. (1987). By fitting an entire pattern, it is not necessary to use only the highly variable smectite reflections (such as the 001). Variations in chemical composition and preferred orientation can also be compensated by using entire patterns (normalizing peaks that are too intense with those that are too weak). Smectite standard patterns, collected at differing RH, will allow compensation of variable 001 reflection intensities (due to the LP effect) and positions. FULLPAT (Chipera and Bish, 2002) couples the RIR method with least-squares fitting of full patterns to conduct quantitative XRD analyses of complicated mixtures and is publicly available by downloading from http://www.ccp14.ac.uk/ccp/web-mirrors/fullpat/. Chipera, S.J. and Bish, D.L. (2002) FULLPAT: A full-pattern quantitative analysis

program for X-ray powder diffraction using measured and calculated patterns. J. Applied Crystallography, 35, 744-749.

Smith, D.K, et al. (1987) Quantitative X-ray powder diffraction method using the full diffraction pattern. Powder Diffraction, 2, 73-77.

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BENTONITES OVER TIME: GEOLOGICAL SIGNIFICANCE AND IMPORTANT CHARACTERISTICS George E. Christidis 1 and Warren D. Huff 2 1Technical University of Crete, Department of Mineral Resources Engineering, 73100 Chania, Greece; [email protected] 2Department of Geology, University of Cincinnati, Cincinnati, OH 45221, USA. Bentonites are used in industry because of the important physical and chemical properties of smectites, including crystal structure and chemical composition, small crystal size and large specific surface area, cation exchange capacity and ion exchange selectivity, hydration and swelling behavior, colloidal properties, dehydration and reactions with organic and inorganic reagents. The vast majority of commercial bentonites come from the alteration of volcanic glass via a) diagenetic alteration of volcanic glass, b) hydrothermal alteration of volcanic glass, or c) formation in salt lakes and sabkha environments usually associated with sepiolite or/and palygorskite. This last process yields sediments rich in trioctahedral Mg-smectite (saponite and/or stevensite) of inferior commercial quality and does not necessarily require volcaniclastic source rocks. Commercial bentonites have Cenozoic- Late Mesozoic age, because in older strata smectite gradually converts to mixed layer illite-smectite forming K-bentonites and reducing their value for industrial application. Although Paleozoic K-bentonites are generally not commercially mined, they do have geologic value as stratigraphic marker horizons and as remnants of large caldera-forming tectonic events, which represent episodes of explosive volcanism (Huff et al., 1999). K-bentonites, in general, form thin beds, and deposits with thicknesses comparable to that of younger commercial beds are lacking. This is attributed at least partly to compaction during diagenesis. Recent work has revealed important geological characteristics of commercial bentonites that are not visible macroscopically (i.e. they display cryptic variations), and that are related to the distribution of the layer charge of smectites. The layer charge seems to vary in a rather systematic manner within bentonites, reflecting either geological constraints during their genesis or post-formation reworking. The geochemical affinities of the parent rock which was altered to bentonite also seems to affect the chemical characteristics of smectites formed in commercial bentonites. In general, alteration of basic rocks yields Fe-rich montmorillonites or Fe-rich beidellites, whereas alteration of acidic rocks tends to yield Al-rich smectites such as Tatatilla type montmorillonites or beidellites. The reported exceptions to these trends are attributed to the influence of the pore water chemistry on smectite chemistry, with a supply of excess Mg. A series of independent test of evidence indicates that bentonites form in a reducing environment and hence Fe is present as Fe2+. Oxidation to Fe3+ takes place when smectites are brought close to the surface. This suggests that dioctahedral Al- smectites display a smaller layer charge variation and hence have different properties when they form at depth compared to their counterparts at the surface (Christidis, 2008). Christidis, G.E. (2008) Do bentonites have contradictory characteristics? An attempt to

answer unanswered questions. Clay Minerals, 43, 515-529. Huff, W.D., et al. (1999) K-bentonite bed preservation and its event stratigraphic

significance. Acta Universitatis Carolinae-Geologica, 43, 491-493.

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DETERMINATION OF LAYER CHARGE OF SMECTITES IN BENTONITES: AN ASSESSMENT OF THE K-SATURATION METHOD George E. Christidis 1 and D. D. Eberl 2 1Technical University of Crete, Department of Mineral Resources Engineering, 73100 Chania, Greece; [email protected] 2U.S. Geological Survey, 3215 Marine St., Suite E-127, Boulder, Colorado 80303-1066 USA Characterization of smectite layer charge is of economic and geologic importance, because layer charge strongly affects key smectite properties such as swelling, cation exchange capacity, and ion exchange selectivity. These properties are important for the various applications of bentonites. Smectites usually are structurally and compositionally heterogeneous, and this is reflected in the layer charge. We have proposed a method for determination of layer charge of smectites (Christidis & Eberl, 2003). The method is based on the comparison of XRD traces of K-saturated, ethylene-glycol solvated smectites with simulated XRD-traces calculated for three-component interlayering (fully expandable 17.1 Å layers, partially expandable, 13.5 Å layers and non-expandable 9.98 Å layers). Measurement of layer charge and charge distribution is possible by means of the LayerCharge program. Based on the XRD characteristics a classification scheme of smectites according to their layer charge (low, intermediate and high charge smectites) was proposed (Christidis et al. 2006). The validity of the method has been repeatedly evaluated by determination of the layer charge of smectites with the structural formula method. The two methods yielded comparable results. The method has been used for determination of the layer charge distribution of smectites in bentonite deposits and for measurement of layer charge of reduced charge smectites treated by the Greene-Kelly test. The distribution of layer charge in bentonites has shed light on their possible mechanisms of formation and the influence of possible post-formation alteration events. Determination of layer charge is affected by intrinsic parameters (i.e. localization of layer charge) and on experimental constraints (sample preparation and calibration of the X-ray diffractometer). The layer charge of tetrahedrally charged dioctahedral smectites (beidellite-nontronite) is overestimated. Nevertheless the problem can be overcome by applying a correction. Hence it is suggested to apply the Greene-Kelly test (Li saturation followed by heating at 300°C) before determination of the layer charge. Sample preparation is critical because a high degree of preferred orientation and complete ethylene glycol salvation is necessary for optimum results. The reliability of determination of the layer charge with the proposed method is maximized by using sensitive detectors and improved measuring statistics for the count ratio in the diffracted beam. Christidis, G.E. & Eberl, D.D. (2003) Determination of layer charge characteristics os

smectites. Clays and Clay Minerals, 51, 644-655. Christidis G.E. Blum A.E. & Eberl D.D. (2006) Influence of layer charge and charge

distribution of smectites on the flow behaviour and swelling of bentonites. Applied Clay Science, 34, 125-138.

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QUANTIFICATION OF ETTRINGITE FORMATION IN STABILIZED CLAYS Maria Chrysochoou 1 and Dennis G. Grubb 2

1Department of Civil and Environmental Engineering, University of Connecticut, Storrs CT 06269, [email protected] 2 Schnabel Engineering, Westchester PA While ettringite (Ca6Al2(SO4)3(OH)12·26H2O) has been known for years to be associated with cement cracking, it was not demonstrated that it was an active expansion mechanism in lime stabilized clay subgrades until 1984, with the Stewart Ave., NV case. In a classic paper, Mitchell (1986) demonstrated using qualitative X-ray Diffraction (XRD) analyses that ettringite and the isostructural mineral thaumasite (Ca3Si(CO3)(SO4)(OH)6·12(H2O)) were associated with surface heaving. Ettringite and thaumasite were detected in heaved soil layers and absent in non-heaved layers, leading to the conclusion that their formation was the only viable mechanism to explain heaving phenomena. Since then, the role of ettringite formation in swell of stabilized clays has been widely studied, both in forensic investigations and in laboratory controlled swell tests. In each case, the evidence was qualitative. No one still can answer the questions: How much ettringite corresponds to how much swell? What is the rate of its formation in different clay types? Is all sulfate converted to ettringite, and if no, why? Is there a minimum amount of ettringite that can be tolerated without causing swell, and if yes, under which compaction conditions and confining pressure? The answers to these questions could, for example, provide a platform for the development of quantitative guidelines for risk assessment of heave in lime-stabilized clays. The National Lime Association currently sets a maximum sulfate level of 0.8 wt.%. This study presents the application of quantitative XRD using the Rietveld method in stabilized dredged material (a highly plastic clay) to evaluate ettringite formation and swell potential. The sulfate concentrations in the 17 dredged material blends tested in this study by far exceeded the recommendations of the National Lime Association, which sets the threshold for unacceptable risk at 0.8 wt% sulfate in lime-stabilized clays. Quantitative XRD analyses showed that the total sulfate concentrations in the SDM blends were not a good predictor of ettringite formation in the long term. At 28-days curing, only 0-50% of the maximum ettringite concentration was actually observed in all SDM blends. At 6 months curing, lime-based blends showed a dramatic increase in ettringite, while Cement Kiln Dust (CKD)-based blends showed no change or even a decrease. Mixed lime-CKD blends had variable behavior. Cement-treated blends showed no affinity for significant ettringite formation at any curing time. Lime-based blends released soluble Al very slowly, exhibiting delayed strength development and ettringite formation at 6 months curing. Ettringite-induced swell may thus be a concern in lime-based SDM blends in the long term. Mitchell, J.K. (1986) “Practical problems from surprising soil behavior,” J. Geotech.

Eng., 112(3), 255-289.

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A MODEL FOR POTASSIUM GAIN AND RADIOGENIC ARGON LOSS DURING BURIAL ILLITIZATION BASED ON ANALYTICAL DATA Norbert Clauer 1 and Abraham Lerman 2

1Centre de Géochimie de la Surface, CNRS and Université Louis Pasteur, Strasbourg, France; [email protected] 2Department of Earth and Planetary Sciences, Northwestern University, Evanston, Illinois, USA Illitization of smectite in sedimentary sequences or, more generally, the diagenetic evolution of K-bearing clays is associated with changes in their atomic ratio 40Ar/40K and K-Ar apparent age. However, the newly formed illite-smectite particles of progressively buried sedimentary rocks such as shales are systematically mixed with detrital mica-type particles of the same size-range. In the present attempt, we tried to identify the burial-induced evolution of the newly formed particles in the illitization process, from that of the altered detrital particles that occur concomitantly in the separated size fractions, by fitting one integrated model to the two processes. To do so, we used the 40Ar/40K data from published sources on Neogene shales and sandstones of the Mahakam Delta formation in Eastern Borneo, the Late Oligocene-Early Miocene sequence in the Texas Gulf Coast, and the Early Jurassic-Late Cretaceous section in the North Sea, and modeled their changes as a two-process mechanism. The model describes the dependence of the changing K-Ar apparent ages of the separated size fractions on the rate of K addition to, and radiogenic 40Ar release from, particles. It simulates reasonably well the changes with depth or depositional time in the K-Ar apparent ages of both fine (generally <0.4 μm) and coarse (generally >2 µm) clay fractions in the four sedimentary sequences. The analyzed decreases with depth in the K-Ar apparent age of the mainly detrital coarser fractions (generally >2 µm) are bracketed by the calculated values of a K-addition rate ranging from 0.2 to 3.5 %/Ma and the 40Ar release rate ranging from 0.5 to 4.5 %/Ma. For the fine fractions (generally <0.4 μm) consisting mainly of newly formed authigenic particles, and for which the mass fraction increases with increasing sediment depth relative to the detritus in the overall clay fraction, the K gain rate varies from 3.5 to 6 %/Ma and the 40Ar release rate from 0.7 to 6 %/Ma. It can also be shown that smaller rates of K addition and 40Ar escape, each about 1 %/Ma, simulate the cases where the mean K-Ar apparent ages of the fine fractions remain constant with depth, clearly confirming that such relationships between K-Ar ages and stratigraphic depth do not represent a steady state, as claimed in several cases, but a continuing dynamic process of diagenesis that is a result only of varying addition and release rates. The modeled results help identify and quantify the illitization reactions in mixtures of authigenic and detrital clay-type fractions of varied sizes in sediment sections extending over stratigraphic intervals of 103 m or 101 Ma.

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LI AND B ISOTOPIC TRACING OF ILLITE NUCLEATION AND GROWTH IN BENTONITE UNITS OF THE EASH SLOVAK BASIN Norbert Clauer 1, Lynda Williams 2, Miroslav Honty 3 and Vladimir Sucha 4

1Centre de Géochimie de la Surface, CNRS et Université de Strasbourg, France; [email protected] 2 Arizona State University, School of Earth & Space, Tempe, AZ 85287-1404, USA 3 SCK•CEN, Environment, Health and Safety Institute, Waste and Disposal, Mol, Belgium 4 Faculty of Sciences, Comenius University, Mlynska Dolina, Bratislava, Slovakia

Clay minerals, especially mixed layers illite-smectite (I-S) are predominant minerals in sedimentary and volcano-sedimentary rocks worldwide. Their study has been very useful for understanding the thermal histories and fluid flows in sedimentary basins. The systematic fractionation of light stable isotopes, such as B, Li or N that are common elements in sedimentary organic and mineral matter, has been investigated over the last two decades. As the B and Li isotopic composition of sedimentary pore fluids (interstitial waters) are recorded in illite crystals that nucleate and grow at increasing burial temperature, these isotopic systems might be used to reconstruct the interactions between maturating organics, and nucleating and growing illite particles. Illite “fundamental particles” represent the initial illite crystals nucleated from a saturated aqueous solution. Their formation requires either dissolution of smectite followed by nucleation and growth of illite, or a surface controlled growth (e.g. a solid-state process). This phase transition occurs over a temperature and pressure range that coincides with hydrocarbon (oil and gas) generation from sedimentary organic matter (kerogen), and during the release of isotopically light B and Li from organic compounds. While the mechanism of illite growth varies with the aqueous chemistry (e.g. saturation state controls supply and surface area controls rate), one observes varied geochemical and isotopic signatures under the changing chemical conditions encountered during burial history. Combined to other isotopic data, the determining potential of this stable isotope approach results from the fact that B is preferentially hosted by the tetrahedral sites of illite-type crystals, while Li is hosted by the octahedral sites of the same mineral structures. It can, therefore, be assumed that contents and fractionation rate delineate the origins of both elements in the initial fluids and how they are incorporated into the crystalline structures depending on the type of growth process. For instance, K-Ar dating of sized illite fundamental particles can provide K-Ar ages for the smallest particles that are similar to or older than those of larger ones. Consequently, by examining the B and Li isotope compositions of illite-rich fundamental particles as a function of crystal size, therefore as a function of process duration, modifications in the chemical composition of interactive fluids may relate during growth to isotopically lighter fluids issued from maturating hydrocarbons. In a preliminary attempt, B and Li contents and isotope compositions were determined on the <0.02, 0.02-0.05 and 0.05-0.2 µm size fractions of illite-rich fundamental particles extracted from I-S of nine bentonite core samples collected in various parts and at various depths of the East Slovak Basin. The B contents range from 30 to 486 µg/g, with a δ11B varying from +6.8 to -26.9 per mil. The Li contents of the same size fractions from I-S of the same samples scatter less between 5 and 139 µg/g, with a δ 7Li varying from +8.3 to -21.7 per mil. These results are evaluated by comparison with different parameters that potentially could have interfered with the nucleation and growth of these fundamental particles. The location, age and burial temperature are among the criteria that were tested as potential interfering processes having an impact on the B and Li contents and isotope compositions. The mechanism of crystal growth was also evaluated, as well as a possible contribution of organic matter during fluid migration.

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ESTIMATION OF ORIGINAL POTTERY FIRING TEMPERATURE THROUGH X-RAY DIFFRACTION Connie I. Constan Department of Anthropology, MSC01-1040 Anthropology, 1 University of New Mexico, Albuquerque, NM 87131, USA; [email protected] X-ray diffraction was used to compare the clay mineralogy of ceramic matrices from prehistoric pre-Colombian Gallina pottery and natural clays from the Gallina region. The area of the Gallina culture is located in northwest New Mexico and dates between A.D. 850 and 1275. The Gallina ceramic assemblages include both decorated and utility wares with only extremely rare evidence of exchange of finished ceramics. It appears that Gallina potters were using quartz, feldspar, and mica sand-size temper in their ceramics. The ceramic matrix seems to be a poorly crystallized illite-smectite mixed-layered clay mineral with perhaps a small amount of discrete illite. Also there could be a kaolin mineral present in trace amounts. The potters themselves may have mixed natural clays from more than one geologic unit, which could lead to this composition. When the primary clays are illites, X-ray diffraction can be helpful in verifying firing temperatures (Maggetti 1982). Based on refiring color changes, the firing process for these ceramics reached temperatures between 750º and 850º C. This temperature range is typical for open fired ceramics in the American Southwest. At these temperatures, many clays begin to lose their characteristic crystalline structure. Natural clays were collected from seven geologic formations in the central Gallina area. One sample from each unit was made into tiles and fired at temperatures of 300º, 600º, 750º and 900º C. The choice of temperatures was based on mineral transformations (Grim 1968), open firing temperatures (Shepard 1976), and archaeothermometry studies (Rice 1987). The fired natural clay patterns were compared to the ceramic patterns. It appears that the X-ray diffraction results are consistent with the refiring color changes and indicate a firing temperature between 750º and 900º C. In addition, the X-ray diffraction patterns show evidence of an amorphous material, indicating vitrification in the formation of the ceramic. Grim, R.E. (1968) Clay Mineralogy. 2nd edition. McGraw-Hill, New York. Maggetti, M. (1982) Phase Analysis and Its Significance for Technology and Origin. Pp.

121-133 in: Archaeological Ceramics (J.S. Olin and A.D. Franklin, editors). Smithsonian Institute, Washington DC.

Rice, P.M. (1987) Pottery Analysis: A Sourcebook. The University of Chicago Press, Chicago.

Shepard, A.O. (1976) Ceramics for the Archaeologist. Carnegie Institution of Washington, Washington, DC.

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BEHAVIOR OF NANOCONFINED WATER IN PALYGORSKITE AND SEPIOLITE Randall T. Cygan 1, Nathan W. Ockwig 1, Jeffery A. Greathouse 1 and Tina M. Nenoff 2 1Geochemistry Department, Sandia National Laboratories, Albuquerque, NM 87185, USA; [email protected] 2Surface and Interface Sciences Department, Sandia National Laboratories, Albuquerque, NM 87185, USA Inelastic neutron scattering, density functional theory, ab initio molecular dynamics, and classical molecular dynamics were used to examine the behavior of nanoconfined water in the channels of palygorskite and sepiolite. The complementary methods provide a strong basis to illustrate and correlate the significant differences observed in the behavior of nanoconfined water in two unique clay minerals. Palygorskite and sepiolite are 2:1 magnesium-rich phyllosilicate minerals characterized by modulated structures having silicate sheet inversions to accommodate the strain associated with the coordinating magnesium octahedral sheet. Distortions of silicate tetrahedra in the smaller-pore palygorskite exhibit a limited number of hydrogen bonds with water, with relatively short bond lengths. However, without the distorted silicate tetrahedra, an increased number of hydrogen bonds are observed in the larger-pore sepiolite with corresponding longer bond distances. Because there is more hydrogen bonding at the pore interface in sepiolite than in palygorskite, we expect librational modes to have higher overall frequencies (i.e. more restricted rotational motions). Inelastic neutron scattering data clearly illustrate this shift. It follows that distortions of the silicate tetrahedra in the clay minerals effectively disrupts hydrogen bonding patterns at the silicate-water interface, and this has a greater impact on the dynamical behavior of nanoconfined water than the actual size of the pore or the presence of coordinatively-unsaturated magnesium edge sites. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

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ABIOTIC NITRATE REDUCTION BY REDOX ACTIVATED Fe-BEARING SMECTITES Zachary B. Day and Joseph W. Stucki Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, IL 61801; [email protected] Reduction of nitrate and nitrite by bacteria is well documented, occurring in a vast array of soil types via several distinct and well described biotic pathways, but significant evidence also indicates the potential for nitrate reduction via abiotic pathways, which have yet to be fully investigated. The inorganic portion of soils may play a larger role in these redox reactions than previously thought, particularly Fe-containing clay minerals and various Fe (oxyhydr)oxides. The synergistic effects of these clay minerals and Fe oxides within reducing soil environments have yet to be fully understood as studies looking at the inorganic aspects of such systems have tended to focus on one part, to the exclusion of the other. A study of Danish soil profiles described a redox interface occurring at varying depths, above which exists an oxidizing zone and below which exists a reducing zone. This boundary coincides with a sharp change in nitrate concentrations, dropping below detectable limits beneath the boundary and being replaced by ammonium. Previous assays of biological activity found few bacterial denitrifiers in similar soils, leading to the conclusion that the reductant was structural Fe(II) within the clay minerals activated by biological activity. Other work points to nitrate reduction in soils being the product of reactions with Fe(oxyhydr)oxides. In particular, green rusts—Fe(II)-Fe(III) layered double hydroxides—have been found to be excellent for reducing nitrate and are thought to occur naturally in soils, albeit their extreme sensitivity to oxygen has limited their in situ characterization. The objective of the present study was to investigate the synergistic relationships between nitrate reduction and the various Fe phases that may exist in soil environments under reducing conditions. Using several different systems, both including and excluding Fe oxides, the reductive capacity of Fe-rich clay minerals towards nitrate was explored. These systems were prepared by (1) reduction of the smectite with dithionite or bacteria, which produced extensive amounts of Fe(II) in the clay octahedral sheet; (2) reaction of the oxidized smectite with Fe(0) under either inert- or oxygenated-atmosphere conditions, which produced limited, but significant, structural Fe(II) in the clay and Fe (oxyhydr)oxides such as magnetite and possibly others; and (3) reaction of the clay prepared as in (1) with the subsequent addition of anthraquinonc-2,6-disulfonate (AQDS) prior to reaction with nitrate, which enabled the reduced AQDS to serve as an electron shuttle between the reduced clay and the nitrate. Experiments involving solely a reduced clay mineral phase show no reductive activity towards nitrate, probably due to electrostatic repulsion. However, systems consisting of mixtures of reduced clay and Fe oxides are capable of nitrate reduction. Our results suggest that neither clay minerals nor Fe oxides alone are responsible for abiotic redox reactions involving such anions as nitrate within soils, but that they are likely to be synergistically linked in this capacity.

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DELIVERING INNOVATION Chris DeArmitt Hybrid Plastics, Hattiesburg MS 39401, USA [email protected] Innovation! Everyone talks about it but no one is delivering it. We know we need it, but how can we produce the new products we need to keep our companies thriving? This talk is written from the perspective of an innovator, someone with a track record of introducing new products and processes, someone who has experienced the frustration of trying to introduce novelty into a resistant organization. First, the innovation process is examined to identify where the weak points are and what steps can be taken to ameliorate the problems. Secondly some guidelines are given so you can choose which people and companies to work with. A screening method will be shown that flags signs that indicate danger or positive indications when you make contact with a company and want to work with them on a new product. This allows you to choose your development partners more carefully. Finally, a prototype system for quantifying the "Innovation Index" of a company will be presented. It will be demonstrated that one can estimate the innovation ability of a company based on simple, readily available facts.

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PROBE ADSORBED AFLATOXIN B1 MOLECULES IN SMECTITE Youjun Deng, Ana Luisa Barrientos Velazquez and Joe B. Dixon

Department of Soil and Crop Sciences Texas A\&M University College Station, TX 77843-2474; [email protected]

Numerous trials have demonstrated that certain bentonites can effectively reduce the toxicity of aflatoxin B1 when a small amount of the clays, e.g., 0.5% (wt), was incorporated into animal feed. Recent studies in human diet have shown promising results. The detoxification mechanism, however, is still not well understood. The objectives of this study are to reveal (1) the bonding mechanism between aflatoxin and smectite and (2) the impact of adsorbed aflatoxin on the surface properties of smectite. The < 2 µm clay fraction of a bentonite from Gonzales Texas, USA was separated and used in the study. Smectite (montmorillonite) and minor amount of opaline-CT are present in this fraction. Two types of aflatoxin B1-smectite complexes: one with aflatoxin adsorbed on external surfaces only and the other one with aflatoxin adsorbed both on external surfaces and in the interlayer, were prepared in acetonitrile and water respectively. The d(001)-spacing of the complexes were monitored at elevated temperatures up to 550 C. The complexes were saturated with Na+, K+, Ca2+, Mg2+, Al3+, La3+, Mn2+, Ni2+, or Cu2+. Variable temperature X-ray diffraction analysis indicates that the d(001) spacing of aflatoxin B1-smectite complexes prepared in acetonitrile collapsed to 1.0 nm at 150 C or higher temperatures, but the d(001) spacing of the complexes prepared in water remained > 1.2 nm up to 400 C, confirming interlayer adsorption of aflatoxin when water was used as the solvent. Infrared bands of smectite did not shift after adsorbing aflatoxin B1. The in-phase vibrations of the dicarbonyl bonds of aflatoxin B1 showed a greater than 26-cm 1 red shift on both complexes prepared in acetonitrile and in water. This shift was affected by the exchangeable cations under fully dried condition (purged with dry N2). From the monovalent cations Na+- and K+-saturated complexes to the transition metal Ni2+- and Cu2+- saturated complexes, the carbonyl band shifted from 1734 cm 1 to 1685 cm1. Meanwhile, blue shifts from the methoxy group were observed. The exchange cations also caused color difference in the complexes: the Na+- and K+-saturated complexes were white, the Ca2+- or Mg2+-saturated light yellow, and Al3+-, La3+-, Mn2+-, Ni2+-, or Cu2+-saturated dark yellow. Under humid conditions, the type of cations had less impact on the infrared band position or the color. The d(001) spacing of complexes also changed with humidity. These observations suggest that aflatoxin molecules can be adsorbed on both external surfaces and in the interlayer spaces of smectite via two similar mechanisms: (1) H-bonding (under humid condition) through water molecules in hydration shell of the exchange cations and (2) direct ion-dipole interaction and coordination (under dry condition) between the exchangeable cations and the carbonyl groups of aflatoxin B1. The reversible changes in color, infrared band position, and d(001) spacing of the complexes with humidity suggest that water molecules can still access the interlayer space that are occupied by the adsorbed aflatoxin molecules.

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K-Ar DATING OF THE Fe-ILLITE FROM LE PUY (FRANCE) APPLYING SEQUENTIAL ACID DISSOLUTION Arkadiusz Derkowski 1, Jan Środoń 1, Marc Amouric 2 and Michał Banaś 1 1 Polish Academy of Sciences, Senacka 1, 31-002 Kraków, Poland; [email protected] 2 CRMC2-CNRS, Campus de Luminy, Case 913, 13288 Marseille cedex 09, France

The Fe-illite is a characteristic mineral of the alkaline lacustrine environment. It is formed syn-depositionally in these rare geochemical conditions and it contains a significant portion of Fe3+ substituting Al3+ in the octahedral sheet. A clay sample rich in Fe-illite from the Oligocene alkaline lake sediments (Gabis, 1963) near Le Puy (Massif Central, France) was Na-exchanged and separated into clay subfractions. The subfractions were dated using the K-Ar method, but no date (83-103 Ma) came even close to the expected Oligocene age of ca. 30 Ma. Since the expected mechanism for such an effect was an overgrowth of Fe-illite on a detrital, Al-rich mica, the acid treatment experiment was set up to dissolve the Fe-illite, leaving the detrital component in the residuum (Derkowski et al., in press). The Fe- and Mg-rich 2:1 phyllosilicates are known for their higher solubility in low pH than the Al-rich 2:1 phyllosilicates (Novák and Číčel, 1978) The subfractions were treated with 5M HNO3 at 100°C, with solid-to-liquid ratio 2 g/L, for 6 and 24 hours, than washed, dried and dated for their K-Ar isotopic age. The dates received were unexpectedly high: from 220 to 507 Ma, and very low %K2O indicated significant contents of the amorphous silica, produced as a residuum of the acid treatment. In order to remove the silica, the acid-treated subfractions were reacted with hot NaCO3 (Rodríguez et al., 1995). The K-Ar dating performed after the silica removal resulted in a significant decrease of the isotopic age, to 195 - 155 Ma. The “differential K-Ar age” (Derkowski et al., in press) calculated for the subfractions between the natural and the acid- and NaCO3-treated portions, resulted in relatively constant values of 65-75 Ma. This experiment produced a strong indication that the amorphous silica, formed during acid attack from the tetrahedral sheet, retains a significant portion of 40Ar* - from 178 to 870 pmol/g. The alkaline leaching is then a necessary last step of the sequential dissolution experiments performed in order to date the non-dissolved residuum. Neither the residua gave the expected detrital Hercynian isotopic age of ca. 300 Ma, nor the differential ages came close to the expected stratigraphic age of ca. 30 Ma. Perhaps this result indicates a very intimate intergrowth of the detrital and the authigenic 2:1 mineral, so that at every step they dissolve together, though at very different rates. This conclusion is supported by the HRTEM images, showing the 1Md Fe-illite intergrowing the external layers of a well-ordered mica.

Derkowski, A., Środoń J., Franus W., Uhlik P., Banaś M., Zieliński G., Čaplovičová M., and Franus M. (2009) Progressive dissolution of glauconite and its implications for the methodology of K-Ar and Rb-Sr dating. Clays Clay Min., in press.

Gabis, V. (1963) Etude mineralogique et geochimique de la serie sedimentaire oligocene du Velay. Bull. Soc. Francaise de Mineralogie et Cristallographie, 86, 315- 354.

Novák, I. and Číčel, B. (1978) Dissolution of smectites in hydrochloric acid: II. Dissolution rate as a function of crystallochemical composition. Clays Clay Min., 25, 5, 341-344.

Rodríguez, M.A.V., López Gonzáles, J. de D., and Bañares Muñoz, M.A. (1995) (1995) Preparation of microporous solids by acid treatment of a saponite. Microporous Mat., 4, 251-264.

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APPLICATION AS ELECTRODE MODIFIERS OF NANOHYBRID MATERIALS OBTAINED FROM THE GRAFTING OF ORGANIC UNITS ON THE INTERLAYER SURFACES OF KAOLINITE Ignas K. Tonle 1,2 Emmanuel Ngameni 3, Thomas Diaco 1, Sadok Letaief 1 and Christian Detellier 1

1Centre for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa (Ontario), K1N 6N5, Canada [email protected] 2 Département de Chimie, Faculté des Sciences, Université de Dschang, B. P. 67 Dschang, Cameroun 3 Laboratoire de Chimie Analytique, Faculté des Sciences, Université de Yaoundé 1, B. P. 812 Yaoundé, Cameroun This work reports the preparation and characterization of new nanohybrid materials obtained by the grafting of organic units on the interlayer surfaces of kaolinite by utilizing kaolinite pre-intercalates (dimethylsulfoxide or urea) as starting materials. The chemical modification process involves the in-situ displacement of the pre-intercalated dipolar organic molecule by ionic liquids, as well as by amine or organosilane derivatives, followed by their grafting under carefully controlled melt reaction conditions. The structure of the resulting materials was characterized by X-ray Diffraction (powder and oriented sample), thermal analysis (TG, DTG and DTA), FTIR, as well as by 29Si and 13C MAS NMR spectroscopy. It demonstrated the covalent binding of the cationic species on the kaolinite internal surfaces. Ion-exchange and permeation properties of the new nanohybrid materials were tested upon their deposition onto the surface of glassy carbon or platinum electrodes by means of multisweep cyclic voltammetry, in comparison to electrodes coated with unmodified kaolinite.

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MORPHOLOGICAL PROPERTIES OF SMECTITE ADSORBENTS OF AFLATOXIN AS REVEALED BY LATTICE FRINGES J.B. Dixon 1, A.L. Barrientos Velazquez 1, Z. Luo 2 and Y. Deng 1 1Soil and Crop Sciences Department, Texas A&M University, College Station, TX 77840 2Microscopy and Imaging Center, Texas A&M University, College Station, TX 77840 Email address: [email protected] Research on aflatoxin adsorption by bentonites has shown a clear relationship to clay content yet the high abundance of silt-size particles in the most effective adsorbing bentonites raises questions about the avenue for diffusion of the mycotoxin molecules into the coarse particles. The objective of this study is to reveal the accessibility of the adsorbing sites at the nanometer scale in order to better understand the apparent contradiction of adsorption and particle size. The hypothesis is that lattice fringes would be a useful source of information to identify particle traits that influence aflatoxin adsorption. The morphology of two Texas bentonites, which are coded as 4TX and 1TX, with high aflatoxin adsorption were examined with a transmission electron microscope (JEOL 2010). Lacy holey carbon grids (Ted Pella, Inc. # 01883-F) were chosen to give particles various orientations and open access for viewing thin smectite. Bentonites were dispersed in water as control samples. Duplicate samples were saturated with aflatoxin and washed once with water to prepare the samples for x-ray diffraction (Bruker D8) and TEM mounts. Particle size was determined by laser diffraction (Beckman Coulter LS230) using dispersion in Na-hexametaphosphate solution and ultrasonic treatment. Structural composition was indicated by Fourier transform infrared analysis. Particle size ranges from 0.06 to 80 μm for 4TX and from 0.08 to 32 μm for 1TX. The contents of <2 μm fractions are 35 % and 14 %, respectively. The bentonites contain numerous aggregates of 2 to 5 μm breadth and may exceed clay in abundance with visual evidence of porosity in electron micrographs. Electron diffraction fringes indicate that the two smectites were expanded from 1.2 nm when untreated to 1.5 nm when reacted with aflatoxin, confirming the interlayer adsorption of the aflatoxin molecules in these samples, which have been shown previously by XRD of other bentonites. These observations support a concept of smectite aggregates in bentonites persist through typical laboratory dispersion procedures yet many are sufficiently porous to be effective adsorbents. These bentonites contain numerous smectite particles that are lath shaped. The laths are flexible and curvature is common. They usually are a few layers thick and rarely 25-layer thickness indicated by lattice fringes. The particle terminations may be frayed or convergent. Convergent ends have orderly fringes and frayed terminations tend to be curved and disorderly. The smectites are very aluminous and the better adsorbent had evidence for structural iron in the octahedral sheet as observed previously in other smectites. There remain other questions as to why some smectites are relatively poor adsorbents of aflatoxin aside diluents of prismatic minerals such as quartz, feldspar, and cristobalite.

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THE USE OF CLAY MINERALS FOR TREATMENT OF COAL FLY ASH AND FLY ASH LEACHATE Rona J. Donahoe, Sidhartha Bhattacharyya and Ghanashyam Neupane Department of Geological Sciences, University of Alabama, Tuscaloosa, AL 35487-0338; [email protected] About half of the fly ash produced by coal-fired power plants in the United States is buried in landfills or impounded in ash lagoons. Ash lagoons receive fly ash and other coal combustion products (CCPs) as slurry, which is sent by pipe from the power plant to the lagoon. Contact between the fly ash and sluicing water or meteoric water generates leachate. Fly ash leachate solutions contain elevated levels of several different trace elements which can be damaging to the environment and to human health. Because older CCP disposal facilities were unlined, low-cost and effective methods for the treatment of coal fly ash and fly ash leachate are needed. Further treatment challenges are presented by the fact that both cationic and oxyanionic elements must be immobilized simultaneously. Due to their high surface areas and high adsorption capacities, clay minerals have potential application for the treatment of trace element contaminants associated with coal fly ash. Fly ash samples were collected from four power plants for use in batch experiments examining the use of the clay minerals ferrihydrite and surfactant-modified clinoptilolite for treatment of fly ash and fly ash leachate, respectively. Treatment of fly ash with a ferrous sulfate (FS) solution, at a solid:liquid ratio of 1:30, coated the ash particles with amorphous ferric hydroxide. FS-treated and untreated fly ash samples were leached using a synthetic acid rain solution to evaluate trace element mobility and the effectiveness of the treatment method. Results showed that FS treatment significantly reduced the mobility of oxyanionic trace elements As (24-91%), Cr (82-97%), Mo (74-100%), Se (41-87%) and V (55-100%) in all of the fly ash samples studied. Ferrous sulfate treatment was not effective for B, which commonly occurs as a neutral specie, B(OH)3, or for the cationic trace elements Ni and Sr, all of which were mobilized by the treatment solution. The second set of batch experiments tested the ability of surfactant-modified clinoptilolite to decrease the concentrations of oxyanionic and cationic trace elements in fly ash leachate. Leachate was generated by shaking 30 g of ash in 450 ml of DDI water for 48 hours. The leachate solutions were separated from the fly ash and treated with different percentages of HDTMA-modified clinoptilolite. Comparison of the compositions of treated and untreated leachate solutions showed that HDTMA-modified clinoptilolite is effective in decreasing the concentrations of both oxyanionic and cationic trace elements. Treatment with 10% HDTMA-modified clinoptilolite removed up to 28%, 69%, 16%, 15%, 22%, 15% and 13%, respectively, of the As, Cr, Mo, Ni, Se, Sr and V from the fly ash leachate solutions. These results support the use of ferrihydrite and HDTMA-modified clinoptilolite to reduce the mobility of trace elements associated with coal fly ash.

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MICROBIAL REDUCTION OF IRON IN SMECTITE (NONTRONITE), MIXED-LAYER SMECTITE/ILLITE, AND ILLITE: CORRELATING THE RATE AND EXTENT OF BIOREDUCTION WITH LAYER CHARGE AND EXPANDIBILITY

Hailiang Dong, Shanshan Ji, Junjie Yang, Michael Bishop, and Jing Zhang Department of Geology, Miami University, Oxford, OH 45056, USA, [email protected] Clays and clay minerals are ubiquitous in soils, sediments, and sedimentary rocks. They play an important role in environmental processes such as nutrient cycling, plant growth, contaminant migration, organic matter maturation, and petroleum production. The changes in the oxidation state of the structural iron in clay minerals, in part, control their physical and chemical properties in natural environments, such as clay particle flocculation, dispersion, swelling, hydraulic conductivity, surface area, cation and anion exchange capacity, and reactivity towards organic and inorganic contaminants. The structural ferric iron [Fe(III)] in clay minerals can be reduced either chemically or biologically. Biological reduction of ferric iron has been performed for a number of clay minerals, including smectite (nontronite), illite, chlorite, and palygorskite, but the quantitative relationship between the extent/rate of bioreduction and clay mineral properties is still not well understood. The objective of this study was to assess how layer charge and layer expandability in the dioctahedral clay mineral series smectite-illite affect the extent and rate of bioreduction. The experiments were conducted with structural Fe(III) in the clay minerals smectite (nontronite), mixed-layer illite/smectite (70/30), rectorite (I/S, 50/50), and pure illite as the sole electron acceptor and lactate as the sole electron donor in the presence or absence of AQDS as a electron shuttle in bicarbonate buffer. The results showed the extent of nontronite (NAu-2) bioreduction reached ~40% in about a week, whereas the extent of illite (3605) bioreduction reached ~15% over longer time (~2 weeks). The mixed-layer illite/smectite exhibited intermediate extents and rates of bioreduction. In addition, the effect of electron shuttle, AQDS, was greater on illite than it was on smectite. When the extent of bioreduction was plotted against the layer charge and expandability of the four clay minerals, a positive correlation was obtained, demonstrating that bioreduction of structural Fe(III) in clay minerals was controlled by its accessibility by iron-reducing bacteria. These results have important implications for estimating reducing power of soils and sediments in natural environments and the role of reduced clay minerals in remediating organic and inorganic contaminants.

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NEAR INFRARED SPECTRA OF ILLITE AND MUSCOVITE IN VERY LOW-GRADE METAMORPHIC ROCKS OF THE BELT SUPERGROUP, MONTANA AND IDAHO Edward F. Duke 1 and Reed S. Lewis 2 1Department of Geology and Geological Engineering, South Dakota School of Mines and Technology, Rapid City, SD 57701-3995, USA, [email protected] 2Idaho Geological Survey, University of Idaho, Moscow, ID 83844-3014, USA The Mesoproterozoic Belt Supergroup extends across western Montana and northern Idaho into eastern Washington, and the stratigraphically equivalent Purcell Supergroup covers parts of southwestern Alberta and southeastern British Columbia. The thickness of Belt sediments increases from near zero in central Montana to over 16 km in western Montana and northern Idaho. The thick section of Belt argillites and siltites was the subject of seminal studies on the transformation of white mica (illite and muscovite) from the 1Md and 1M to the 2M1 polytype as a function of depth of burial (e.g., Maxwell and Hower, 1967). In the present study, the wavelength of the white mica Al-OH combination band near 2200 nm was determined in 1036 samples with a portable visible and near infrared reflectance spectrometer. The Al-OH wavelength decreases systematically with increasing depth of burial and metamorphic grade, from 2225 nm in areas of high-grade diagenesis, to 2205 nm at the garnet isograd. Though slightly less systematic, wavelength values continue to decrease in the garnet through sillimanite zones, reaching a low of 2194 nm. The wavelength shift is negatively correlated with the Al content of the white mica; total Al increases as a function of metamorphic grade from ~2.0 to ~2.8 atoms per 11 oxygens, accompanied by decreases in Si, Fe, and Mg. The overall chemical change in white mica is therefore attributed to the aluminoceladonite exchange (IVSi + VI[Mg,Fe2+] = IVAl + VIAl). Correlation between the wavelength of the Al-OH band and Al content in white mica was first pointed out by Post and Noble (1993). Later Martínez-Alonso et al. (2002) explored the relationship using quantum mechanical calculations and confirmed that the OH frequencies could be explained by the octahedral cations (Al, Fe, Mg, Fe3+), with a possible small effect from the tetrahedral sheet but no effect from interlayer cations. The results of this study indicate that infrared spectra of rocks containing white mica provide a sensitive method to monitor metamorphic intensity and depth of burial in the transition from high-grade diagenesis to low-grade metamorphism. These simple and rapid measurements can be performed in the field, and similar data can also be acquired from airborne and spaceborne imaging spectrometers. Although this study does not include x-ray diffraction characterization, it will be important to determine how the spectroscopic and mineral-chemical variations correlate with transformations in white mica crystal structure. Martínez-Alonso, S., Rustad, J.R., and Goetz, A.F.H. (2002) Ab initio quantum mechanical

modeling of infrared vibrational frequencies of the OH group in dioctahedral phyllosilicates. Part II: Main physical factors governing the OH vibrations. American Mineralogist, 87, 1224–1234.

Maxwell, D.T. and Hower, J. (1967) High-grade diagenesis and low-grade metamorphism of illite in the Precambrian Belt Series. American Mineralogist, 52, 843–857.

Post, J.L. and Noble, P.N. (1993) The near infrared combination band frequencies of dioctahedral smectites, micas and illites. Clays and Clay Minerals, 41, 639–644.

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CALCULATION OF THE CHEMISTRY OF MINERALS IN MIXTURES: VERIFICATION AND APPLICATION OF THE HANDLENS PROGRAM D. D. Eberl U.S. Geological Survey, 3215 Marine St., Suite E-127, Boulder, CO 80303, USA; [email protected] HandLens is a computer program, written by this author in Excel macro language, that calculates the chemistry of minerals in mineral mixtures (for example, in rocks, soils and sediments) for related samples from inputs of quantitative mineralogy and chemistry. For best results, the related samples should contain minerals having the same chemical compositions; that is, the samples should differ only in the proportions of minerals present. Concentrations of major and trace elements in the minerals are determined by solving a set of simultaneous linear equations using the Solver tool in Excel. A unique mathematical solution requires that there be at least as many samples entered into the program as there are different types of minerals in the samples. In addition, HandLens calculates the major element chemistries for each mineral. This calculation applies material and charge balance constraints to mineral compositions, and a well-constrained solution to the set of linear equations requires that there be approximately as many samples entered into the program as there are variable-composition minerals in the samples. A third type of calculation allows the measured chemistry and/or mineralogy to vary within the experimental uncertainty to refine mineral chemistries. Other program features include utilities for calculating the weight percent of elements from the weight percent of elemental oxides, and the weight percent of Si by difference when this element is missing from the analyses. Required input for HandLens includes quantitative mineralogical data, obtained, for example, by RockJock analysis of X-ray diffraction (XRD) patterns, and quantitative chemical data, obtained, for example, by X-ray florescence (XRF) analysis of the same samples. Other quantitative data, such as sample depth, temperature, surface area, also can be entered. The minerals present in the samples are selected from a list, and the program is started. The results of the calculation include: (1) a table of linear coefficients of determination (r2’s) which relate pairs of input data (for example, Si versus quartz weight percents); (2) a utility for plotting all input data, either as pairs of variables, or as sums of up to eight variables; (3) a table that presents the calculated chemical formulae for minerals in the samples; (4) a table that lists the calculated concentrations of major, minor, and trace elements in the various minerals; and (5) a table that presents chemical formulae for the minerals that have been corrected for possible systematic errors in the mineralogical and/or chemical analyses. In addition, the program contains a method for testing the assumption of constant chemistry of the minerals within a sample set. HandLens is available for downloading at: http://pubs.usgs.gov/of/2008/1244/.

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HYDROTHERMAL ALTERATION AND ORIGIN OF THE KAOLIN-ALUNITE DEPOSITS: DUVERTEPE DISTRICT, SIMAV GRABEN, TURKEY Ömer I. Ece, Bala Ekinci and Fahri Esenli

Istanbul Technical University, Faculty of Mines, Department of Geological Sciences, Mineralogy-Petrography Division, Maslak 34469 Istanbul, TURKEY; [email protected] The Simav Graben extends about 80 km long in northeastern area of Aegean region and advanced argillic alteration zones constitute for major alunite (+/- kaolin) deposits at the eastern end and kaolin (+/- alunite) deposits at the western end of the graben. The Duvertepe kaolin district is the largest hydrothermal kaolin deposit in Turkey; with the kaolin used mainly for ceramic and cement industry. The kaolin developed at the expense of Miocene rhyolitic - dacitic lavas and tuffs, through intense hydrothermal activity along tectonically active graben system, which is a part of young Aegean magmatism and N-S extentional young Aegean tectonism. Silicification, brecciation and opalization are also observed along the fault which constitutes the boundary between the Upper Cretaceous mélange and Miocene volcanics. Besides, there are many epithermal mineralizations which are situated in the silica gossans zone within the metamorphics is represented with sulfur minerals, along the graben, but none of them are economically significant. Due to the nature of hydrothermal alteration of rhyolitic tuffs and lavas, all kaolin deposits are associated with certain degrees of alunite mineralization. In order to constrain the region of alunite, it is necessary to define criteria to discriminate sulfur and origin of water in hydrothermal source system. Epithermal kaolin+alunite mineralization was the result of intense hydrothermal alteration of rhyolitic-rhyodacitic tuffs under acid-sulphate-rich geothermal solutions and these mineralization commonly occurred along small faults which cut almost vertically to the E-W trending Simav Graben. Silicification becomes more intense upward; for instance, funnel-shape silicification at the top of fault zone, silica precipitation or replacing with surrounding rocks - silica gossan - above the kaolin deposits as a result of spraying and infiltration of geothermal waters are commonly observed features in the field. Mineralogic assemblage of the Duvertepe kaolins consist of kaolinite, quartz, alunite, jarosite, goethite, dickite, plagioclase, K-feldspar, Fe-oxides and Fe hydroxides, depending on formation temperature, parent rocks and chemical compositions of ascending geothermal waters. XRD studies revealed that mineralogical composition of kaolinite (+/- alunite) deposits are consist of kaolinite (1T polytype)+alunite+quartz and alunite deposits are consist of alunite+opal-CT +quartz and minor halloysite. Si- and S-inputs along fault zones are common because they are the products of late-stage ascending products of geothermal solutions. SEM studies show that those kaolinite crystals are well-formed hexagonal shaped and alunite crystals are idiomorphic rhombohedral forms. Needle-shape and from stubby to long tubular structure with open-ends halloysites are also determined in some alunite samples. Alunite crystals generally occur as fine-crystalline pseudocubic morphology. Minor faults zones in clay quarries are rich in silica and/or alunite mineralization indicating Si- and S-inputs came through ascending geothermal systems.

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BENTONITE AND ITS IMPACT ON MODERN LIFE Don Eisenhour 1 and Richard Brown 2 1Amcol International, 2870 Forbs Avenue, Hoffman Estates, IL 60192, USA; [email protected] 2Wyo-Ben Inc., PO Box 1979, Billings, MT 59103, USA The use of bentonite dates back at least 3000 years to ancient Greece where it was mined on the island of Kimolos and distributed throughout the Mediterranean (Aristophanes 405 bc). This white Kimolian bentonite was prized for its ability to clean wool and was used as a component of soap. From the time of Aristophanes to about 1900 the uses for bentonite remained limited (Robertson 1986). However, after 1900 the applications for bentonite grew significantly. The use of bentonite in drilling fluids and in making green sand molds for metal casting began in the early 1900s. In the 1950s, the development of iron ore pelletizing created an additional high-volume market for bentonite. And, in the 1980s sodium-bentonite-based clumping cat litters were developed. All of these applications continue to grow and account for more than 70% of world wide bentonite consumption today (Eisenhour and Brown 2009). Hundreds of other applications are responsible for the remaining 30% of consumption; almost all of these have been developed in the past century. In environmental applications bentonite is used in the treatment of waste waters, for sealing bore holes and well casings, and in the manufacture of geosynthetic clay lines which are used in land fills and reclaimed mines. Acid-activated bentonites are used to clarify edible oils, as coatings on carbonless copy paper, and as catalysts in the manufacture of petroleum products. Sodium bentonites are widely used to clarify wines in the USA, Europe, and Australia. Both sodium and calcium bentonites are used in animal feeds to absorb mycotoxins. When treated with cationic surfactants, organo-bentonites are formed which are used in paints, inks, greases, cosmetics, and oil-based drilling fluids. More recently, organo-bentonites have been developed for use in polymers to increase strength, lower permeability, and improve weather resistance. Highly-purified sodium bentonites are used in a variety of cosmetics and pharmaceuticals as suspending agents and emulsion stabilizers, and in computer chip manufacturing in specialized polishing compounds. The rapid growth in the number and sophistication of bentonite applications has led to a corresponding growth and specialization in bentonite mining, testing, and processing methods. This trend shows no sign of slowing.

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DIAGENESIS OF THE CRETACEOUS MARIAS SHALE, DISTURBED BELT, MONTANA W. Crawford Elliott 1, R. Douglas Elmore 2 and Michael H. Engel 2 1Department of Geosciences, Georgia State University P.O. Box 4105 Atlanta, GA 30302-4105; [email protected] 2 School of Geology and Geophysics, College of Earth and Energy, The University of Oklahoma Norman, OK 73019 Previous studies of the Cretaceous Marias River Shale in the Disturbed Belt in NW Montana proposed that illitization occurred as a result of increased burial because of thrust loading. In addition to numerous bentonites, the unit contains limestone concretions that contain a chemical remnant magnetism (CRM) that may provide another means to date the timing of diagenetic alteration in the unit. Our results suggest a possible relationship between increased levels of thermal maturity based on organic geochemical biomarkers, acquisition of increased magnetic intensity in concretions, and increased amount of illite layers in I-S and a decrease in intra-sample variation of K-Ar ages of diagenetic I-S. The differences can be explained by higher burial in some areas than in others and are consistent with the hypothesis that thermal maturation leads to illitization which in turn can also result in the acquisition of a CRM in limestone concretions. Preliminary carbonate isotopic results, however, raise another possibility. Carbon (δ13C) and oxygen (δ18O, PDB) isotopic results are variable. Depleted δ13C values (-20 ‰) suggest the microbial oxidation of organic matter. Strontium isotopic data (87Sr/86Sr) show that concretions which contain the CRM and higher maturity indicators were altered by fluids with a radiogenic signature (0.707813 - 0.70772). A concretion with lower thermal indicators which does not contain the CRM to the east of the Disturbed Belt in relatively un-deformed rocks contains coeval Sr values (0.70727). The Sr isotope results suggest that fluid alteration could have been a factor in setting the thermal indicators and causing the formation of the CRM.

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IRON-BEARING CLAY-COATED SAND FOR WATER REMEDIATION Claire I. Fialips, Yan-Feng Zhuang, Maggie L. White, Dulce Perez Ferrandez

Newcastle University, School of Civil Engineering and Geosciences, Drummond building, Newcastle-Upon-Tyne NE1 7RU, United-Kingdom; [email protected] Laboratory scale experiments have shown that reducing iron in clay minerals can be used to promote the reductive degradation of various contaminants such as nitroaromatics and chlorinated compounds. Yet, Fe-bearing smectites are never used in permeable remediation systems, such as permeable reactive barriers (PRBs), and in situ redox manipulation has never been applied for reducing Fe-bearing minerals in PRBs. The main reason for not using clay minerals in PRBs is that clay minerals have very low permeability and that physical mixture of clay minerals with coarser materials, such as sand, lead to progressive failure of the permeable system due to the migration of the clay particles and clogging. We have developed a new Fe-bearing clay-material suitable for permeable water treatment systems, including PRBs. Fe-smectite particles were tightly attached to the surface of sand grains using polyvinyl alcohol (PVA). An optimum coating of 62 mg clay/g sand was obtained using the nontronite Nau-2 and sand of medium grain size (0.3-0.6mm). The clay-coated sand is stable to changes in pH and redox conditions and is reducible, with a maximum reduction level of 83% (Fe(II)/Fe total). Though a net decrease in CEC is observed, the coated clay retains its swelling behaviour and the clay-coated sand has a stable and suitable permeability of ~1×10-4 m/s. The reduced Fe-bearing clay-coated sand is able to reductively transform redox-sensitive contaminants, such as nitrobenzene (to aniline) and Cr6+ (to Cr3+), making it a suitable permeable reactive material for many remediation applications, including PRB systems.

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CARBOXYLATE FUNCTIONAL GROUPS MEDIATE ADHESION OF CRYPTOSPORIDIUM PARVUM ÖOCYSTS AT THE HEMATITE/WATER INTERFACE Xiaodong Gao and Jon Chorover Department of Soil, Water and Environmental Science, University of Arizona, Tucson, AZ, 85721, USA; [email protected] Cryptosporidium parvum is a protozoan pathogen that infects a wide range of hosts, including livestock and humans. Öocysts, the encysted, environmental form of this pathogen, are capable of surviving in most natural environments. Due to the threat they pose to human health, the transport and fate of öocysts in the environment has been widely studied during the past decade. However, most of the previous studies focused on examining öocyst transport at the bench scale using classical column experiments. The specific surface interaction mechanisms of öocysts with substrate minerals, in particular, the role of molecular scale chemistry of the öocysts themselves, are still poorly resolved. In this study, in situ attenuated total reflectance (ATR)-FTIR spectroscopy was employed to investigate the adhesion of öocyst cells to a ZnSe internal reflectance element (IRE) and to the same IRE coated with nanoparticulate α-Fe2O3 in aqueous systems over a wide range of solution chemistry. The ATR-FTIR spectra of öocysts on ZnSe IRE alone exhibit amide, carboxylate, phosphate, and polysaccharide functional groups. The spectra show small systematic variation with solution pH and ionic strength. Öocyst adhesion, as measured by the absorbance of the amide II band, increased with decreasing pH or increasing ionic strength due to a decrease in the electrostatic repulsive force. ATR-FTIR spectra of öocysts on the hematite surface show distinct changes in carboxylate vibrations (not observed for the uncoated ZnSe IRE) that indicate direct bonding of carboxylate groups to the hematite surface. Spectral data are consistent with R-COO-Fe bonding and provide a molecular basis for the strong positive influence of iron oxides on retardation. Furthermore, modes of complexation vary with solution chemistry. In a NaCl background, öocysts are bound to the hematite surface via both monodentate and binuclear bidentate complexes. The monodentate complex predominates at low pH, whereas a binuclear bidentate complex becomes increasingly predominant with increasing pH. In a CaCl2 background, only the binuclear bidentate complex is observed. When the solution pH is 9.0, thereby exceeding the point zero net proton charge (PZNPC) of hematite, öocysts are bound to the mineral surface via outer-sphere complexes in both CaCl2 and NaCl background electrolytes. These results provide important molecular scale information on öocyst adhesion and have important implications with respect to prediction of öocyst transport and fate in Fe-rich variable-charged soils.

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BARRIER PEFORMANCE OF BENTONITE TO HYPER-ALKALINE CONDITIONS Will P. Gates 1, Craig H. Benson 2 and Peter Hines 3 1SmecTech Research Consulting, Morrabbin, Victoria, Australia [email protected]; and Monash University, Clayton, Victoria Australia. 2Chairman and A.H. Fuller Distinguished Chair, Dept. of Civil and Environmental Engineering, University of Washington, Seattle, Washington, USA. 3Australian Key Centre for Microscopy and Microanalysis, The University of Sydney, Sydney, New South Wales, Australia. Recently, many mining industries have been interested in the possibilities of geosynthetic clay liners (GCLs) as components of replacements for traditional compacted clay liners. GCLs are made up of a thin (generally 10 mm) layer of natural or activated sodium bentonite physically contained between two layers of geotextile. Typically one layer of geotextile is woven and the other nonwoven; the whole geosynthetic composite is held together by needling the nonwoven fibers through the bentonite and into the woven geotextile, where they are fixed by heat. Bentonites are thus the hydraulic barrier in GCLs. Mineral processing liquors often have extreme pH values, ranging from very acidic (pH< 2) to very alkaline (pH >12) and nearly all of these liquors and leachates have elevated ionic strength. The need for improved understanding of the reactions of sodium bentonites to leachates having extreme pH values is needed to better engineer cost-effective environmental barriers with useful service lifetimes. GCL ‘biscuits’ were loaded into triaxial cells and subjected to either deionized water (as baseline) or to 1 M NaOH (plus 1.3 mM CsCl) to determine the effect of leachate pH on the hydraulic conductivity of the GCL. Following permeation, the GCLs were sectioned and examined using scanning electron microscopy (SEM). Sodium bentonite used in the GCL was also subjected to 1 M solutions of NaOH in batch studies at 20-25 oC for up to one year to follow alkaline induced changes to the bentonite mineralogy. The permeability of GCLs to 1 M NaOH was greater compared to that in deionized water, but the ratio of the coefficients of hydraulic conductivity, KNaOH/KDI, increased by ~4 times, but the longer running replications clearly showed a leveling off and then a decrease of KNaOH after 6-8 pore volumes of flow. Elution with NaOH also increased the effective sodicity of the bentonite, as observed by the release of bound K, Ca, and Mg. SEM images provided evidence of the formation of a non smectite aluminosilicate mineral phase responsible for pore-filling. Batch dissolution studies revealed that the main components of the bentonite (quartz, feldspars and opaline silica, as well as smectite) were subject to differential dissolution and with time, new phases were produced. These new phases were identified by X-ray powder diffraction, thermal analysis, and infrared spectroscopy as hydrous forms of sodium aluminium silicate (SAS) and alumohydrocalcite (AHC), as well as trona-like (T) and vaugnitite-like (V) phases. X-ray absorption spectroscopy revealed a decrease in tetrahedral Al of about 25% after 6 months reaction, compared to non reacted bentonite, indicating that smectite is likely the dominant source of Al for the pore-filling phases identified in the post NaOH elution GCLs. Part of this research was undertaken on beamline 14ID-01 at the Australian Synchrotron, Victoria Australia. The views expressed are those of the authors and not necessarily those of the owner or operator of the Australian Synchrotron. Wholly funded by ELCO Solutions Pty Ltd (Queensland) and Geofabrics Australasia, Pty Ltd (Victoria).

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CURRENT STATE OF SITE OCCUPANCY BY IRON IN SMECTITES Will P. Gates SmecTech Research Consulting, Morrabbin, Victoria, Australia [email protected] ; and Monash University, Clayton, Victoria Australia Smectite is an important industrial mineral, traditionally serving as components in drilling muds, as catalysts and catalyst supports for petro-chemical cracking, as sorbents for a variety of chemicals, as carriers for agrichemicals and as hydraulic barriers, but also more recently as an integral part of nanotechnology. Because the chemical identity of various substitutions within the crystallite lattice controls the surface properties of smectites, an understanding of the site occupancies should serve to improve control of industrial applications. This paper will briefly review the results of several research groups on the current state of understanding of site occupancy by iron in the octahedral and tetrahedral sheets of nontronites, ferruginous smectites and montmorillonites. Application of synchrotron based X-ray absorption spectroscopy has permitted re-assessment of assignments of iron in tetrahedral and octahedral sheets in nontronites and new approaches using Mössbauer and infrared spectroscopy to samples have contributed to a greater understanding of the distribution of iron and other metals within neighboring octahedral sites of smectites in general. For example, the lower limit of total iron content at which Fe3+ appears to fill tetrahedral sites corresponds to the nontronite - ferruginous smectite join (Gates et al., 2002). The available evidence suggests that iron occupies indifferently cis and trans sites in cis vacant varieties, and this results in considerable broadening of the quadrupole splitting as measured by Mössbauer (Cashion et al., 2008), especially in ferruginous smectites with considerable octahedral Mg (Gates, 2008). Iron within the octahedral sheets of Otay type montmorillonite is clustered, whereas iron atoms are isolated octahedral in Wyoming type montmorillonite (Vantelon et al., 2003). In combination with new synthesis methods which promise to provide greater control over smectite chemistry (Deacarreau et al., 2008), these spectroscopic techniques promise to offer more definitive interpretations and site occupancy assignments in these important minerals. Cashion JD, Gates WP, Thomson A. (2008) Mössbauer and IR study of of iron sites in

four ferruginous smectites. Clay Minerals, 43, 83-93. Decarreau A, Petit S, Martin F., Farges, F, Viellard P, Jousein E. (2008) Hydrothermal

synthesis, between 75 and 150 oC, of high-charge ferric nontronites. Clays and Clay Minerals, 56, 322-337.

Gates WP. (2008) Cation mass – valence sum (CM-VS) approach to assigning OH-bending bands in dioctahedral smectites. Clays and Clay Minerals. 56, 10-22.

Gates WP, Slade PG, Lanson B, Manceau A. (2002) Site occupancy by Fe in nontronite. Clays and Clay Minerals, 50, 223-239.

Vantelon D, Montarges-Pelletier E, Michot LJ, Briois V, Pelletier M, Thomas F. (2003) Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study. Physical Chemistry of Minerals, 30, 44–53.

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THE BENTONITE PUZZLE: A STABLE ISOTOPE AND GEOCHEMICAL PERSPECTIVE H. Albert Gilg 1 and Alexander Rocholl 2

1Engineering Geology, TUM, 80333 Munich, Germany; [email protected] 2Dept. of Earth and Environmental Sciences, LMU München, 80333 Munich, Germany Bentonite deposits form by alteration of intermediate to acidic glassy volcaniclastic rocks to smectite either in a proximal volcanic or a distal sedimentary environment. The mechanisms of bentonite formation in such distinct geological settings are still disputed. It is generally agreed that large water-rock ratios, near neutral pH conditions, and major chemical reorganization, e.g. mobilization of alkaline and earth alkaline elements and silica, are required to form significant deposits. However, the temperatures and timescales of smectite formation, the source and composition of involved fluids, the architecture of the hydrological system, and the role of protolith composition on the type of smectite are still poorly understood. We discuss some of these issues on the basis of new and published stable isotope and selected geochemical data by focusing on German (distal) and Greek (proximal) bentonite deposits. We show that both the temperature of bentonite genesis and the origin of the involved fluids, i.e. meteoric versus seawater, can be derived from combined oxygen and hydrogen isotope data measured on smectites. These clay minerals retain their original isotopic signature if not subjected to deep burial (>80°C), while associated residual volcanic glasses may adjust their H-O-isotopic signature to changes in pore water isotope composition even at ambient temperatures. Isotopic data demonstrate that, in most cases, bentonite formation took place on land, even if the tuffs had been originally deposited in a marine environment. The exchangeable interlayer cation composition of smectites can also be related to source of fluids responsible for the conversion of glass to smectite. Hydrothermal processes in bentonite formation with temperatures exceeding 40°C have rarely been documented, e.g. in case of the thick proximal deposits of Milos. Here, extensive bentonite formation took place in less than 2 million years. Deciphering the type of the volcanic protolith is problematic if alteration is advanced and no original glass remains. Immobile trace element ratios, such as Zr/Ti or Nb/Y, of bulk bentonite samples have often been used to characterize the protolith in such cases. We show here that this approach introduces serious errors in case of distal deposits, if minerals derived from the sedimentary environment contaminated the epiclastic accumulation of air-fall ash. Furthermore, new EMPA and LA-ICP-MS data on residual glass shards from Bavarian bentonite deposits reveals that Al, Ti, and Fe do not fractionate as glass is converted to smectite.

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SOURCE AND ORIGIN OF SEDIMENTARY KAOLIN DEPOSITS IN EGYPT H. Baioumy 1, H. A. Gilg 1, E. Hegner 2, S. Hölzl 3, H. Taubald 4 and L. N. Warr 5

1Lehrstuhl für Ingenieurgeologie, TUM, 80333 Munich, Germany; [email protected] 2Department of Earth Sciences, LMU München, Munich, Germany 3Bayerische Staatssammlung für Paläontologie und Geologie, Munich, Germany

4Lehrstuhl für Geochemie, Univ. Tübingen, Tübingen, Germany 5Institut für Geographie und Geologie, Ernst-Moritz-Arndt Univ., Greifswald, Germany Cretaceous continental sedimentary kaolin deposits of economic significance occur in the Sinai, Red Sea and Aswan regions in Egypt, while Carboniferous sedimentary kaolins are present only in the Sinai. We present a combined mineralogical, geochemical and Pb-Sr-Nd isotope study on the kaolins to better understand the origin and sources of these clays. The Cretaceous kaolins share some geochemical characteristics, such as high TiO2 (1.3-3.8 wt.%), Zr (450-1500 ppm), Nb (50-190 ppm), and Cr (88-1300 ppm) contents in the clay fraction, that distinguish them from sedimentary kaolins in other parts of the world. High Zr, Hf, Nb, Ta, Cr, and V contents are associated mainly to anatase, while Sr, Pb, and REE are hosted by clay-sized aluminum phosphate minerals. The presence of Y- and P-bearing 30-nm-sized zircons is confirmed by TEM studies. The 206Pb/204Pb (18.67-19.13), 208Pb/204Pb (38.76-39.30), 87Sr/86Sr ratios (0.7072-0.7085), and εNd values (-3.2 to -1.2) recalculated at the time of sedimentation are uniform. They represent a well-homogenized isotopic signature of the weathering crusts of the juvenile Arabian Nubian Shield. The unique pisolitic flint clays at Kalabsha, Aswan area, were formed by deferration and resilicification of lateritic sediments, as indicated by low trace element contents, LREE depletion, positive Ce anomaly, geochemical homogeneity, and unusually high kaolinite crystallinity (Hinckley Index > 1.0). The overlying plastic kaolins were not formed by reworking of the pisolitic kaolins, but probably derived from the saprolites underlying the lateritic crusts in the source area. The Carboniferous kaolin deposits are mineralogically and geochemically diverse. The Khaboba and Hasbar deposits are characterized by the presence of illitic material and alunite in veins and disseminations. The clays are characterized by lower Zr, Nb, and Ti contents, higher initial 87Sr/86Sr (0.7095-0.7125) and lower εNd(300 Ma) values (-9.3 to -7.9), but similar initial Pb isotope ratios, as compared to the adjacent Cretaceous kaolins indicating a chemically different and older local crustal source. A Carboniferous kaolin sample from Abu Natash shows the lowest Nb (40 ppm) and Zr contents (200 ppm), but high TiO2 (3.1 wt.%), Cr (360 ppm), and very high Pb (150 ppm) concentrations. The initial 87Sr/86Sr ratio (0.7077) is low, and εNd(300 Ma) high (+1.0). The clay fractions from relictic saprolites on metasediments of the crystalline basement at Wadi Khaboba and Wadi Abu Natash have similarly distinct Sr isotope compositions as the adjacent Carboniferous sedimentary kaolins.

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SMECTITE CONTENT OF CRUSHED BASALTIC AGGREGATE: ROCK RESPONSE TO DMSO ACCELERATED WEATHERING TEST J. Reed Glasmann Willamette Geological Service, 31191 Peterson Rd, Philomath, OR; [email protected] Crushed basaltic aggregate from 12 locations scattered across Oregon, Washington, and western Idaho was studied in order to determine variations in petrographic character, rock texture, and extent of alteration, with the goal of carefully quantifying total swelling clay content. Crushed aggregate from each quarry contains a swelling clay component, typically nontronite, with amounts ranging from <6% in relatively fresh subaerial flows of Columbia River basalt to approximately 40% in severely altered Eocene sea floor pillow basalts. In many instances, total swelling clay content in excess of 15% results in moderate to high DMSO Loss (20-60% loss). However, a group of closely related Columbia River Basalts with intermediate total clay content (15-17%) yielded lower than anticipated DMSO Loss (5-10% DMSO Loss). Significant variations in basalt microfabric occur as clay content increases over the range of 10-20%. As clay content increases, the potential for continuous zones of pseudomorphous clay replacement increases, providing discrete zones of weakness in affected aggregates that are susceptible to spalling upon exposure to DMSO. In rocks with well-developed 3-dimensional crystal intergrowths (e.g., Esmond Creek diorite), higher clay content may be required to weaken the strong micrographic texture of quartz and feldspar. Although the results of several important engineering tests show poor correlation to DMSO Loss, the correlation of several indexes of aggregate stability is significantly improved when plotted against total clay content determined by a combination of XRD and petrographic techniques. The DMSO test provides a reasonable estimation of rock durability in various road bed applications where smectitic clays are a primary factor in aggregate stability.

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APPLICATION OF QUANTITATIVE CLAY MINERALOGY IN DEVELOPING PREDICTIVE NIR MODELS FOR ANALYSIS OF GANGUE MINERALS ON CONVEYORS Alexander F. H. Goetz, Brian Curtiss, Daniel A. Shiley ASD Inc., 2555 55th St., Boulder, Colorado 80301; [email protected] Near Infrared (NIR) reflectance spectroscopy is being used increasingly as a laboratory technique to supplement XRD analysis and other measurements of blast hole cuttings for ore processing decision making. The advantage of the technique is the speed of measurement and no need for sample preparation. NIR is a surface measurement that responds to transition element, electronic transitions and molecular vibrational transitions in crystal lattices. The constituents of a sample are quantified by statistical techniques to create predictive models by regression against primary sample analyses through XRD, XRF and CEC (Goetz et al., 2009). The quality of the models is directly related to the quantitative primary technique. In heap leach, copper metallurgical processing the abundance of phyllosilicates, in particular muscovite, biotite, chlorite, pyrophyllite and clays kaolinite, illite and smectite are important in defining the ultimate permeability of the leach pile. Experience has shown that the quantitative results for clays vary widely among commercial laboratories and, if NIR techniques are to succeed, higher quality, consistent results are required We have developed predictive models for concentrations of swelling clays, kaolinite, muscovite and biotite from conveyor samples of materials from a copper mine using a QS 8000 over-the-conveyor system. The results are promising and potentially useful for making ore processing decisions. Goetz, A.F.H., et al. Rapid gangue mineral concentration measurement over conveyors

by NIR ... Miner.Eng. (2009), doi:10.1016/j.mineng.2008.12.013, in press.

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ADSORPTION OF ISOXAFLUTOLE DEGRADATES TO HYDROUS METAL OXIDES Keith W. Goyne 1, Si-Hyun Wu 1, Robert N. Lerch 2, and Chung-Ho Lin 3

1Department of Soil, Environmental and Atmospheric Sciences, University of Missouri, 302 ABNR Bldg., Columbia, MO 65211, USA; [email protected] 2U.S.D.A, Agricultural Research Service, Cropping Systems and Water Quality Research Unit, University of Missouri, 265 Ag. Eng. Bldg., Columbia, MO 65211 3Center for Agroforestry, University of Missouri, 203G ABNR Bldg., Columbia, MO 65211 Isoxaflutole (IXF) is a pre-emergence herbicide that is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application. Subsequently, DKN can be degraded to benzoic acid derivative (BA) within soil. Due to their anionic nature in the pH range of natural waters and longer half lives (t1/2), DKN and BA are more prone to migration through soil to water resources than IXF. However, very little research has been conducted to investigate DKN and BA sorption to soil minerals. The primary objective of this research is to determine if DNA and BA are readily adsorbed by variable charged minerals and to elucidate the mechanism(s) through which DKN or BA interact with variable charged mineral surfaces. The IXF degradates were adsorbed by hydrous aluminum and iron oxides (HAO and HFO, respectively), and slight hysteresis is observed between the adsorption and desorption isotherms of DKN reacted with HAO. Adsorption and desorption isotherms were generally well-fitted by the Freundlich isotherm model (r2 ≥ 0.87). Adsorption edge diagrams show a dramatic decrease in DKN and BA adsorption between pH 4 to 5 and adsorbed amounts continue to decrease, although more gradually, as pH is further increased. Presumably, this can be attributed to unfavorable electrostatic interactions between the IXF degradates and dissociated surface functional groups on the mineral surface at higher pH values. Diffuse reflectance Fourier transformed infrared (DRIFT) spectra and attenuated total reflectance Fourier transformed infrared (ATR-FTIR) spectra suggest that DKN and BA interact with the mineral surfaces through weak outer-sphere complexes, as no major shifts in spectra features are noted. This study demonstrates that DKN and BA can be adsorbed onto the surfaces of HAO and HFO and the IXF degradates interact with HAO and HFO via electrostatic outer-sphere complexes.

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QUANTITATIVE MINERALOGY OF FINE-GRAINED SEDIMENTARY ROCKS: AN EXAMPLE FROM THE MANCOS SHALE AND A PRELIMINARY LOOK AT QEMSCAN® Richard I. Grauch 1 and D. D. Eberl 2

1US Geological Survey, Denver Federal Center, MS 973, Denver, CO 80225. [email protected] 2US Geological Survey, 3215 Marine Street, Suite E-127, Boulder, CO 80303 Quantitative mineralogical data are required for a variety of purposes including rock classification, understanding rock genesis, and geochemical modeling. Obtaining those data and verifying their accuracy is difficult, especially for fine-grained rocks. We report on a comparison between two methods for the determination of quantitative mineralogy and compare their results to traditional chemical tests used to quantify mineralogy: a grain by grain elemental analysis based on the use of an automated scanning electron microscope (QEMSCAN®) and a spectral method utilizing X-ray diffraction (RockJock). 27 samples of 2¼ inch drill core of Mancos Shale representing a range between inhomogeneous and relatively homogenous material taken from quarter sections of 1 to 3 inch long intervals of core were examined. A thin-section billet was cut from the sample and the remainder was powdered and used for chemical and X-ray diffraction analyses. The thin-section billet was used for a polished thin section and the remainder as a polished mount for QEMSCAN® analysis. Optimum QEMSCAN® conditions were determined by repeated modal analyses of the same 9 mm2 area using different pixel spacing. The results demonstrate good precision and the practicality of using short analytical times. Those results compare well, despite some sample heterogeneity, with analyses of a larger portion, ~ 250 mm2, of the same sample. Although the Species Identification Protocol (SIP) used for correlating individual grain chemistry to a specific mineral yields a similar mineral list to that observed from non-quantitative optical petrography and SEM examination of the polished thin section, it requires some modification to reflect the true mineralogy of the samples. The “K Al Silicates” mineral category is a chemical category for volumes of analysis that contain grains too small to be resolved. Modal analyses were used to construct a mineralogic/stratigraphic sequence with lithologic breaks which is in general agreement with megascopic core logging. Comparing QEMSCAN® modal analyses of small volumes (even over large portions of a thin section) to quantitative mineralogy or chemistry of the powders is, at best, an approximation. However, that approach may be the best way to independently test the validity of the modal analyses. QEMSCAN® and RockJock values of modal carbonate-bearing phases compare very well with the chemically determined carbonate content of the rocks, r2 = 0.86 and 0.98, respectively. Differences between RockJock and QEMSCAN® may be explained by the heterogeneity of the samples, but the correlation between total carbonate minerals determined by the two methods is good, r2 = 0.82. Direct comparison of quartz content determined by both methods yields a fairly good correlation (r2 = 0.82, 2 extremes excluded) but very different values, suggesting that QEMSCAN® missed some quartz. The missing quartz may be in the general category of “K Al Silicate” or possibly in the Micrite category.

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LAYER-BY-LAYER ASSEMBLY OF MULTIFUNCTIONAL CLAY-POLYMER THIN FILMS Jaime C. Grunlan 1,2, Daniel Gamboa

1, Woo-Sik Jang 1, Yu-Chin Li 2, Morgan A. Priolo

2, Ian Rawson

1 and Jessica Schulz 1 1Department of Mechanical Engineering, 3123 – Texas A&M University, College Station, TX 77843-3123, USA; [email protected] 2Materials Science and Engineering Program, 3003 – Texas A&M University, College Station, TX 77843-3003, USA A variety of functional thin films can be produced using layer-by-layer (LbL) assembly. Thin films ( < 1µm) are created by alternately exposing a substrate to positively- and negatively-charged molecules or particles in water. This deposition process is repeated until the desired number of “bilayers” (or cationic-anionic pairs) is achieved. Films made with anionic clay and cationic polyacrylamide, have a nano-brick wall structure. Film growth is measured using ellipsometry and a quartz crystal microbalance. Thirty bilayers of clay and polymer result in a 570 nm thick film with > 90% transparency and an oxygen transmission rate below 0.005 cm3/m2day. These films also have a relatively high dielectric constant (> 10) and they are able to render foam anti-flammable. All of the properties of these thin films can be tailored by altering pH, concentration, and ionic strength of deposition mixtures, along with varying the type of polycation.

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CARBON BLACK HALOING OF CLAY AND ITS INFLUENCE ON ELECTRICAL AND MECHANICAL PROPERTIES OF EPOXY COMPOSITES Jaime C. Grunlan 1,2, Krishna Etika 2, Lance Hess 1 and Lei Liu 2 1Department of Mechanical Engineering, 3123 – Texas A&M University, College Station, TX 77843-3123, USA; [email protected] 2Materials Science and Engineering Program, 3003 – Texas A&M University, College Station, TX 77843-3003, USA Studies of acetone-based suspensions suggest a synergistic stabilization of clay by carbon black (CB) that involves a haloing effect. This unique microstructural development ultimately influences the electrical and mechanical properties of epoxy composites that contain both particles. With the addition of 0.5 wt% clay, electrical conductivity increases by an order of magnitude for CB-filled epoxy (relative to composites containing no clay), but no significant improvement is observed in storage modulus. Composites containing equal concentrations of CB and clay show reduced electrical conductivity, but significant improvement in storage modulus. Both electrical conductivity and storage modulus improve in composites containing a 1:2 clay:CB (wt/wt) ratio. This synergy between CB and clay is a useful tool for simultaneously improving the electrical and mechanical properties of solution processed composites.

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CLAY AS RIGID SURFACTANT FOR DISPERSION OF CARBON NANOTUBES IN POLYMER Jaime C. Grunlan 1,2, Krishna Etika 2, Lance Hess 1 and Lei Liu 2 1Department of Mechanical Engineering, 3123 – Texas A&M University, College Station, TX 77843-3123, USA; [email protected] 2Materials Science and Engineering Program, 3003 – Texas A&M University, College Station, TX 77843-3003, USA Carbon nanofillers, such as nanotubes, nanofibers and carbon black, are electrically conductive and useful for improving polymer properties. Carbon black-filled polymers are widely used in industrial applications due to their cost advantage over other fillers. In this study, clay was incorporated into carbon black filled epoxy to simultaneously increase electrical and mechanical properties. A composite containing 2.5 wt% carbon black has an electrical conductivity on the order of 10-6 S/cm. With the addition of 0.5 wt% clay, conductivity increases by an order of magnitude, but no significant improvement was observed for storage modulus. Composites containing equal amounts of carbon black and clay showed significant improvement in storage modulus as compared to those containing an equivalent amount of only one type of filler. Studies of liquid suspensions were performed to investigate the dispersion state of carbon black and clay prior to composite formation. Suspensions containing carbon black and clay showed superior stabilization to those containing only clay or carbon black alone in acetone. These results indicate an interaction between carbon black and clay that influences the dispersion of carbon black in epoxy. Moreover, clay may impart other properties, such as flame retardancy and gas barrier that will make these composites useful for a wide variety of applications.

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ANTI-FLAMMABLE and FOIL REPLACEMENT TECHNOLOGIES BASED UPON CLAY-CONTAINING THIN FILMS: EFFORTS TO OBTAIN SPONSORSHIP AND/OR PARTNERSHIPS FOR COMMERCIAL DEVELOPMENT Jaime C. Grunlan 1,2,3

1Department of Mechanical Engineering, 3123 – Texas A&M University, College Station, TX 77843-3123, USA; [email protected] 2Department of Chemical Engineering, 3122 – Texas A&M University, College Station, TX 77843-3122, USA 3Materials Science and Engineering Program, 3003 – Texas A&M University, College Station, TX 77843-3003, USA Some anecdotal information will be presented in terms of patenting and attracting investment interest from potential industrial partners for commercializing layer-by-layer technology developed in my laboratory. The benefits and challenges associated with both of these practices will be described. The experiences are focused specifically on a technology known as layer-by-layer (LbL) assembly. In this case, thin films ( < 1µm) are created by alternately exposing a substrate to positively- and negatively-charged molecules or particles in water. This deposition process is repeated until the desired number of “bilayers” (or cationic-anionic pairs) is achieved. Films made with anionic clay and cationic polyacrylamide, have a nano brick wall structure. Film growth is measured using ellipsometry and a quartz crystal microbalance. Thirty bilayers of clay and polymer result in a 570 nm thick film with > 90% transparency and an oxygen transmission rate below 0.005 cm3/m2day, making this a potential “foil replacement” material for food and flexible electronics packaging. These films also have a relatively high dielectric constant (> 10) and they are able to render foam anti-flammable. All of the properties of these thin films can be tailored by altering pH, concentration, and ionic strength of deposition mixtures, along with varying the type of polycation. It is the thin, conformable nature of these coatings, paired with their unique properties that make them very interesting for a variety of commercial applications.

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CONVERSION OF ANIONIC CLAYS TO CATIONIC CLAYS Necip Guven Center for Nanophase, IEIS – Texas State University, San Marcos, Texas 78666; [email protected] Cationic clays such as smectites and anionic clays such as layered double hydroxides (LDH) are rather unusual layered nanoparticles displaying highly reactive surfaces. “Cationic” and “anionic” clays often complement each other as solid acids and bases. Together they cover a wide range of catalysts and catalyst supports in organic reactions of interest to petroleum industry. Synthesis of cationic and anionic clays offers a very promising adventure to discover new materials. LDH is a reactive nanofiller; organically modified LDH’s (organo-LDH) can be used for making polymer nanocomposites, especially polymers with acidic functional groups. Anionic clays have rather similar morphological features as the smectites; they appear in the form of thin platelets and crumbled foils. The charge deficiency in the octahedral sheets is balanced by the anions or anion complexes (An−

x/n) between the octahedral sheets occupied by M 2+

and M 3+ cations.

A large group of synthetic and natural compounds known as anionic “clays” can be represented by the chemical formula: [M 2+

1-x M 3+x (OH)2 ] x+ [An−

x/n · mH2O] x− brucite-like layer interlayer anion-water Theoretically the anionic complexes An−

x/n can be exchanged by monomers or dimers of silicate anions such as SiO(OH)-

3 and Si2O3(OH)2-4.

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INVENTIONS TO BENEFIT MANKIND AND MAKE MONEY Richard W. Helfrich Alameda Advisors Inc., Pleasanton, CA, [email protected] Scientists and Engineers worldwide produce many thousands of inventions every year. It is estimated that 5% of these inventions can benefit mankind and make a profit within a few years. While the US is one of the better at converting inventions to products, several studies estimate that about 0.1% of inventions are actually converted to commercial products. Most useful inventions result in reports on some shelf. Many recent inventions now involve multiple sciences and engineering and that makes commercialization more challenging. Inventing and commercializing inventions requires multiple skill sets, personality types, global connections, and sources of capital that rarely reside in a single person or even a few individuals. History shows that great teams of people with differing skills along with revolutionary inventions and know-how have achieved a better rate of success. In 2009 the world of capital and commercialization is undergoing major changes due to global economic conditions, increased competition and reduced levels of risk capital. While these issues increase the challenges of commercialization, the rewards to mankind, inventors, entrepreneurs and investors will likely be greater than most periods in the past. Navigating the commercialization process requires both experience and a willingness to adjust to dynamic market and financial forces. Selecting the best course depends on market sector, technology and regional factors. An unbiased and knowledgeable approach that adapts to each specific case has been used by experienced venture investors to enhance the probability of success. Some typical issues that should be addressed including "101 Questions" for entrepreneurs to prepare for investors are in the resources at http://www.alamedaai.com/resources.html.

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BENEFITS OF MICROPOROUS CERAMIC MEDIA IN BRICKS Marc A. Herpfer Oil-Dri Innovation Center, 777 Forest Edge Drive, Vernon Hills, IL 60061; [email protected] Physical and thermal processing of minerals to make structural bricks is well known in the art, but a new granular microporous ceramic media (MCM) added up to 15 wt% provides unique performance and significant economic benefits during the forming, drying and firing stages. The brick industry produces a wide variety of products to satisfy the marketplace, but the high costs associated with production breakage, stringent specifications, energy, and better feed preparation have economically forced usage of higher quality raw materials. Bricks are made from combinations of malleable common clays, fine-sized minerals, colorants, and coarser rigid grog filler that allow sufficient plasticity for both ease of forming yet rapid heating of the matrix. The raw mass is extruded through a shaping die and cut to dimensions. The “green-body” is then stacked, dried and fired in a kiln to generate the brick product. The ideal materials have different vitrification points that make it possible to heat and cool the ceramic body to a “steel-hard” state without extensive distortion and cracking. Manufacturers have survived because of such practices, but their many different formulations yield a wide range of physical properties related to plasticity, compressive strength, shrinkage, vitrification temperatures, and fired colors that production must handle. Unlike typical grogs such as crushed waste bricks or local sediments, this unique MCM functions as a non-slaking “aluminosilicate sponge” by leveraging internal porosity to deliver its benefits. This thermally-modified montmorillonite-based granular additive is stable at temperatures up to 1200°C, and its structure contains enormous amounts of porosity interconnected via networks of capillary channels or pathways. MCM shows minimal collapse of microstructure during subsequent rewetting, extrusion, or reheating. These features provide multiple benefits for brick-making including: precise control of “effective” moisture during extrusion; increasing dehydration rates; and controlling volatiles degassing, minimizing bloating and increasing “carbon burnout” during kiln firing. To avoid explosive release of volatile gases such as water, carbon dioxide and organics compounds into the atmosphere, manufacturers monitor both dehydration and firing to ensure a gradual degassing without rupturing the brick-body. Adding <15% MCM into the matrix enhances degassing and modulates pressure release because such gases now diffuse more uniformly throughout the network of pores and capillaries until released in a controlled fashion to the brick’s exterior. Additionally, MCM improves brick uniformity (by reducing dimensional shrinkage and warping) and enhances their quality (by minimizing cooling cracks and deformation breakage) as a result of increasing the compressive green-strength of intermediary wet and dried bricks and their fired modulus of rupture. Beyond these physical process and product benefits, MCM yields lighter weight (lower bulk density) bricks while maintaining dimensional specifications. Hence, a plant can either consume less energy per unit volume, or use the same amount of fuel and increase its production capacity (since heating less mass to a specified temperature needs less energy). A final economic “transportation bonus” results from lighter weight bricks since more can be shipped per truckload while staying under the legal weight limits of the vehicle.

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CRYSTAL GROWTH HISTORY OF QUARTZ IN THE ORDOVICIAN MILLBRIG K-BENTONITE Warren D. Huff and Funda O. Inanli Department of Geology, University of Cincinnati, Cincinnati, OH 45221, USA [email protected] Crystal size distribution (CSD) analysis has been applied to quartz crystals of the Ordovician Millbrig K-bentonite, which represents one of the largest known fallout ash deposits in the Phanerozoic Era, to establish crystal growth histories and conditions in the magma chamber prior to eruption. Specific CSDs of the quartz crystals of the Millbrig K-bentonite were examined to establish their growth conditions prior to the eruption. On the crystal size distribution plot, all Millbrig samples exhibit concave-down shapes in agreement with previously reported CSDs on large silicic systems (e.g. Bindeman, 2003) but in contrast to more mafic systems characterized by linear CSDs. Crystal growth mechanisms responsible for the concave down CSDs are thought to be surface-controlled crystal growth followed by a episode of textural coarsening. Although all samples follow concave-down shapes, two samples (AL 14-1, GA:DD:2-2) exhibit rather different CSD shapes. These findings appear to fingerprint a separate magma batch with different crystal growth conditions. These ash beds appear to be a product of a series of separate eruptions that represent separate magma layers or batches, each with slightly different crystal growth conditions. Haynes (1994) examined the internal stratigraphy of the Millbrig and reported that the bed is composed of several distinct layers of altered ash. Haynes (1994) interpreted the multiple ash layers as either a product of several periods of eruptive activity or the cumulative effect of an evolving magma chamber during a single massive eruptive event. Our data support the model of several periods of eruptive activity that was closely spaced in time. The two of the eight Millbrig samples must have come from an earlier phase eruption and are part of a basal section that have not been preserved in the stratigraphic record and lacks lateral continuity in distal parts of the deposits. The other six samples are better sorted, characterized by narrower CSDs, which suggest that they might have originated from a separate magma batch. Therefore, the multiple ash beds in the Millbrig must have been a product of series of separate eruptions that represent separate magma layers or batches that had different crystal growth conditions. Although conclusions on crystallization processes and the origin of deposits cannot be drawn from CSD shapes alone, it is shown here that CSDs of a fallout ash deposits can be used to fingerprint separate magma batches, provide valuable information on crystal growth rates as well as nature of the crystal growth mechanisms of quartz crystals. Bindeman, I.N. (2003). Crystal sizes in evolving silicic magma chambers. Geology, v.

31, p. 367-370. Haynes, J. (1994). The Ordovician Deicke and Millbrig K-bentonite beds of Cincinnati

Arch and the Southern Valley and Ridge Province. Geol. Soc. Am Spec. Pap. 290, 1-80.

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SIDEROPHORE-LEAD MUTUAL SORPTION IN THE INTERLAYER OF Na-SATURATED MONTMORILLONITE Erin Hunter, Andrew N. Quicksall, Elizabeth Haack, Ashok Patra and Patricia Maurice Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556, USA; [email protected] Lead is a widespread contaminant whose fate and transport are affected by sorption to clays and clay minerals. One factor that can affect the sorption of Pb and other high charge density metals to clays is the presence of siderophores. Siderophores are low molecular weight organic ligands produced by many aerobic organisms and graminaceous plants to acquire nutrient Fe. Siderophores also have high binding affinities for many metals such as Pb and Cd as well as U and Pt. In previous work, our group investigated the sorption of the trihydroxamate siderophore desferrioxamine B (DFOB) to montmorillonite, demonstrating that DFOB absorbs in the interlayer region. In the work described here, we expanded this work to investigate how Pb and DFOB affect each other’s sorption. We found that Pb sorption to Na-saturated montmorillonite was enhanced in the presence of DFOB across the pH range from 3 to 7.5. For example, DFOB enhanced sorption of Pb at pH 4 and 5.5 from only trace sorption to 0.08 and more than 0.1 µmol Pb m-2, respectively. XRD analysis conducted both on air-dried samples and following desiccation (approximately zero relative humidity) were consistent with DFOB absorption in the interlayer. Desiccated samples containing just DFOB (without Pb) yielded a single d-spacing near 13.35 Å. Samples containing both lead and DFOB at pH 3 yielded a single d-spacing near 13.35Å, whereas two spacings were present (~13.57Å and ~16.51Å) at pH 5.5 and 7.5 when both Pb and DFOB were present. We are currently applying Fourier transform infrared spectroscopy and synchrotron-based X-ray absorbance spectroscopy to discern the mechanisms of Pb and DFOB sorption as a function of pH.

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AFLATOXIN B1 ADSORPTION TO CLAYS: pH, UV, and IR SPECTRA William F. Jaynes and Richard E Zartman Plant and Soil Science Department, Texas Tech University, Plant Science Bldg, Lubbock, Texas 79409-2122, USA; [email protected] Aflatoxins are chemical compounds produced by Aspergillus fungi in crops, such as corn and peanuts, which are toxic and carcinogenic to animals and humans. Clay minerals, such as montmorillonite, used as feed additives (<2% by weight) reduce aflatoxicosis in animals caused by contaminated feed. Animal feeding studies have shown that some feed additives are more effective than others. Less expensive methods are needed to identify effective clay additives. Previous research has shown that low-charge clays more effectively adsorb aflatoxin B1 (AfB1) from corn meal than high-charge clays and that surface modification and charge reduction can increase adsorption. Aflatoxins have dicarbonyls that should exhibit keto-enol tautomerism. Acidic or alkaline pHs catalyze conversion of keto (C=O) into enol (COH) tautomer, and one tautomer might adsorb to clays more effectively. Hence, pH might affect AfB1 adsorption to clays. In this study, AfB1 adsorption to clays was measured using batch adsorption isotherms. AfB1 concentrations were measured using enzyme-linked immunoassay (ELISA) and ultraviolet/visible absorption (UV) techniques. Infrared spectra (FTIR-ATR) of clay/AfB1 were collected to examine aflatoxin binding to clays. Aqueous AfB1 UV-spectra indicate that acidic and alkaline pHs change AfB1 into the enol tautomer. UV spectra of AfB1-treated montmorillonite dried on quartz slides were used to confirm AfB1 adsorption. Infrared spectra indicate AfB1 adsorption to montmorillonite displaced interlayer water and shifted the Si-O stretch band, which suggests that AfB1 adsorbed to siloxane surfaces. Absence of the AfB1 ketone C=O band in AfB1/montmorillonite spectra suggests the AfB1 dicarbonyl system might also affect adsorption.

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PROBING THE MICROSCOPIC HYDROPHOBICITY OF SMECTITE SURFACES Cliff T. Johnston 1, Kiran Rana 1, Stephen A. Boyd 2, Brian J. Teppen 2, and Thomas J. Pinnavaia 3 1Crop, Soil and Environmental Sciences, Purdue University, West Lafayette, IN 47907, USA; [email protected] 2Department of Crop and Soil Sciences, Michigan State University, E. Lansing, MI 48824, USA 3Department of Chemistry, Michigan State University, E. Lansing, MI 48824, USA Certain congeners of the chlorinated planar tricyclic aromatic ether compounds known as dioxins and furans are among the most harmful compounds known to man due to their toxicity and carcinogenicity. Recent studies have confirmed that certain smectites exchanged with weakly hydrated cations (e.g., Cs+) have a higher than expected affinity for these strongly hydrophobic compounds. This surprising link is counterintuitive as the dioxins are strongly hydrophobic and the smectites are generally viewed as being strongly hydrophilic. This paper will explore the nature of these heterocyclic molecule interactions at the molecular level using a combined strategy of in situ polarized attenuated total reflectance FTIR, Raman, structural methods and batch sorption methods. A structural model will be presented to account for different sorption affinities among various smectites and coupled sorption-spectroscopic-structural data will be presented on dibenzo-p-dioxin and 1-chloro-dibenzo-p-dioxin. Emphasis in this talk will focus on the site-specific solute-surface interactions occurring in the interlamellar region of the clay.

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NANO CONFINED WATER IN CLAY MINERALS Marika Santagata 1, Gnasiri Premachandra 2 and Cliff T. Johnston 2 1 School of Civil Engineering, Purdue University, West Lafayette, 47907, USA 2 Crop, Soil and Environmental Sciences, Purdue University, West Lafayette, 47907, USA, [email protected] Kaolin-group minerals are among the most abundant and industrially important minerals on Earth. Halloysite, a naturally occurring hydrated polymorph of kaolinite, is emerging as an attractive material for use in a variety of industrial applications, which take advantage of the distinct nano-tubular morphology of this mineral as a reinforcing material in polymer nanocomposites, as well as a vehicle for the controlled release of drugs or enzyme immobilization. From the perspective of surface chemistry, a unique attribute of hydrated halloysite is the presence of a confined monolayer of water between the siloxane and hydroxylated surfaces. Additionally, halloysite is typically characterized by a tubular or spheroidal meso-structure, leading to further organization of water molecules at the particle scale. Finally, the presence of some “free” water is apparently necessary to maintain the system fully hydrated. While water plays a critical role in controlling the structure of halloysite, surprisingly, relatively little is known about the chemical and physical properties of water associated with halloysite. At the same time industrial applications of halloysite are limited by the presence of water on this strongly hydrophilic clay, making knowledge of the types of water and their properties critical to extend our ability to exploit halloysite as an industrial mineral. The study presents an integrated experimental study of water on samples of halloysite which have been kept fully hydrated since collection, and samples prepared in the laboratory at different water contents. A novel application of low temperature differential scanning calorimetry is presented to identify and probe the nature of the three different populations of water molecules. In the fully hydrated halloysite, the calorimetry results show anomalies in the freezing and melting peaks with distinct peaks reflecting freezing of the bulk water and the capillary water confined inside the nano-tubular pores; the latter freezing process is observed to occur at temperatures as low as -37°C; upon re-heating two melting events are also observed, albeit in a much narrower temperature range. Air drying leads to the deintercalation of water but similar calorimetric curves are observed after rehydration of the clay. In all samples, a significant amount of water – as large as 16% w/w - is found not to freeze. The calorimetric data are supported by: low temperature (~ 20 K) FTIR spectroscopy which shows clear changes that occur upon freezing in the vibrational bands of the water and of the clay itself; ATR-FTIR spectroscopy to study the nature of water in halloysite; and XRD for monitoring the loss of the interlayer water.

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SODIUM PYROPHOSPHATE – BENTONITE SUSPENSIONS FOR USE IN LIQUEFACTION MITIGATION Julia P. Clarke 1, A. Bobet 2, V.P. Drnevich 2, Chadi El Mohtar 3, Cliff T. Johnston 4, and Marika Santagata 2 1Fugro Consultants, Inc., Houston, 77081, USA 2School of Civil Engineering, Purdue University, West Lafayette, 47907, USA, 3Department of Civil, Architect. and Environmental Engineering, University of Texas, Austin, 78712, USA 4Department of Agronomy, Purdue University, West Lafayette, 47907, USA; [email protected] Liquefaction of loose granular soils is an important cause of damage to civil infrastructures during earthquakes, and there is great interest in the development of methods for reducing the susceptibility of sand deposits to this phenomenon. Recent research (El Mohtar et al. 2008) indicates that the liquefaction resistance of sand is greatly enhanced in presence of small percentages (~3% by mass of the sand) of bentonite in the soil pores. This effect is ascribed to the nature of the pore fluid formed under these conditions: a concentrated bentonite suspension with gel like structure, suggesting that permeation of a sand deposit with a bentonite suspension may represent an effective approach to liquefaction mitigation. Practical application of this method requires that the rheology of the bentonite suspension be engineered so that on the short term the suspension has properties that allow its permeation inside a porous medium; but that once inside the sand pores, it regain the gel-like nature, which ensures its effectiveness in mitigating the effects of cyclic loading. The work presented here explored the use of sodium pyro-phosphate (SPP) to modify the rheology of bentonite suspensions prepared using a commercial Wyoming sodium-bentonite. A Physica MCR 301 Rheometer was utilized to investigate the changes in the flow and viscoelastic properties of 10% bentonite suspensions treated with SPP (at dosages ranging from 0% to 5% by mass of the bentonite,) over time. It is found that even small additions of SPP impact the rheology of the suspensions, and that the effects are more marked as the SPP% increases. At early ages suspensions with SPP > 0.5% are shown to be suitable permeation materials, based on permeation tests conducted through laboratory prepared sand columns. Compared to the bentonite-only suspension, these materials display a significantly reduced storage modulus, an increased loss modulus, minimal yield stress, and little to no thixotropy. Over time the rheology of all SPP treated bentonite suspensions evolves significantly, and after 7 months of ageing all the suspensions display a gel-like structure; the greater the SPP %, the more delayed the formation of the gel. Preliminary results from tests conducted on sand treated with a 10% bentonite and 0.5% SPP suspension demonstrate the effectiveness of the treatment in increasing the resistance of the sand to liquefaction. El Mohtar, C.S, Clarke, J.P, Bobet, A. Drnevich, V.P., Johnston, C., Santagata, M. (2008). Cyclic

response of a sand with thixotropic pore fluid. Proc. 4th Intern. Conference on Geotechnical Earthquake Engineering and Soil Dynamics (IV GEESD), Sacramento, USA.

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CURRENT LEVEL AND TRENDS IN QUANTITATIVE PHASE ANALYSIS OF GEOLOGICAL MATERIALS Reinhard Kleeberg

Technical University Bergakademie Freiberg, Mineralogical Institute, Brennhausgasse 14, D-09596 Freiberg, Germany; [email protected] Quantitative phase analysis (QPA) was developed as a tool for research as well as for product or process control and troubleshooting in the mining and processing industry. Despite the long history and early publications of theoretical principles and possible applications of X-ray powder diffraction (XRPD) for this purpose, the accuracy of QPA results often has been criticized, and, indeed, the level is not yet comparable with that usually reached in the analysis of major chemical elements. This fact is highlighted in the outcomes of some inter-laboratory round robin tests. Even if the qualitative composition of mixtures is rather easy and known to the operator, significant errors and uncertainties occur in practice (Rafaja & Valvoda, 1996; Madsen et al., 2001; Scarlett et al., 2002). Typically, the estimated standard deviation of a group of laboratories for intermediate mass fractions is in the magnitude of 3 % absolute. In the case of complex mixtures containing disordered phases like clay minerals, and if the qualitative composition is unknown to the operators, the QPA results can be very inaccurate (Ottner et al., 2000; McCarty, 2002; Kleeberg, 2004). On the other hand, impressive accuracy (better than 1 %) can be obtained even for complex mixtures by careful application of well known techniques (Kleeberg, 2004; Omotoso et al., 2006). In the field of clay mineralogy, full pattern fitting methods and Rietveld based techniques dominate the daily practice. Not surprisingly, XRD single line methods tend to perform worse than the full pattern techniques. The great impact of the users’ experience on the quality of the results can be seen from the very different quality of results from laboratories using the same software for phase quantification. The reasons for poor QPA results can be identified from the participant’s reports. There are some major groups of sources of errors: (i) inadequate sample preparation, (ii) wrong phase identification, and (iii) a lack of understanding of the principles and weaknesses of the applied technique. In detail, well known problems like microabsorption, preferred orientation, line overlap, and uncertainties about the structural features of the phases seem to be more important than the measurement and data quality. Rietveld based techniques often suffer from convergence into wrong minima by correlation of parameters, frequently resulting in meaningless profile shape parameters and inaccurate scale factors. In order to raise the level of QPA, users must learn the basics of the methods as well as the potential sources of error in as great detail as possible. Also, the software developers for QPA should support the users by providing more user-friendly programs, stable algorithms, and physically based and tested structure models in the case of Rietveld analysis. Kleeberg, R. (2004) Results of the second Reynolds Cup contest in quantitative mineral analysis. IUCr CPD

Newsletter 30, 22-24. Madsen, I.C. Nicola, Scarlett, N.V.Y., Cranswick, L.M.D., and Lwin, T. (2001) Outcomes of the International

Union of Crystallography Commission on Powder Diffraction round robin on quantitative phase analysis: samples 1a to 1h. J. Appl. Cryst., 34, 409-426.

McCarty, D.K. Quantitative mineral analysis of clay-bearing mixtures: The Reynolds Cup contest (2002). IUCr CPD Newsletter 27, 12-16.

Omotoso, O., McCarty D.K., Hillier, S. and Kleeberg, R. (2006). Some successful approaches to Quantitative mineral analysis as revealed by the 3rd Reynolds Cup contest. Clays and Clay Minerals, 54 (6) 748-760.

Ottner, F., Gier, S., Kuderna, M. and Schwaighofer, B. (2000): Results of an inter-laboratory comparison of methods in quantitative clay analysis. Applied Clay Science 17, 223-243.

Scarlett, N.V.Y., Madsen, I.C., Cranswick, L.M.D., Lwin, T., Groleau, E., Stephenson, G., Aylmore, M. and Agron-Olshina, N (2002). Quantitative phase analysos round robin. J. Appl. Cryst., 35, 383-400.

Valvoda, V., Rafaja, D., Kužel, R and Dobiášová, L. (1996). Summary of main results of the round robin test on powder diffraction sensitivity. Materials Structure, 4, 299-305.

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ACID DISSOLUTION OF BENTONITES Peter Komadel, Martin Pentrak, Jana Madejova Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, Bratislava, SK-845 36, Slovakia; [email protected] Acid activated bentonites are well known as bleaching earths. They have been widely used for a broad range of decolourising applications, as solid acid catalysts and catalyst supports. Acid treatment of a bentonite removes readily soluble phases such as carbonates or iron oxides. It also affects the main mineral, smectite, via the exchange of the interlayer cations for hydrated protons and the removal of octahedral cations and any isomorphously substituted tetrahedral cations from the layers. The extent of smectite dissolution affects the properties of the product obtained. Many laboratory assays of acid treatments under various conditions provided valuable information on the reactivity of different clay minerals with acids and on the kinetics and mechanisms of these reactions. Very important is that direct comparison of the results obtained in different laboratories is difficult because various variables of the experiments, e.g. acid concentration, temperature and time of the treatment, clay/acid ratio, intensity of stirring of the reaction mixture, etc., which affect substantially the reaction process and the results obtained, are rarely sufficiently characterized. The extent of clay mineral dissolution is affected by several variables, which can be divided into groups: Reaction conditions: temperature, time, type and concentration of the acid used, clay/acid ratio, and stirring of the reaction mixture. Most of these variables are usually well defined, except for stirring. The reaction rate may depend substantially on the intensity of stirring. This is why direct comparison of the results on acid dissolution of bentonites obtained in different laboratories is difficult, if possible at all. Chemical composition of smectite layers and extent of isomorphous substitutions. Effect of chemical composition of layers is well illustrated on smectites; trioctahedral minerals dissolve in acids much faster than their dioctahedral counterparts. Comparable reaction rates were reported for dissolution of hectorite in 0.25 M HCl at 20 °C and for an Al-rich Jelšový Potok montmorillonite in 6 M HCl at 95 °C. Both Fe(III) and Mg(II) substitution for Al(III) in the octahedral sheets increase substantially mineral dissolution rate. The effect of Mg(II) is more pronounced than Fe(III). Particle size and non-swelling interlayers. Protons attack the clay structure not only from the particle edges, but also from the interlayers. Finer particles dissolve faster if kept in dispersion, Mixed-layer clay minerals, typically illite/smectites, occur frequently in bentonites. Higher content of non-swelling layers decreases the dissolution rate of these minerals in HCl. However, most recent results show that the effect of chemical composition of the layers is more important than presence of non-swelling interlayers.

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REDUCTION AND REOXIDATION OF NONTRONITE: HOW WAS MAXIMAL REDUCTION ACHIEVED IN 1986-87 Peter Komadel 1,2, Paul R. Lear 1 and Joseph W. Stucki 1,3 1Department of Agronomy, University of Illinois, Urbana, IL 61801, USA 2Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, Bratislava, SK-845 36, Slovakia; [email protected] 3Department of Natural Resources and Environmental Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA Iron in the octahedral sheets of layer silicates has been reduced from Fe(III) to Fe(II) using a number of different methods and reducing agents. The level of Fe(II) achieved in the clay structure cannot be predicted. For example, hydrazine and dithionite have approximately the same electrode reduction potential; however, dithionite is a more effective reducing agent. It is the only inorganic agent tested thus far that can reduce virtually all structural Fe under ambient conditions (Stucki et al., 2002). Nontronite was suspended in citrate-bicarbonate buffer solution in an inert-atmosphere reaction vessel. Iron was reduced by briefly removing the cap from the reaction vessel and adding solid sodium dithionite (Na2S2O4) directly to the clay suspension. Under these conditions dithionite can disproportionate into sulfoxylate free radicals, which enhances its electron activity and reducing capacity. The suspension was then circulated in a closed loop from the reaction vessel through a flow cell mounted in a UV-Visible spectrophotometer, using a peristaltic pump fitted with flexible tubing. Needles mounted to each end of the tubing provided supply and return access to the sample through the septum cap of the vessel. The atmosphere within the vessel was maintained by inserting two additional needles: one carried the purge gas deep into the suspension; the other served as a vent. Gas bubbles flowing through the clay suspension furnished sufficient agitation to maintain a uniform solid:solution ratio in the optical cell. The temperature of the sample was maintained stable by placing 2/3 of the reaction vessel in a water bath (Komadel et al., 1990). The reduction and re-oxidation of nontronite was followed with visible absorption spectroscopy by continuously monitoring the intervalence electron transfer band at 730 nm during reduction and re-oxidation. The intensity of the band followed the number of Fe(II)-O-Fe(III) groups in the clay crystal, increasing to a maximum at about Fe(II):total Fe = 0.4; upon complete reduction, the band decreased to about the intensity of the unaltered, oxidized sample. Upon re-oxidation of the sample with O2, the intensity of the band increased sharply, followed by a gradual decay back to the original, oxidized intensity. The ultimate level of Fe reduction achieved was at least 92%, probably more. Concomitantly, the color changed from yellow through green, blue-green, dark blue, light blue, and light gray as the Fe(II) content increased. These changes in color were followed also by eye. The rate and level of reduction increased with the amount of reducing agent added. Stucki, J. W., et al. (2002) The effects of iron oxidation state on the surface and structural

properties of smectites. Pure and Applied Chemistry, 74, 2079-2092. Komadel, P., et al. (1990). Reduction and reoxidation of nontronite: Extent of reduction and

reaction rates. Clays and Clay Minerals, 38, 203-208.

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BLACK CARBON, THE PYROGENIC CLAY MINERAL? David Laird USDA, ARS, National Soil Tilth Laboratory, 2110 University Blvd., Ames IA 50011 USA; [email protected] Most soils contain significant amounts of black carbon, much of which is present as discrete particles admixed with the coarse clay fraction (0.2–2.0 μm e.s.d.) and can be physically separated from the more abundant diffuse biogenic humic materials. Recent evidence has shown that naturally occurring black carbon particles contain ~60% by mass aromatic C, with the remainder being a mixture of aliphatic, anomeric and carboxylic C. Black carbon particles have rounded morphologies with both porous and glassy internal structures. Radiocarbon dates of black carbon rich fractions physically isolated from soils indicate that black carbon is old and hence black carbon is assumed to be very stable in soil environments. By contrast, biogenic humic materials isolated from the same soils have modern radiocarbon dates and are more readily metabolized by soil microorganisms during incubations. Such evidence strongly suggests that most black carbon particles were originally charcoal formed during vegetation fires. Fresh charcoal has a low surface charge density and is hydrophobic; however, as charcoal ages in soil environments the surfaces oxidize forming carboxylic groups. Thus explaining why naturally occurring black carbon particles have a high density of variable surface charge and are hydrophilic. Clay size black carbon particles exhibit colloidal behavior in aqueous systems. X-ray diffraction analysis of freshly prepared charcoal reveals short-range order indicating the presence of disordered graphene sheets. Although not traditionally considered clay minerals; the properties and occurrence of black carbon are consistent with the broader definition of a clay mineral.

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DEVELOPMENT OF NANOCLAY FOR PLASTIC ADDITIVE APPLICATIONS Tie Lan Nanocor, Inc., Hoffman Estates, IL 60192, [email protected] Bentonite clays have been used in industrial and consumer goods for many years. New applications from this very versatile mineral are still emerging. Use of montmorillonite clay as a plastic additive to make nanocomposite is one of the hot research subjects. This paper will include the development of montmorillonite surface chemistry, nanoclay / nanocomposite processing technology and discuss current commercial applications. This presentation will focus on technology development and value creation of nanoclay technology.

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HEAVY METAL UPTAKE AT THE MUSCOVITE-SOLUTION INTERFACE OBSERVED USING IN-SITU X-RAY REFLECTIVITY* Sang Soo Lee 1, Paul Fenter 1, Changyong Park 1, Neil C. Sturchio 2, and Kathryn L. Nagy 2 1Chemical Sciences and Engineering, Argonne National Laboratory, Argonne, IL 60439, USA; [email protected] 2Department of Earth and Environmental Sciences, University of Illinois at Chicago, Chicago, IL 60607, USA

Clay minerals and detrital micas are ubiquitous in the near-surface environment and play an important role as sorbents of heavy metal pollutants. Understanding molecular-scale reactions at phyllosilicate-solution interfaces is essential for assessing the mobility and bioavailability of toxic elements in soils and natural waters. We investigated the uptake and adsorption structure of heavy metals (Cu2+, Zn2+, Sr2+, Hg2+, and Pb2+) on the basal surface of muscovite in solutions at acidic to neutral pH by using in-situ X-ray reflectivity combined with resonant anomalous X-ray reflectivity. The results show characteristic distributions of adsorbed heavy metals with sub-Ångström resolution. Heavy metals adsorb on the muscovite (001) surface as both inner-sphere (IS) and outer-sphere (OS) complexes, and the IS:OS partitioning is closely related to the hydration energy of the sorbate. A comparison between Sr2+ and Zn2+ results is representative. Sr2+ has a hydration enthalpy of -1445 kJ/mol (Richens, 1997), adsorbs as IS and OS in equal proportions (i.e., [ISSr]/[OSSr]~1), and the coverage fully compensates the negative charge of muscovite in a 110-2 m Sr(NO3)2 solution at pH 5.5 (Park et al., 2006). On the other hand, Zn2+ has a higher hydration enthalpy (-2044 kJ/mol; Richens, 1997) and adsorbs mostly as an OS complex (i.e., [ISZn]/[OSZn]~0) to compensate ~80 % of the surface charge in a 110-3 m Zn(NO3)2 solution at pH 5.5. Under more acidic conditions, hydronium appears to modify the coverage and distribution of adsorbed metals. Hydronium has a smaller hydration enthalpy (-401 kJ/mol; Bockris et al., 2000) and is expected to adsorb mostly as an IS complex, and therefore can compete with IS metals. For example, Sr2+ coverage was reduced by ~50 % in a 110-2 m Sr(NO3)2 solution at pH 3.7 compared to pH 5.5, mainly due to the significant decrease in the amount of its IS complex. Conversely, uptake of Zn2+ was less affected (i.e., ~10 % coverage decrease) by hydronium competition in 110-2 m Zn(NO3)2 at pH 3.7. Sorption of hydronium can be thought to partially neutralize the muscovite surface charge, leading to decreased electrostatic attraction of metal ions. As a result, the modified muscovite surface may become similar to dioctahedral clay mineral surfaces, such as vermiculite or montmorillonite, and the results from the low pH experiments can provide insight into how metal cations adsorb on phyllosilicate clay minerals with lower surface charge. *This work is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Geoscience Research Program. Bockris, J.O. et al. (2000) Modern Electrochemistry 2nd Ed., Springer. Park, C., et al. (2006) Hydration and distribution of ions at the mica-water interface. Physical

Review Letters, 97, 016101-1-4. Richens, D.T. (1997) The Chemistry of Aqua Ions, John Wiley & Sons, Ltd.

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LINCOMYCIN SORPTION BY SMECTITE CLAYS Hui Li, Cuiping Wang, Yunjie Ding, Brian J. Teppen and Stephen A. Boyd Department of Crop and Soil Sciences, Michigan State University, East Lansing, MI 48824, USA; [email protected] Lincomycin, an antibiotic widely administered as a human and veterinary medicine, is frequently detected in soil and water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin sequestration. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e. saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e. montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment which reduced sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

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BACKSCATTERED ELECTRON MICROFABRIC OF BLACK SHALES Nchekwube Mbamalu, Logan Kirst and Ray E. Ferrell, Jr. Department of Geology & Geophysics, Louisiana State University, Baton Rouge, LA 70803. [email protected] Black shales are important hydrocarbon sources, reservoirs, and seals. Changes in the quantities of microfossils, quartz, feldspars, carbonates, pyrite, phosphates and clay minerals as well as their spatial arrangement are directly related to the depositional and diagenetic environment and exert a control on the physical properties of mudstones and shales. Clay-rich, highly organic, fissile black shales formed in the condensed section related to a transgressive sequence are most likely to be good seals and highly productive source rocks. The recognition of petrographic characteristics used to identify black shale facies and environments of deposition is facilitated with the use of backscattered electron (BSE) imaging in a scanning electron microscope. Variations in the intensity of backscattering are directly related to the chemical composition of the particles and help to establish their mineral identity. Image analysis methods can be applied to assess mineral abundance. Laminae, graded bedding and other sedimentary structures are easy to recognize. This presentation uses BSE images obtained from polished specimens to identify the microfacies occurring in samples of the Woodford and Fayetteville shales. These shales are representative of the Paleozoic black shales that are major producers of gas in North America. The most significant differences are related to the relative quantities of quartz, carbonates and clay minerals present and whether the minerals are segregated in layers or randomly mixed.

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A ZONED K-BENTONITE FROM THE MONTANA DISTURBED BELT REVISITED: NEW IMPLICATIONS FOR SMECTITE ILLITIZATION Douglas K. McCarty 1, Boris A. Sakharov 2 and Victor A. Drits 2

1Chevron ETC, 3901 Briarpark, Houston, TX, 77063 USA [email protected] 2Geological Institute of the Russian, Academy of Science, Pyzevskij per. D.7, 119017 Moscow, Russia The illitization reaction in a thick K-bentonite bed located in upper Cretaceous marine shale in the Montana disturbed belt was studied by X-ray diffraction, chemical, and thermal gravimetric analysis. Modeling of the experimental XRD patterns from oriented clay specimens show that at each sample location in the bentonite bed a mixture of R0 illite-smectite (I-S) and R1 I-S coexist. Each of these phases in all samples consists of the same content of illite and expandable layers. In particular, the illite content in the R0 I-S and the R1 I-S from <0.5 µm fractions are equal to 30% and 62% respectively. The main difference between the samples at different locations in the bed is the different weight concentrations of the coexisting I-S phases. The R1 I-S content decreases progressively from the lower and upper contacts of the bed to its center and the reverse trend was observed for the R0 I-S. The DTG patterns of the samples contain two endothermic maxima at about 640° and 470°C corresponding to cis-vacant (cv) illite and trans-vacant (tv) smectite layers coexisting in the R1 I-S and R0 I-S. The layer unit cell parameter b for the samples located near the middle of the bed increase toward samples located near the bed margins. Both I-S phases in the middle of the bed have the lowest octahedral Mg and the highest tetrahedral Al content. In the structural formula of the R1 I-S, the tetrahedral Al content is significantly higher than (K+Na) content independent of sample location. In contrast tetrahedral Al in the R0 I-S located near the bed boundaries is lower compared with (K+Na) content. It was assumed that the initial volcanic ash was altered into tv smectite having a homogeneous Al-rich composition throughout the bed. Later, along with K, the active role in illitization was controlled by Mg. Mineralogical zonation of the K-bentonite is explained by the progressive migration of K from the margins toward the bed center with the associated decrease of K cations in the pore fluids. However, the decrease in K concentration was accompanied the successive increase in the content of the R0 I-S, but not a progressive decrease in illite layer content of a single I-S phase. These results demonstrate new insight into the intermediate members of smectite illitization. Instead of statistically homogeneous and continuous reaction associated with the increase of illite layers in a single I-S and the simultaneous increase in the order of the layer stacking sequence, the illitization reaction in thick K-bentonite consists of formation of a physical mixture of two I-S phases having a contrasting layer content and distribution. The interparticle model fails to account for the illitization reaction in this study.

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DATING THE PROGRESSIVE BURIAL OF THE SOURCE ROCKS OF THE ALBERTA TAR SANDS DEPOSITS Edward Meyer 1, James Aronson 1, Paul Nadeau 2, Cindy Riediger 3, Steve Hillier 4, Barry Richards 5 and Michele Asgar-Deen 6 1Department of Earth Sciences, Dartmouth College, HB 6105, Hanover, NH 03755 USA 2StatoilHydro ASA, Stavanger, Norway; [email protected] 3University of Calgary, Calgary, AB (present address: Shell Canada Ltd., Calgary, AB) 4Macaulay Institute, Aberdeen, UK 5Geologic Survey of Canada, Calgary, AB 6University of Calgary, Calgary, AB The location and time of maturation of the source rocks for the massive Tar Sands Deposits (TSD’s) emplaced along the eastern (craton-ward) edge of the Western Canada Sedimentary Basin remains a fundamental problem in Earth Sciences. Two source strata, the Devonian Exshaw Fm. and the Jurassic Gordondale Member of the Fernie Fm., historically have been proposed to have passed through the oil generation window during Laramide (late Cretaceous/Paleocene, 80-55Ma) burial by thrust sheets and clastic wedges within the Rocky Mountain Thrust Belt (RMTB). However, recent direct Re-Os dates of the TSD kerogen of ca 112-90 Ma require a re-evaluation of the entire petroleum system (Selby and Creaser, 2005). Here, we provide a newly expanded dataset of conventional K-Ar dates of the time of maturation of these source rocks by dating diagenetic illite that formed in K-bentonites that are fortunately contained within both of these source rock intervals. The mean age over which the kerogen in the source shales thermally matured is equivalent to the K-Ar date of illitization of the enclosed K-bentonites. We evaluate maturation dates of these potential source rocks from several of the thrust sheets in the RMTB in a framework of their approximate palinspastically restored pre-thrust positions. Samples from the most westerly, and earliest thrust sheets, like the Hosmer-Borgeau and Lewis thrust sheets, restore westward as much as ~200km to positions that would have been in front of the Purcell Mountain thrust uplift of the Late Jurassic-Early Cretaceous Columbian Orogeny. All dates of Exshaw and of Gordondale maturation increase westward. The Exshaw mean dates of illitization increase more dramatically westward from 81-145 Ma, while the increase in the Gordondale mean dates of illitization is subdued from just 60-81 Ma. The Gordondale maturation is younger than the 112-90 Ma Re-Os age window of oil emplacement. If the latter is valid, it would rule out the Gordondale as a source rock for the TSD’s. We propose that a vast Exshaw "kitchen" area was deeply buried beneath several kilometers of a now-eroded proximal part of the Late Jurassic –Early Cretaceous clastic wedge of Kootenay and Mannville-equivalent sediments that developed in front of (east) of the Purcell Mountain thrust uplift during the Columbian orogenic phase. The oil from the westernmost Exshaw in the RMTB matured at 145-138 Ma, before the Early Cretaceous (~125-110 Ma) reservoir rock was deposited, and either would have to have been lost or re-migrated later into the TSD’s. Oil sourced from the easternmost Exshaw in the RMTB is too young to have contributed to the TSD’s. These dates define a significant “kitchen” area that underwent maturation at times consistent with the Re-Os window. Our interpretation implies that the pre-Laramide (Columbian) orogenic phase, which buried these sources rocks, was more significant in forming the Canadian Rockies than is commonly acknowledged. Selby, D., and Creaser, R.A., 2005, Direct Radiometric Dating of Hydrocarbon Deposits Using

Rhenium-Osmium Isotopes: Science, v. 308, p. 1293-1295.

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EFFECTS OF USA AND WORLD RECESSION ON BENTONITE MARKETS William J. Miles Miles Industrial Mineral Research, 1244 Columbine Street, Denver, CO 80206 [email protected] Major commodity markets and value for bentonite in the USA have increased over the last 2 decades. New uses for bentonite now dominate major markets. Other commodity markets increased or decreased as changes occurred in each industrial application. Major commodity markets include: absorbents (predominantly pet litter), adhesives, animal feed, ceramics, civil engineering, drilling fluids, fillers & extenders, foundry sand binder, iron ore pelletizing, refractories, water proofing & sealing, and other minor uses. Bentonite has many uses that are tied to the economy and other uses tied to the population of the USA. The USA and world recession, beginning in late 2008, is reducing those markets tied to the economy but not those tied to population. For example, clumping pet litter, the single largest bentonite market, will not decrease significantly because we are now an urban society. However, oil and gas well drilling, the second largest market for sodium bentonite, is decreasing dramatically as active rigs are decreasing with our present recession that is creating a world glut of oil. In March, 2009, the USA is running out of storage capacity for processed gasoline and oil. The USA oil companies are cutting back on both drilling and production. Exports of bentonite, especially for drilling and foundry sand binder, are decreasing significantly with the world recession. Future trends are expected to decrease by market until the recession ends.

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AN ADDITIVE MODEL OF AGGREGATE SURFACE ENERGY BASED ON THE SURFACE ENERGIES OF MINERAL COMPONENTS Clint Miller, Bruce Herbert, Nathan Gardiner and Dallas Little Department of Geology and Geophysics, Texas A&M University, 108 Halbouty, College Station, TX 77840-3115, USA; [email protected] Environmental interactions are controlled by the interfacial characteristics and surface energies of the involved media. Surface energy describes the type and magnitude of the chemically reactive sites on the edges of substances (VAN OSS, 2006). Species chemical availability and reactivity is determined by accessibility to these reactive sites at surfaces. Biotoxicity is determined by bioavailability which is dependent on the ability of the contaminant to come into contact with a complimentary reactive region on the surface of a biomolecule (NEU, 1996). In order to better understand fate and transport of dissolved contaminants, the surface energy components of clays and other common minerals and aggregates must be known and how they change under different environmental conditions can be correlated to real situations. Surface energy of natural substances can be divided into two major components: van der Waals and polar forces (VAN OSS, 2006). Van der Waals forces are present in all molecules to varying degrees and are primarily dependent on molecular weight. Polar forces are found where electron donor/electron acceptor interactions take place. We have measured the surface energy components of a variety of pure phase minerals and aggregates using a Universal Sorption Device (USD) (BHASIN and LITTLE, 2007). The Universal Sorption Device measures the surface energy of all sides of a mineral simultaneously rather than one flat artificially created surface. The minerals and aggregates were characterized with an electron microprobe and the surfaces were analyzed with an X-ray Photoelectron Spectrometer (XPS) and SEM imaging. The SEM was used to qualitatively measure surface roughness and the XPS measured atomic species composition at the surface (upper 21 nm). An imaging scanner was used to quantify surface roughness. The percent composition of each species was compared with the surface energy components within mineral classes. The data gained was used to establish an additive model for aggregate surface energies based on mineralogy. Future research will quantify these substrates’ affinity for organic and inorganic contaminants. Bhasin, A. and D. N. Little, (2007) Characterization of Aggregate Surface Energy Using

the Universal Sorption Device. Journal of Materials in Civil Engineering, 19, 634.

Neu, T., 1996. Significance of bacterial surface-active compounds in interaction of bacteria with interfaces. Microbiology and Molecular Biology Reviews, 60, 151-166.

van Oss, C. J., 2006. Interfacial Forces in Aqueous Media. CRC Press, Taylor and Francis Group.

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THE VARIABLE TOXICITY OF QUARTZ: A COUPLED TOXICOLOGICAL AND MINERALOGICAL STUDY William F. Moll William Moll and Associates, Village of Lakewood, IL 60014-6604 [email protected] Inhalation of quartz can produce biological effects ranging from mild to profound. These responses are related to the character of the quartz particles involved. Crushing quartz greatly increases its bioactivity. Alteration of the surface in response to the geological environment appears to reduce the bioactivity. This study directly compared these two types of respirable quartz particles by in vivo toxicological investigation and by comprehensive mineralogical characterization. The crushed quartz was DQ12<5µm. The quartz with the natural altered surface (“occluded quartz”) was isolated from sodium bentonite by dispersion in water, without use of chemical dispersants, followed by exhaustive centrifugation. The toxicological investigation comprised intratracheal instillation of quartz particles in saline in Wistar rats, followed by bronchoalveolar lavage (BAL) after 3, 28, and 90 days and histopathological examination of lungs after 28 and 90 days. Evaluation of the BAL fluid measured cell damage, membrane permeability, macrophage phagocytic activity, cell count, and types of cells. At 3 days both types of quartz showed a significant inflammatory response. After 28 days the results of the occluded quartz was not different statistically from the saline vehicle control but those of the crushed quartz were much higher. After 28 days, histopathological evaluation showed moderate effects in the occluded quartz but did not progress at 90 days. In contrast, crushed quartz showed more severe effects and exhibited a progression to a persistent and self-perpetuating inflammatory state (Creutzenberg, et al, 2008). Mineralogical characterization included total chemistry, mineral phase identification, surface area, particle size analysis, electron microscope imaging, thermal measurements, X-ray diffraction measurements, electron spin resonance, and zeta potential measurements. The DQ12 had no other mineral phases but quartz, and was fragments of single crystals. The occluded quartz was an edifice of principally polycrystalline quartz and with some entrained montmorillonite. The X-ray domain size of the occluded quartz was very small, compared to the larger size of the crushed quartz. In DSC, the α↔β transition at 573C was not observable with the occluded quartz but was with the crushed quartz. Both the occluded and the DQ12 quartz showed ESR signals. The zeta potential measurements showed the crushed quartz had a much more electrically active surface compared with the occluded quartz (Miles et al, 2008). This research confirmed that biological response to quartz can differ significantly in characteristics and severity according to the nature of the quartz particles involved. Quartz particles with naturally altered surfaces appear much less bioactive than those with freshly fractured surfaces. Any toxicological or epidemiological study of quartz must include a mineralogical characterization if it is to be relevant. Creutzenberg, O., Hansen, T., Ernst, H., Muhle, H., Oberdörster, G., and Hamilton, R. 2008.

Toxicity of a Quartz with Occluded Surfaces in a 90-Day Intratracheal Instillation Study in Rats. Inhalation Toxicology, 20, 995-1008. (free online)

Miles W, Moll W.F., Hamilton R.D., and Brown R.K.. 2008. Physicochemical and Mineralogical Characterization of Test Materials used in 28-Day and 90-Day Intratracheal Instillation Studies in Rats. Inhalation Toxicology 20: 981-993 (free online).

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SAFETY OF CLAY MINERALS AND CLAY MINERAL PRODUCTS William F. Moll William Moll and Associates, Village of Lakewood, IL 60014-6604; [email protected] Ethical considerations alone require producers of clay minerals and clay mineral products to ensure their safety. Further, numerous national and international governmental agencies, non-governmental organizations, and trade associations are issuing more and more regulations and guidelines for workplace and product safety. European Union Regulation (EC) No 1907/2006, “Registration, Evaluation, Authorisation and Restriction of Chemicals” (“REACH”) is an excellent example. These initiatives, although well-intended, often do not take into account the complexities of clay minerals as opposed to straightforward organic chemicals such as benzene, for example. The job of the clay specialist is to examine these initiatives to ensure proper identification, characterization, and analysis of clay materials. The goal is to identify hazards where they exist, and avoid artifacts where hazards do not exist. Those involved include toxicologists, epidemiologists, industrial hygienists, physicians, regulators, and now mineralogists, all of whom have their own frameworks of reference and jargon. The goal is to be sure everyone is aware of the complexities and is careful with definitions. A persistent problem is nomenclature. Many are conversant with the IUPAC naming of organic compounds, but totally unaware of the procedures for naming minerals. Another is the nature of the mineral itself, particularly in terms of differing surface characteristics, solubility of troublesome elements, and polymorphs. Analytical procedures also pose problems. One example is extracting ultratrace organic constituents without introducing artifacts brought on by the catalytic or surface properties of clay minerals. Another is identification of mineral phases by those unaware of complexities. Many laboratories still persist in identifying opal as cristobalite, for example. This paper will detail several of these issues and discuss approaches for their solution.

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MINERAL SAFETY: WHERE ARE THE MINERALOGISTS? William Moll William Moll and Associates, Village of Lakewood, IL 60014-6604, U.S.A. In 1998, a noted toxicologist addressed a geological meeting and said, “In the discussion of biological effects of minerals, you geologists don’t even have a seat at the table. No one will pull one up for you; you have to do it yourselves.” The disciplines that do have seats are particle toxicology, epidemiology, industrial hygiene and medicine. Each of these disciplines has its own nomenclature, assumptions, and ways of doing things, all of which are often quite different from those of mineralogists. So, do mineralogists have anything to offer to the discussion, or are we all better off if they avoid the issues of biological effects of minerals and leave them to the “experts”? I contend that mineralogists have a great deal to offer, even though they are rare birds at toxicological meetings, and with a few notable exceptions, rare in the biological literature. Simple things, like the failure to use proper mineralogical nomenclature in toxicological studies or in regulatory rule making can create profound and long lasting problems. This confusion allowed the European REACH legislation (“Registration, Evaluation, Authorization and Restriction of Chemicals”) to recently declare that bentonite and montmorillonite are the same thing. Many non-mineralogists also often assume that mineral samples they are using are identical merely because they have the same name. They fail to recognize that differences in particle size, growth habit or surface composition often dictate biological effects. They may also fail to recognize the critical importance of properly identifying the minerals they are working with before using them. The relatively new interest in the health effects of nano-particulate materials is now causing toxicologists to rethink the role that proper characterization of these particles may play in understanding their biological activity. Because many of these materials are mineral in nature, the methods and expertise of mineralogists should become increasingly valuable to those interested in the health and safety of nano-particulates. These and other issues associated with the role of mineralogists in the understanding of mineral safety issues will be presented.

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GEOPOLYMERIZATION OF ORGANIC MATTER VIA REDUCTION OF STRUCTURAL IRON (III) IN 2:1 EXPANDABLE CLAY MINERALS Keith D. Morrison 1, Martin J. Kennedy 1 and Thomas F. Bristow 2

1Department of Earth Sciences, University of California Riverside, 900 University Ave. Riverside, CA 92521, USA; [email protected] 2Division of Geological and Planetary Sciences, California Institute of Technology MC170-25 1200 E California Blvd, Pasadena CA, 91125, USA The preservation of organic matter (OM) in sediments has presented a challenging and contentious problem. Evidence indicates that greater than 90% of sedimentary organic matter cannot be physically separated from its mineral medium (Hedges et al, 1995). Clay minerals comprise the bulk of the surface area in marine sediments and may aid in protecting OM from oxidation. Smectite clays in particular comprise the majority of the surface area with values of 750m2 g-1 (measured by water adsorption). These smectite clays contain expandable interlayer sites that can facilitate the adsorption of cations, water and OM. Organic matter can enter the interlayer sites of expandable clays and potentially limit biological remineralization. Verification of the close association between amino acids in smectite interlayer spaces was directly measured by using XRD. The adsorption of reducing amino acids in the interlayer space is coupled to the reduction of octahedral Fe(III) that could result in the formation of organic polymers that are not as readily desorbed from the clays. Reducing conditions in anoxic water columns and sediments may facilitate the reduction of structural iron in clays via electron transfer between phenol and thiol functional groups on amino acids and reducing sugars. The oxidation of functional groups on OM, due to iron reduction, are thought to aid in the creation of free radicals leading to the formation of amorphous OM. Reduction of structural iron in 2:1 clay minerals is also associated with an increased interlayer charge, ultimately lowering the surface area of the clay. Analysis of smectite clays using FITR, XRD and 1,10-phenanthroline (for quantitative measurement of ferrous iron) provides evidence that OM is entombed in coalescing aggregates and adsorbed into interlayer sites where it can be altered by reduction of the Fe(III) in the octahedral sites ultimately producing higher molecular weight polymers that are preferentially adsorbed onto mineral surfaces. Hedges, J., Keil, R. (1995) Sedimentary organic matter preservation: an assessment and

speculative synthesis. Marine Chemistry 49 (1995) 81-115

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KAOLIN MINING AND BENEFICIATION: THE ROLE OF IRON E. Murad, and J.D. Fabris Departamento de Química, ICEx, Universidade Federal de Minas Gerais, Campus – Pampulha, 31270-901 Belo Horizonte, Minas Gerais, Brazil [email protected] Kaolins are products of either intense weathering or hydrothermal alteration of aluminosilicate minerals such as feldspar and mica and often associated with other alteration products, the most deleterious of which are Fe oxides and oxyhydroxides (here termed “Fe oxides”), quartz, and the TiO2 polymorphs rutile and anatase. Depending on the mineralogy of the raw products and their specific uses, kaolins must be processed to remove coloring (mostly Fe oxides) or abrasive components, of which quartz, rutile and anatase are the most common. Because of their intense color (in particular hematite), Fe oxides must be removed from kaolins for most industrial applications. The particular value of Mössbauer spectroscopy lies in the possibility of being able to distinguish between and quantify Fe that is bound in the structure of kaolinite, in which it can replace Al to a certain extent, and Fe that occurs in associated Fe oxides. However, Fe oxides formed in the weathering environment are generally of small particle size and Al substituted. Thus, rather than being pure Fe oxides, hematite and goethite form weathering environments tend to have compositions given by α-(AlxFe1-x)2O3 and α-(AlxFe1-x)OOH, where x can amount to as much as 0.16 and 0.36, respectively (Cornell and Schwertmann, 2003). A distinction between Fe bound in the kaolinite structure and associated Fe oxides therefore requires Mössbauer spectra to be taken at low temperatures, usually ~ 77 K. A further complication can arise because of the generally low structural Fe content of kaolinite, which may lead to slow paramagnetic relaxation and thus non-Lorentzian broadening of spectra at room temperature and “simulation” of magnetic order at low temperatures. As a result, Mössbauer spectra of Fe oxide-free kaolins show non-Lorentzian line broadening of the Fe3+ doublet that is generally observed at room temperature and magnetic splitting at 4.2 K, both of which, however, result from slow paramagnetic relaxation and not from the presence of a possibly associated Fe oxide (e.g. hematite). Studies on Fe-bearing kaolins have furthermore shown that – in spite of the bothersome influence of paramagnetic relaxation – as little as 0.1 % goethite can be detected by Mössbauer spectroscopy at 4.2 K, attesting to the high sensitivity of this technique towards magnetically ordered phases (Murad and Wagner, 1991). Cornell, R.M., and Schwertmann, U. (2003) The Iron Oxides. Structure, Properties,

Reactions, Occurrences and Uses, 2nd edition. Wiley-VCH, Weinheim, Germany, 664 pp.

Murad, E., and Wagner, U. (1991) Mössbauer spectra of kaolinite, halloysite and the firing products of kaolinite: new results and a reappraisal of published work. Neues Jahrbuch für Mineralogie, Abhandlungen, 162, 281-309.

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DOES CLAY RESEARCH IMPROVE THE EFFICIENCY AND ENVIRONMENTAL PERFORMANCE OF ENERGY PRODUCTION? P. H. Nadeau StatoilHydro ASA, Norway, +4795700970, [email protected]

In May, 2008, the Canadian Oil-sands Network for Research And Development, CONRAD, held a workshop on clay mineralogy of the oil-sands. This informal presentation reviews the opening session of that workshop along with implications for clay mineral research related to energy development and environmental performance. It is shown that this approach can lead to significantly increased operational efficiency as well as improved environmental performance in terms of total carbon emissions.

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EARTH’S ENERGY “GOLDEN ZONE”: A TRIUMPH OF MINERALOGICAL RESEARCH P. H. Nadeau StatoilHydro ASA, Norway, +4795700970, [email protected] The impact of diagenetic processes on petroleum entrapment and recovery efficiency has focused the vast majority of the world’s conventional oil and gas resources into relatively narrow thermal intervals, which we call Earth's energy "Golden Zone". Two key mineralogical research breakthroughs underpinned this discovery. The first is the fundamental particle theory of clay mineralogy, which showed the importance of dissolution/precipitation mechanisms in the formation of diagenetic illitic clays with increasing depth and temperature. The second is the surface area precipitation rate models for the formation of diagenetic cements, primarily silica, in reservoirs. Understanding the impacts of these processes on permeability evolution, porosity loss, overpressure development, and fluid migration in the subsurface, lead to the realization that exploration and production risks are exponential functions of temperature. Global compilations of oil/gas reserves relative to reservoir temperature have confirmed the "Golden Zone" theory (Nadeau et al., 2005), as well as stimulated further research to determine in greater detail the geological/mineralogical controls on hydrocarbon migration and entrapment efficiency within the Earth's sedimentary basins. Nadeau, P.H., Bjørkum, P.A. & Walderhaug, O., 2005. Petroleum system analysis:

Impact of shale diagenesis on reservoir fluid pressure, hydrocarbon migration and biodegradation risks. In: Doré, A. G. & Vining, B. (eds) Petroleum Geology: North-West Europe and Global Perspectives – Proceedings of the 6th Petroleum Geology Conference, 1267-1274. Petroleum Geology Conferences Ltd., Published by the Geological Society, London.

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SAMPLE PREPARATION AND DATA COLLECTION STRATEGIES FOR X-RAY DIFFRACTION QUANTITATIVE PHASE ANALYSIS OF CLAY-BEARING ROCKS Oladipo Omotoso 1 and Dennis Eberl 2

1CanmetENERGY, Natural Resources Canada, Devon, Alberta, T9G 1A8, Canada; [email protected] 2U.S. Geological Survey, 3215 Marine Street, Suite E-127, Boulder, Colorado 80303, U.S.A. Historically, the main hindrance to quantitative phase analysis (QPA) of clay-bearing rocks has been the reliability of techniques used for analyzing the X-ray diffraction data. With recent advances in the reliability of whole profile fitting software based on structure refinement (Rietveld) and full pattern fitting that uses measured and calculated patterns (Fullpat, RockJock, Quanta etc.), it has become evident that the reliability of QPA of clay-bearing rocks is highly dependent on the sample preparation and data collection strategies employed. This study highlights sample preparation and data collection practices that have been found to yield consistently accurate QPA results, regardless of the data analysis method used. Extinction and microabsorption effects are best minimized by micronizing samples to sizes smaller than 5 µm, regardless of the radiation wavelength used. Whole profile fitting techniques utilize some form of reference intensity ratios, thereby eliminating the need to correct for sample mass attenuation coefficient. The most intractable problem is preferred orientation of the clay minerals. Although preferred orientation can often be corrected in Rietveld analysis, the refinement is often more stable if the deviation from ideal random orientation is minimal. Full pattern fitting techniques do not have the capability to correct for preferred orientation. Instead, they rely on consistent sample preparation technique for both samples and reference standards. For full pattern fitting techniques especially, randomly oriented samples significantly increase the chances of successful QPA. This study also highlights a new sample preparation method that produces consistently random orientation. The new sample preparation method entails micronizing samples with an alcohol or paraffin-based carrier fluid to increase surface hydrophobicity, followed by mixing and sieving through a small-mesh screen to produce more-or-less spherical aggregates. Aggregates that are sufficiently stable for side-packing are obtained by adding vertrel (0.5 ml/g of sample) prior to mixing. If the sample is clumped after mixing, excess vertrel is allowed to evaporate and the sample is mixed again to produce fine powders ready for sieving. The main advantages of this new method for preparing random aggregates are its simplicity and its use of sample preparation tools found in most laboratories, including micronizing mill, mixer, and sieve. A potential drawback of random aggregates is surface roughness, which often causes intensity aberration as a function of diffraction angle. Whereas this may create problems in the low-angle region if structural parameters are refined, the effect does not significantly impact QPA.

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RIETVELD REFINEMENT OF ALUMINUM-SUBSTITUTED GOETHITE AND HEMATITE IN SOME BRAZILIAN OXISOLS Oladipo Omotoso 1, Douglas, G. Ivey 2 and Marcelo, E. Ives 3

1CanmetENERGY, Natural Resources Canada, Devon, Alberta, T9G 1A8, Canada. [email protected] 2Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada 3Departamento de Ciências Exatas, Escola Superior de Agricultura ‘Luiz de Queiroz’ – ESALQ/USP, Piracicaba, SP, 13418-900, Brasil The main minerals usually found in the clay fraction of Brazilian oxisols include disordered kaolinite, nano-crystalline, Al-substituted goethite, and hematite, gibbsite, and other less abundant phases. Quantitative analysis of these minerals using Rietveld analysis of X-ray diffraction data is often hampered by excessive correlation between the disordered kaolinite model and the structural variations (including atom positions and Fe/Al ratio) imposed by aluminum substitution, especially in goethite. Refining the structural parameters of goethite and hematite during quantitative analysis is impractical and often leads to over parameterization and unreliable reported concentrations. This study aims at refining the structures of Al-goethites and Al-hematite chemically extracted from the clay fraction of oxisols, and using these structures as starting models for Rietveld analysis of such materials. Twelve oxisol soil clays had their iron oxides concentrated by boiling in 5 M NaOH. This treatment dissolved kaolinite and gibbsite, leaving behind a high concentration of Al-goethite and Al-hematite. The structures of the Al-goethites and Al-hematites of these concentrates were evaluated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Both TEM and XRD show that the level of aluminum substitution in goethite ranges from roughly 15 mol% to 40 mol% in the 12 oxisols resulting in structural changes with a significant impact on the intensity distribution in the X-ray diffraction data. Aluminum substitution in hematite is less extensive (up to 18 mol%). By using the refined Al-goethite and Al-hematite structures as starting models, Rietveld analysis of the oxisol clays was quite stable and the quantitative data correlated very well with the elemental analysis obtained by X-ray fluorescence.

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FACTORS INFLUENCING MONTMORILLONITE INTERCALATION BY POLYACRYLAMIDE Sungho Kim and Angelica M. Palomino Pennsylvania State University, Department of Civil and Environmental Engineering, 226A Sackett Building, University Park, PA 16802, USA; [email protected] Clay-polymer nanocomposites have been successfully produced in the material science field. Yet, these nanocomposites are often produced only in small quantities due to the high-energy demand and perceived cost of most intercalation techniques such as melt intercalation and in-situ polymerization. On the other hand, the intercalation of polymer molecules into clay particle interlayers can be achieved using solution intercalation, which utilizes water-soluble polymers, such as polyacrylamide (PAM), and swelling clays such as montmorillonite. Solution intercalation has the potential for large-volume production of intercalated montmorillonitic systems creating materials with beneficial uses in the geotechnical engineering field. The purpose of this study is to identify the optimum conditions for maximizing the production of particles with intercalated structure. Variables investigated using a solution intercalation technique are clay content, polymer concentration, and pH. Changes in the basal spacing of montmorillonite are characterized using X-ray diffraction. Observed intercalated structure formation tends to increase with decreasing clay-to-polymer volume ratio and at pH > 7.

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BORON BEHAVIOR DURING SEAWATER PALAGONITIZATION REVEALED USING SIMS MICROANALYSIS: IMPLICATIONS FOR ENVIRONMENTAL CONTROL Bruce D. Pauly 1, Lynda B. Williams 2, Richard L. Hervig 2 and Peter Schiffman 1 1Department of Geology, One Shields Ave., University of California, Davis, California 95616-5270 USA; [email protected] 2School of Earth and Space Exploration, Arizona State University, Tempe, Arizona 85287-1404 USA In order to make meaningful SIMS microanalyses of B-content and isotopic ratio in thin sections of palagonite, working standard, matrix effects and exchangeability issues were addressed. Clay Minerals Society source clay Silver Hill illite (IMt-1) was found to be an acceptable working standard. Advantages of IMt-1 include partial structural similarity to palagonite and high B content. Although expected matrix effects on SIMS analysis of palagonite remain unknown, they can be approximated based on the partial structural similarity of palagonite to both glass and TOT sheet-silicates. Matrix effects on SIMS analyses of B isotopic ratio in borated glass and illite were measured and found to be similar. Anticipated palagonite matrix effects should also be similar, permitting calibrated analyses of B isotopic ratios of palagonites. Due to palagonite partial similarity to TOT sheet-silicates, the possibility exists for B uptake by palagonite at both tetrahedral and interlayer (exchangeable) sites. Therefore a method for B exchange is required so that bulk, interlayer, and tetrahedral B-content and isotopic ratio can be determined. B-content decreased and δ11B shifted after soaking in a 1M NH4Cl solution for all thin section palagonite samples in this study, indicating that B exchange had occurred. This new exchange technique should have broad applicability for thin section microanalysis of clay minerals. Geochemical reaction modeling indicates that during closed-system (relatively low water/rock) palagonitization, pH shifts higher and authigenic zeolites and smectite are relatively abundant; for open-systems (higher w/r), pH does not shift higher and authigenic zeolites and smectite are relatively less abundant. Since pH controls the relative abundance of aqueous 11B(OH)3 and 10B(OH)4

-, and since clay-like areas of palagonite have tetrahedral sites where isotopic fractionation can occur during B uptake, in theory the B isotopic ratio and B-content of palagonites should reflect the w/r of the palagonitization environment. A carefully-selected sample set of natural palagonites was assembled to test this possibility. Submerged volcano flank and volcaniclastic basin samples have relatively low porosity, and palagonitized during burial and diagenesis; these are closed-system samples, with relatively abundant authigenic zeolites and smectite. Samples of submarine volcanoes/lava flows and marine tuff cones have relatively high porosity and are relatively uncompacted; these are open-system samples, with relatively less-abundant authigenic zeolites and smectite. Measured tetrahedral δ11B values for closed-system samples are relatively heavy and approach seawater δ11B, reflecting the low degree of fractionation expected for closed systems. Open-system calculated δ11B values for both palagonitizing waters and interlayer B are lighter than seawater, indicating likely involvement of hydrothermal fluid during palagonitization. Closed-system tetrahedral B-content is directly proportional to tetrahedral δ11B, and can be interpreted based on the behavior of the B mineral-water partition coefficient with pH. These results indicate that closed- vs. open-system palagonites can be distinguished using B isotopic ratio and content, and that the primary control on the B composition of palagonites is pH, reflecting the relative fluid flux during palagonitization.

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EFFECTS OF MINERAL TRANSFORMATION, CONTAMINANT CONCENTRATION AND C02 PRESSURE ON CONAMINANT SPECIATION AND MOBILITY IN SIMULATED HANFORD SEDIMENTS Nicolas Perdrial 1, Aaron Thompson 2, and Jon Chorover 1 1Department of Soil, Water & Environmental Science, University of Arizona, 429 Shantz Bldg, Tucson, AZ 85721, USA; [email protected] 2Department of Crop and Soil Sciences, University of Georgia, Athens, GA 30602-7272 Large volumes of high-level nuclear waste were generated from plutonium production and separation processes at the Hanford Site, WA. Wastes are present in tanks under conditions of high pH (8 to 14), high ionic strength, high temperature, and high concentrations of dissolved Al. Leaks from several tanks have been detected in the vadose zone sediments. Because these radionuclides may travel through the vadose zone and reach ground water, predicting their migration and sequestration is of critical importance. Our research approach centers on a series of flow-through saturated column studies conducted on Hanford Formation sediments reacted with a caustic (pH > 13) synthetic tank waste leachate (STWL) for up to 1 yr containing “HIGH” (10-3 m Cs and Sr, 10-5 m I) and “LOW” (10-5 m Cs and Sr, 10-7 m I) concentrations of co-contaminants, in the presence and absence of CO2. In all treatments, added Sr, Cs and I were incorporated into the solid phase with more uptake of Sr than Cs, and much smaller uptake of I. Physical characterization of the reacted sediments with reaction time (SSA, CEC, granulometry) is consistent with OH- induced dissolution of clay minerals. EXAFS, XRD, DRIFT and microscopic characterizations indicated the neoprecipitation of Ca-Na rich zeolites for the highest contaminant concentrations and NO3-feldspathoids (sodalite) for the low concentrations with Sr and Cs detectable in the neophases via TEM-EDX for the HIGH treatments. Iodine uptake could not be localized in the solid phase. All neophases are concentrated in the clay + silt fraction. pCO2 effect translates to discrete differences in mineral transformation. Given the dominant presence of zeolite in HIGH compared to the dominance of feldspathoid (sodalite) in LOW even after 1 y, mineral transformation (i.e., ripening) appears to be inhibited for HIGH sediment treatments. When these reacted sediments were leached with simulated pore water (equilibrium with calcite, pH=7) in flow-through saturated columns, major cation release and pH stabilized at pore volumes (PV) > 300. XRD investigations after 600 PV, indicated persistence of NO3-feldspathoids in the LOW and incongruent zeolite dissolution in the HIGH. Reactive transport modeling suggests that in LOW, long-term Sr release is governed by feldspathoid dissolution, whereas Cs release can be explained by ion exchange reactions with frayed-edge sites (FES) of illitic clays. In HIGH, the same mechanisms cannot explain the Cs and Sr long-term release. When considered in light of prior studies on specimen clays and homogeneous nucleation processes, our results on complex sediments indicate that initial contaminant concentration and sediment composition exert a strong impact on the solid phase transformations and contaminant fate/mobility in both STWL and BPW scenarios.

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THE CARBON FOOTPRINT AND LIFECYCLE ANALYSIS OF KAOLIN AND CALCIUM CARBONATE PIGMENTS IN PAPER Robert J. Pruett Imerys, 201 Kaolin Road, Sandersville, GA 31082, USA; [email protected] Paper and paperboard manufactures need to quantify the carbon footprint and environmental impact of their products to satisfy market, social, and government demands. Coated paper products contain minerals such as kaolin and calcium carbonate at significant levels, some coated paper grades have pigment mineral contents as high as 45% by weight. Some uncoated paper can contain no mineral but most uncoated paper contains some mineral to improve appearance, process efficiency, and cost. Uncoated super-calendared paper grades can contain levels of mineral up to 35% by weight. The carbon footprint of pigment minerals is mostly from the energy used in mining, processing, and transportation. The methodology for calculating the carbon footprint of a pigment is based on (a) building process flows that show energy use, major raw materials consumed, and losses, (b) converting energy to CO2e, and (c) adding direct carbon emissions from calcination or subtracting carbon sequestered by precipitated calcium carbonate. The carbon footprint of Brazilian kaolin slurry, Georgia kaolin slurry, Georgia calcined kaolin, wet-ground calcium carbonate (GCC), and a precipitated calcium carbonate (PCC) are compared. The slurry kaolin and GCC products all have lower carbon footprint compared to dry products. The Brazilian kaolin has a lower carbon footprint than the Georgia kaolin because of the lower carbon intensity of the Brazilian electrical power grid. The calcined kaolin and dried PCC have similar carbon footprint because calcination is needed to manufacture both pigments. The carbon footprint of paper has a wide range of reported values because different methodologies are used to calculate its carbon footprint. Generally, kaolin and calcium carbonate pigments have a lower carbon footprint than paper on a mass basis. Minerals can increase mill productivity and reduce drying energy required for paper production. Pigment minerals can reduce the carbon footprint of paper and paperboard.

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SIZE DEPENDENT PHYSICAL PROPERTIES AND CHEMICAL REACTIVITY OF HEMATITE NANOPARTICLES Andrew N. Quicksall, Lauren Barton, Tom Kosel and Patricia Maurice University of Notre Dame, Department of Civil Engineering & Geological Sciences, 156 Fitzpatrick Hall of Engineering, Notre Dame, IN 46556, [email protected] A variety of studies have demonstrated variation in physical properties and chemical reactivities of nano-sized mineral particles relative to their larger counterparts (Hochella et al., 2008; Waychunas et al., 2005). However, a full determination of fundamental physical, thermodynamic, and chemical properties as a function of size is still lacking for most phases. Chemical reactivity of mineral phases is often modeled as a function of available surface area which increases as particle size decreases. Yet, evidence is suggesting that not only surface area but surface structure and reactivity may change with size in the nanoscale, thus having potentially greater ramifications for reactivity changes with size. Here, we probed the fundamental properties of hematite (α-Fe2O3) as a function of size within the nanometer range. Hematite was chosen because of its widespread natural abundance and, as with all iron (hydr)oxides, it helps to control nutrient, toxic metal, and organic compound dynamics in natural environments. Moreover, hematite is amenable to synthesis from aqueous solution at discrete particle size ranges. Four distinct sizes of hematite nanoparticles were synthesized from solution with average diameters: 7nm, 37nm, 60nm, and 100nm. Particles were characterized for phase, degree of crystallinity, morphology, and surface area using a combination of electron diffraction, TEM, and BET surface area analysis. The amounts of incorporated and surface water were also investigated by thermal analysis. All of the samples were found to be highly crystalline hematite, with excellent lattice fringes. As expected, BET surface area (as measured by a 7 point N2 adsorption isotherm) increased with decreasing particle size, ranging from 5m2/g to 120m2/g for the 100nm to 7nm particles, respectively. Total hydration loss, as measured by thermogravimetric analysis, was only large (>1% by mass) in the smallest particles and was identified as dominantly surficial water loss over a wide temperature range. Differential thermal analysis measurements were consistent with exothermic processes from 30 to 850 °C. The data set is consistent with moderate, consistent recrystallization and surface dehydration of all particle sizes. These data show particle size dependent variation in surface hydration. This would suggest a resolvable change in chemical reactivity of these mineral surfaces due to a change in surface structure in addition to the typical increased surface area effects. Examples of surface area normalized, size driven, chemical reactivity (i.e. ligand promoted dissolution and metal sorption studies) for these particles will be discussed. Hochella, M.F., Lower, S.K., Maurice, P.A., Penn, R.L., Sahai, N., Sparks, D.L., and

Twining, B.S. (2008) Nanominerals, mineral nanoparticles, and Earth systems. Science, 319(5870), 1631-1635.

Waychunas, G.A., Kim, C.S., and Banfield, J.F. (2005) Nanoparticulate iron oxide minerals in soils and sediments: unique properties and contaminant scavenging mechanisms. Journal of Nanoparticle Research, 7(4-5), 409-433.

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THE MINERALOGY AND GEOCHEMISTRY OF BEDLOAD SEDIMENTS, TAIERI RIVER, SOUTH ISLAND, NEW ZEALAND N.J. Reid and C.E. Martin

Department of Geology, University of Otago, Dunedin, New Zealand [email protected] While the geochemistry of dissolved and suspended loads in global river systems have been widely studied, bedload sediments have received comparatively little attention. The Taieri River, located in East Otago, is New Zealand’s fourth longest river and drains an area of 5650 km2. The bedrock geology of the drainage basin is dominated by Paleozoic schist, with other less extensive units including the mafic volcanics and sediments of Cretaceous to Quaternary age. The aims of this study are to quantify the mineralogy of Taieri River bedload sediments, examine patterns of elemental transport, use Sr isotopes as provenance indicators and thereby determine the relationship between the bedrock geology and sediment geochemistry. Bedload samples were taken at intervals from the length of the river and sieved to produce six grain size fractions (4-2 mm, 2-1 mm, 1-0.5 mm, 0.5 mm-355 µm, 355-63 µm and <63 µm). Bulk and clay mineralogy of the different size fractions were determined by quantitative XRD using RockJock (Eberl, 2003). Major elements were analyzed by XRF, and trace elements by LA-ICP-MS. All size fractions at all locations contain quartz, albite, muscovite and chlorite, with less frequent epidote and clay minerals. Clay mineral separates consist of chlorite, illite, illite-chlorite ± vermiculite, with two samples also containing kaolinite. The presence of montmorillonite in an area draining mafic volcanics, reflects the influence of bedrock geology and weathering on bedload sediment composition. Quantitative XRD highlights the importance of analyzing different grain size fractions within the bedload sediment. Major and trace element concentrations of the grain size fractions reflect the continuum between quartz-rich coarser grain size fractions and the phyllosilicate-rich fine fractions. Eberl, D.D. (2003) User’s guide to RockJock – A program for determining quantitative

mineralogy from powder X-ray diffraction data. USGS Open-File Report 03-78. Boulder, Colorado.

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CO2 TRAPPING IN CLAYEY MATERIALS Vyacheslav N. Romanov 1, 2, Yee Soong 1, Bret H. Howard 1, Elizabeth A. Frommell 1, Robert L. Kleinmann 1 and George D. Guthrie 1

1U. S. Department of Energy, National Energy Technology Laboratory, P. O. Box 10940, Pittsburgh, PA 15236, USA 2Parsons Corporation, P. O. Box 618, South Park, PA 15129, USA; [email protected] Understanding of physical and chemical reactivity of clay-bearing materials with regard to the CO2 sequestration in geological formations is critical for validation of the field-scale reactive transport models. The clay mineral content can play an important role in defining both the reservoir storage capacity and trapping mechanisms and the sealing and confinement function of the cap-rock. We investigated CO2 interaction with clay and shale materials under various pressure and temperature conditions. Our recent manometric, infrared and X-ray diffraction data indicate that some smectites (STx-1b and SWy-2) can become a permanent trap for CO2 if sufficiently heated and then cooled. During these studies, the source clay samples from The Clay Minerals Society repository were exposed to CO2 pressure, up to 8MPa at 55oC, heated to 105oC in a sealed pressure vessel and then stored for 8 months at the ambient conditions. There were indications that the initially loosely-bound CO2 formed chemical bonds with alkaline cations over the following several months. Comparison of the CO2 sorption in powdered and non-powdered (SAz-2) montmorillonite samples showed that diffusion is not a limiting factor.

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SMECTITE AND SILICEOUS SINTER FORMATION IN OCTAPUS SPRING, YELLOWSTONE NATIONAL PARK, WYOMING, USA Paul A. Schroeder 1 and Jennifer E. Kyle 2

1Department of Geology, University of Georgia, Athens, GA, 30602-2501, USA, [email protected] 2Department of Geology, Earth Sciences Centre, 22 Russell Street, Toronto, Ontario, M5S 3B1, CANADA A siliceous sinter collected from Octopus Spring in Yellowstone National Park, USA contains an occluded volcanic rock fragment that has undergone alteration. The sinter piece beyond the fragment is mostly dominated by opal-A with trace amounts of bacterial cells, calcite, and detrital quartz. Within the altered rock region, the mineral assemblage is dominated by dioctahedral smectite and quartz with trace amounts of pseudobrookite, ilmenite, rutile, and hematite. Onset of opal-CT formation was only found in the outer spicular region of the sinter, which is unexpected given this outer part represents newest growth. A reaction mechanism is proposed whereby the alteration of feldspar to smectitic clay locally produces excess silica, alkali metal, and raises pH (Kyle and Schroeder, 2007). As the clay mineral forms it sequesters ions from pore fluids thereby inhibiting the opal-A phase change to more ordered opal-CT. Ions such as magnesium are known to promote the opal-A to opal-CT reaction. Smectite formation therefore may assist microbial texture preservation processes as excess silica produced increases the rate at which primary opal-A is formed. The altered zone also retains the greatest amount of fixed-C and fixed-N (operationally defined as C and N retain upon combustion at 450° C). The fixed-N likely represents ammonium trapped in the exchangeable interlayer site of the smectite. This fixed-N may serve as a potential biological signature of microbial activity in ancient rocks formed in similar environments (Kyle et al, 2007). Kyle, Jennifer, Schroeder, P.A., and Wiegel, J. 2007 Microbial silicification in sinters

from two terrestrial hot springs in the Uzon Caldera, Kamchatka, Russia. Geomicrobiology Journal, 24, 627-641.

Kyle, Jennifer and Schroeder, Paul A. 2007 Role of smectite in siliceous sinter formation and microbial texture preservation: Octopus Spring, Yellowstone National Park, Wyoming, USA. Clays and Clay Minerals, 55(2), 189-199.

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USE OF MINERALS TO ASSIST DETECTION OF BIO/ORGANIC SIGNATURES IN THE SEARCH FOR LIFE Jill R. Scott 1, C. Doc Richardson 2, J. Michelle Kotler 2, and Nancy W. Hinman 2

1Chemical Sciences, Idaho National Laboratory, Idaho Falls, ID 83415 [email protected] 2Department of Geoscience, University of Montana, Missoula, MT 59812 Detection of bio/organic signatures, defined as an organic structure produced by living organisms or derived from other biogenic organic compounds, is essential to investigating the origin and distribution of extant or extinct life in extraterrestrial and ancient terrestrial materials. In conjunction with mineralogical data, the detection and identification of bio/organic signatures can assist in linking biochemical and geochemical processes. Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is a method of obtaining bio/organic signatures from a range of geological materials with little or no sample preparation (Yan et al., 2007). We have been investigating how well bio/organic signatures can be detected when associated with a variety of both laboratory and natural minerals using GALDI-FTICR-MS (Kotler et al., 2008). Because the minerals essentially play the role of “matrix” to assist desorption and ionization of the bio/organic compounds, it is not surprising that some bio/organic-mineral combinations work better than others. Even for the minerals that work well, one of the key challenges is that the bio/organic constituents are not homogeneously distributed; hence, there is a need for high sensitivity to detection ions from single laser desorption events because typical signal averaging can actually obfuscate rare biological organic signatures, such as those obtained at Washburn Springs in Yellowstone National Park. The heterogeneity is addressed by taking advantage of the imaging capability associated with our FTICR-MS to search across a sample. While our detection limits can be as low as 3 parts per trillion for some bio/organic-mineral combinations (Richardson et al., 2008), it can be as poor as none for other combinations (Scott, et al., 2007). Even in the best case, it is estimated that the best ionization efficiency is only ~10%. Therefore, at least 90% of the bio/organic molecules are left undetected. Hence, efforts to improve the ionization efficiency and the signal-to-noise are currently being explored. Yan, B., et al. (2007) Detection of Biosignatures by Geomatrix-Assisted Laser

Desorption/Ionization (GALDI) Mass Spectrometry. Geomicrobiology J., 24, 379–385.

Kotler, J. M., et al. (2008) Glycine Identification in Natural Jarosites Using Laser-Desorption Fourier Transform Mass Spectrometry: Implications for the Search for Life on Mars. Astrobiology, 8, 253–266.

Richardon, C. D., et al. (2008) Exploring Biosignatures Associated with Thenardite by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (GALDI-FTICR-MS). Geomicrobiology J., 25, 432–440.

Scott, J. R., et al. (2007) Searching for Biosignatures as Signs of Life using GALDI-FTMS. J. Idaho Academy of Science, 43, 26–27.

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BENTONITE CLAY FOR NUCLEAR WASTE DISPOSAL Patrik Sellin Svensk Kärnbränslehantering AB (SKB), Box 250, S-101 24 Stockholm, Sweden; [email protected] The Swedish concept for the disposal for spent nuclear fuel is based on the multi-barrier principle. This means that the safety of a repository is ensured by a number of different barriers which are mutually independent and based on different processes. The principal barriers are: • the canister, which provides total isolation of the waste for very long time scales • the buffer, which restricts the flow of groundwater around the canister and gives a mechanical

protection • the bedrock, where the primary purpose is to create a hydraulically, mechanically and

chemically favourable environment for the other barriers, but also to restrict and delay possible releases of radioactive substances from the repository.

Ever since the repository concept was originally developed in the mid-70s, the idea has been to use a highly compacted bentonite as a buffer. The requirements on the buffer material are: • a low hydraulic conductivity (<10-12m/s), to ensure that transport is dominated by diffusion • a swelling pressure(>1MPa), to ensure that engineering voids are filled and guarantee a self-

sealing ability • long-term durability, the required assessment time-scale is one million years. A bentonite with a montmorillonite content of >75% and compacted to a dry density of ~1,550-1,600 kg/m3 would fulfil the requirements. Over the years there has been an extensive research programme ongoing to investigate how a bentonite buffer would perform in a repository environment. Activities have been and are ongoing in a number of the different areas. A few examples are: • The water uptake and swelling of bentonite blocks and pellets have been studied in laboratory

scale as a well as in full scale field experiments in underground laboratories. • Hydraulic and swelling properties at full saturation have been determined for a range of

different bentonites. • Recently, the stability of bentonite in the low-ionic strength groundwaters that could occur

after the melting of an ice-sheet have been investigated in a project comprising of laboratory studies together with the development of conceptual as well as mathematical models.

• The mineralogical stability of montmorillonite is evaluated with the aid of studies of bentonite in nature together with field experiments at elevated temperature.

A license application for a spent nuclear fuel repository in Sweden will be submitted to the government in 2010, with the aim to start repository construction in 2013 and operation in 2020. The production of the bentonite buffer comprises of three main steps: excavation and delivery, conditioning, preparation and manufacturing and finally deposition. The excavation and delivery process do not differ significantly from that of other industrial applications. Conditioning and preparation involves adjustment of water content and grain size of the bentonite to be suitable for the compaction. The reference technique for the manufacturing of buffer blocks is uniaxial compaction. The compaction stress varies between 40-100 MPa. The cylindrical blocks will have a diameter of 1640 mm, a height of 500 mm and a dry density of ~1630 kg/m3. The use of bentonite for the buffer is expected to be 20 tonnes/day.

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STRUCTURAL INCORPORATION OF MULTIPLE METALS IN GOETHITE AND ITS MINERAL PROPERITES Balwant Singh 1, Navdeep Kaur 1, Markus Gräfe2 and Brendan J. Kennedy 3 1Faculty of Agriculture, Food and Natural Resources, The University of Sydney, NSW 2006, Australia; [email protected] 2CSIRO Land and Water, PMB 2, Glen Osmond, SA 5064, Australia. 3School of Chemistry, The University of Sydney, NSW 2006, Australia Iron oxides are dominant adsorbents for trace metals in soils at low elemental concentrations. However, in highly contaminated environments such as acid mine drainage and acid sulfate soils, co-precipitation of trace metals with Fe may result in their incorporation in the Fe oxides crystal structure. We studied co-precipitation of trace metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in goethite at different solution pH (6-13) and nominal metal concentrations in order to evaluate the extent of metal incorporation and mineralogy of the solids formed. Single and multiple metal cation substituted goethites were synthesized under industrial (Fe3+, 70oC) and environmental (Fe2+, 25°C) relevant conditions. In slightly acidic environments (pH 6-7), the formation of lepidocrocite and goethite is dependent on which foreign metals were present with FeSO4 in solution. For example, Cu2+ promoted the formation of goethite over lepidocrocite, while Mn2+, Cd2+ and Pb2+ all favored the crystallization of well-ordered lepidocrocite. The complexity of the conversion of FeSO4 into a FeOOH polymorph was illustrated by the formation of green rust and siderite prior and simultaneously with goethite and, their formation and dissolution controlled the solution pH and the fate of foreign metals in the system. For single metal substituted goethite formed by the Fe3+ pathway (pH 12-13), the general sequence for metal substitution was Cr = Zn > Cd > Cu > Pb. In the presence of multiple metal cations, the extents of metal incorporation into the goethite structure depended on the combination of the metals present in system. X-ray absorption fine structure spectroscopy and X-ray diffraction results revealed that symmetric Cr/Cd octahedra lower the overall steric strains in the structure as compared to asymmetric Zn/Pb octahedra. The metals forming symmetrical octahedra (Cr and Cd) were evenly distributed in the crystal and appear to enhance the incorporation of co-metals. For example, Cr and Cd have significant positive effects on their mutual incorporation and the incorporation of Pb in goethite’s structure. Contrary to this, Zn limited the incorporation of Cr, Cd and Pb in the structure of goethite. The flexibility of the goethite structure for metal incorporation is thus illustrated by its ability to incorporate multiple metals with the extents of metal incorporation not being predictable from single metal level substitutions. The research provides new insights into the co-precipitation process of trace elements with Fe to form goethite and lepidocrocite structures under various conditions and thus show potential to be applied in highly contaminated environments.

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MODIFICATION OF ANION RETENTION BEHAVIOR OF CLAY MATERIAL Sudhakar M. Rao, and S. Sivachidambaram

Centre for Sustainable Technologies, Indian Institute of Science, Bangalore, 560012, India. [email protected] Clay based-inorganic-organic materials have extensively been studied because of their applicable to improve anion retention behavior of waste repository buffer material such like bentonite. Selection of host material and guest species is important for the design of admixtures to improve the anion retention behavior of bentonite. Long-chain organic polymers though can improve the anion adsorption capacity of bentonites; they would exchange the inorganic interlayer cations (Bors et al., 1999). Kaolinite, a 1:1 type clay mineral is frequently used as host materials for the formation of clay–polymer nanocomposites (Papp et al., 2004). Direct intercalation of polymer into kaolinite has been reported so far. A very limited number of kaolinite-alkali salts compounds prepared by hydrothermal reactions. On heating at temperatures below 600˚C kaolinite reacts with salts of alkali metals according to the equation 2SiO2.Al2O3.2H2O+2nMX→2SiO2.Al2O3. 2nM2O+2nHX+ (2-n) H2O. The reaction commences with the dehydroxylation of the clay and is favored by high Solubility of the salt and small size of the alkali ion. It appears that on dehydroxylation the clay becomes reactive and, concurrently, the water liberated dissolves adjacent salt particles and catalyses the reaction (Heller-kallai., 1978). Studies of Daniels and Rao (1983) have found that silver treated kaolinites have excellent sorption capacity for iodide ions. So in the present study explored the possibilities of formation of the silver-kaolinite compound by controlled hydrothermal reaction, which may be a suitable additive to improve the anion retention behavior of bentonite. The silver-kaolinite compound was prepared and examined by X-ray diffraction (XRD), thermal analysis, infra-red spectroscopy and X-ray photoelectron spectroscopy measurements. Anion retention behavior of silver-kaolinite was examined by using Iodide spiked natural and synthetic ground water samples. Bors, J., et al. (1999), Retention of radio nuclides by organophilic bentonite. Engineering

Geology, V 54, 195-206. Papp, S., et al. (2004) Synthesis and characterization of noble metal

nanoparticles/kaolinite composites. Progr. Colloid Polym. Sci., 125: 88–95. Heller-Kallai, L. (1978) Reaction of salts with kaolinite at elevated temperatures; I. Clay

Minerals, 13, 221. Daniels, E. A. and Rao, S. M. (1983). Silver sorption by kaolinite. International Journal

of Applied Radiation and Isotopes, Vol. 34, 981-984. Daniels, E. A. and Rao, S. M. (1983). Silver sorption by metakaolinite from molten silver

nitrate. Zeitschrift fur Physikalische Chemie Neue Folge, Vol. 137, 247-254.

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SORPTION OF IODIDE AND SODIUM IONS ON MODIFIED CLAY MATERIALS S. Sivachidambaram and Sudhakar.M.Rao Centre for Sustainable Technologies, Indian Institute of Science, Bangalore-560012, India; [email protected] Clays are important constituent of waste containment barriers and have specific role in designing the waste containment materials. Improving anion retention behavior of bentonite is important in limiting anionic contaminants and their transport in soil systems. Iodine-129 (I-129) is a fission product from nuclear power plant which is hazardous to biological systems and has long half-life (1.59 x 107 yrs). Clay based organic-inorganic materials have been investigated to improve anion retention behavior since many decades. Long-chain organic polymers though can improve the anion adsorption capacity of bentonites; they would also exchange the inorganic interlayer cations (S.Dultz, J.Bors., 1999). It is essential to design and prepare an admixer of bentonite without compromising its cation exchange capacity. Kaolinite (1:1 type clay mineral) is frequently used as host materials for the formation of clay–polymer nanocomposites (Szilvi et al., 2004). Daniels and Rao (1983) have found that silver treated metakaolinite had excellent sorption capacity for iodide ions. We show that silver treated kaolinite (silver-kaolinite) can be used as an admixer to bentonite with enhanced iodide retention capacity. Batch experiments were performed for iodide and sodium retention for which the corresponding values were 31-36 meq/100g and 25-27 meq/100g. On comparison, the sodium retention capacity of silver-kaolinite was higher than kaolinite(1-5 meq/100g). This support that silver-kaolinite can be a candidate admixer to buffer backfill material (bentonite) to retain radioactive iodide without compromising cation retention. Dultz. S, Bors. J (1999) Retention of radio nuclides by organophilic bentonite.

Engineering Geology, 54, 195-206. Szilvi et al. (2004) Synthesis and characterization of noble metal nanoparticles/kaolinite

composites. Progr. Colloid Polym. Sci., 125, 88–95. Daniels, E. A. and Rao, S. M. (1983). Silver sorption by kaolinite. International Journal

of Applied Radiation and Isotopes, 34, 981-984. Daniels, E. A. and Rao, S. M. (1983). Silver sorption by metakaolinite from molten silver

nitrate. Zeitschrift fur Physikalische Chemie Neue Folge, 137, 247-254.

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STRUCTURE OF POLYVINYLPYRROLIDONE (PVP) ON SMECTITE BASED ON COMPUTER SIMULATIONS Marek S. Szczerba 1, Jan Środoń 1 and Michał Skiba 2 1Institute of Geological Sciences, Polish Academy of Sciences, Senacka 1, 31-002 Kraków, Poland; [email protected] 2Institute of Geological Sciences, Jagiellonian University, ul. Oleandry 2A, 30-063 Kraków, Poland An alternative approach to the structural investigations of exfoliated polymers was developed. This approach is based on modeling of LpG2 factors recorded from oriented samples. A Java computer program which calculates the one-dimensional structure of the polymer on the surface of smectite was written. The program uses genetic algorithms as a minimalization procedure, to optimize the structure by minimizing the differences between the experimental LpG2 factor and the theoretical X-ray pattern of smectite layer with a hypothetical structure of polymer on its basal surfaces. It allows to solve an approximate one-dimensional structure of polymer adsorbed on the 001 surface of smectite, but requires the assumption about the polymer/smectite mass ratio. This approach was used to solve the structure of polivynylpyrrolidone (PVP) adsorbed on the surface of smectite. It was found that, although LpG2 factors for various smectites are quite different, the structure of polymer is not affected by the charge of smectitic layer, nor by the location of this charge in the tetrahedral or octahedral positions. There is an enhancement of the polymer concentration at distances closer to the clay layer. It seems that PVP chains that are directly bonded to the surface are more rigid, while the outer parts - more flexible. Using this approach it was also possible to determine the average thickness of the polymer layer, which is of about 6-7 Å. The generalized configuration of PVP on smectite can be used as a model for other surfaces of smectitic character, e.g. the surface of illite fundamental particles.

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BENTONITE RESOURCES IN JAPAN, SUPPLY AND FUTURE DEMAND Tetsuichi Takagi Institute of Geo-Resources and Environment, Geological Survey of Japan, AIST, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 Japan; [email protected] The Japan Arc has an abundance of bentonite resources. So far, production from domestic mines has been almost enough to fully meet the demands of Japanese industry. Bentonite deposits in the Japan Arc are embedded entirely in Miocene to Pliocene sedimentary rocks accumulated in extensive back arc basins, and are largely divided into the following two types in terms of their field occurrences: stratified deposits and irregular-shaped massive deposits. The former are generally middle- to large-scale Na or Ca-Na bentonite deposits of diagenetic origin, whereas the latter are small-scale Ca bentonite deposits of hydrothermal origin (Takagi et al., 2005). The former and latter type deposits tend to occur in the northeastern and southwestern Japan Arc, respectively. Tsukinuno deposit is typical of the former type, comprising 31 bentonite layers of several cm to 7m thick; the only source of Na bentonite in Japan. Tsukinuno mine, the largest bentonite mine in Japan, has been mining underground since 1949. Kunigel V1, standard Na bentonite in Japan, is a representative product of this mine. Kawasaki deposit is also typical of the former type, comprising a bentonite (Ca-Na) layer some 20m thick; here, an open-pit of some 450m in diameter is still being worked. Production from these two deposits alone accounts for almost 50% of total domestic production. The latter type deposits (e.g., Dobuyama deposit) are commonly of small-scale, and their production is insignificant. The total consumption of bentonite in Japan is approximately 600,000 tonnes/year, of which 140,000 to 200,000 tonnes/year are imported from China, the United States, and India. Domestic production has been almost stable since the 1980s due to the stable demand of domestic automobile industries (foundry) and civil engineering. In Japan, use of a large volume of Na bentonite for buffer materials of radioactive waste disposal sites has been scheduled for the near future (low-level waste) and beyond 2040 (high-level waste). The estimated demand for buffer materials totals at least 2 to 3 million tonnes. To meet future demands, further development of supply sources of Na bentonite is an important issue for Japanese bentonite users. In Japan, exploration targets for Na bentonite may only include subsurface deposits because Na bentonite is not well preserved on/near the surface due to the pluvial climate. However, such development requires large expenditure in terms of both cost and time. In the case of imported ore, few Na bentonite deposits have been found in China and Southeast Asia. The potential source areas are the United States, India, and the Russian Far East; we need more detailed information on geology and economic methods of ore freight regarding these areas. Takagi, T., et al. (2005) Geology and properties of the Kawasaki and Dobuyama

bentonite deposits of Zao region in northeastern Japan. Clay Minerals, 40, 333-350.

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RESERVOIR QUALITY OF LOUISIANA MIOCENE SHELF SANDSTONES, GULF OF MEXICO: CLAYS ARE THE KEY Andrew Thomas 1, Doug McCarty 1, Mark Filewicz 2, Matt Johnson 2, Tom Dunn 1 and Marek Kacewicz 1 1 Chevron Energy Technology Co, Houston, TX [email protected] 2 Chevron GOMDW Exploration Miocene reservoirs in south-central Louisiana were deposited in a variety of shelf environments ranging from distributary channels, fluvial point bars, to upper/middle shoreface sequences as interpreted from logs and cores. These reservoirs are found today at >150C, increasing geologic risk due to porosity reduction. Two conventionally cored wells were assessed for reservoir quality variability and mineralogy using computer simulation of X-ray patterns from oriented clay mineral preparations, sandstone petrographic methods, basin modeling methods, and diagenesis modeling methods. Diagenetic trends reveal that there is a negative correlation between porosity and quartz cement. Additionally, clay coatings are found to exist over the same interval in varying quantities, and where present inhibit quartz cementation. Highly bioturbated lower shoreface rocks contain clay coatings which range from 40% to 65% grain coat completeness. These coatings are more complete than those found in other non-bioturbated deltaic environments. The coated sandstones have significantly lower quartz cement volumes than their nearshore equivalents and consequently better reservoir quality present day. The origin of the higher grain coat completeness in the distal shoreface sands is not clear, but is thought to be related to interaction between the sediments and bioturbating organisms in the depositional system. Clay mineralogical detail reveals the coatings contain dominantly R1 illite/smectite and minor chlorite.

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CHOICE OF STANDARDS: A MAJOR VARIABLE IN QUANTITATIVE X-RAY DIFFRACTION (QXD) WITH ROCKJOCK Christine L. Thomas and Ray E. Ferrell, Jr. Department of Geology & Geophysics, Louisiana State University, Baton Rouge, LA 70803. [email protected] The Reynolds Cup has promoted a renewed interest in quantification of mineral abundance by XRD methods and many analytical innovations have been spurred by the competition. One of these, RockJock, is an EXCEL spreadsheet developed by D. Eberl (2003). It employs an internal intensity standard, reference intensity ratio corrected single mineral standards and whole pattern fitting to determine quantities of minerals in complex mixtures. This presentation explores the effects of standard selection on quantitative analysis bias. Patterns obtained by Eberl for the 2004 Reynolds Cup were analyzed by RockJock with five different forms of K-bearing feldspar; intermediate microcline, ordered microcline, sanidine, orthoclase, and anorthoclase. Typical results (not normalized) varied from 4.0 to 10.9 wt% K-spar for a sample containing 2.1 wt% K-spar, producing a bias ranging from 1.9 to 8.8. Ordered microcline produced the lowest bias. The sum of all minerals present ranged from 125.9 to 127.1 wt%. Significant differences were observed for all samples used in the competition. The magnitude and variability of the bias is strongly dependent on the standard utilized. In samples with feldspar quantities below approximately 5 wt%, it may be very hard to obtain XRD criteria to aid in the selection of the standard. The bias can only be reduced if other techniques can be employed to identify the feldspar(s) present. Standards representing other minerals with greater chemical and structural variability are even more difficult to select, adding to the potential analytical bias. Eberl, D.D., 2003 User guide to RockJock - A program for determining quantitative

mineralogy from X-ray diffraction data: U.S. Geological Survey Open File Report 03-78, 36 p.

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CHARACTERIZATION OF CLAY MINERALS IN THE ALBERTA OIL SANDS Peter Uhlik 1,2, Ali Hooshiar 1, Oladipo Omotoso 3, Thomas H. Etsell 1, Qi Liu 1 and Douglas G. Ivey 1 1Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, T6G 2V4, Canada; [email protected] 2Department of Geology of Mineral Deposits, Comenius University in Bratislava, Slovakia 3Natural Resources Canada, CETC-Devon, #1 Oil Patch Drive, Devon, AB, T9G 1A8, Canada The Athabasca oil sands are large deposits of bitumen located in northeastern Alberta, Canada. The amount of clay minerals in the oil sands is relatively low, usually under 10 wt%. However, clay minerals play an important role in the aqueous extraction of bitumen from surface-mined oil sands. The clay minerals influence process water chemistry, interact with bitumen to reduce bitumen recovery and froth quality, and control the settling behaviour of fine tailings. The waste tailings are primarily clay slurries, and close to 1 Bm3 are currently stored in containment ponds. Although a viable nonaqueous bitumen extraction process is yet to be commercial demonstrated for the Athabasca oil sands, it has the potential for high bitumen recovery and elimination of large containment facilities for clay slurries. This study evaluates the distribution of clay minerals in the process streams of a nonaqueous extraction process. Two oil sands ores were studied, a high grade, low fines (< 45 µm), good processing ore and a low grade, high fines, poor processing ore (here “good’ or “poor” processing is with reference to the Clark Hot Water Extraction process). The clay mineralogy of the separated solids from the solvent extraction product - a supernatant and the associated tailings, as well as the raw oil sands ores and solids from streams after the hot water extraction was investigated. Treated samples were quantitatively analysed by x-ray diffraction (XRD) to determine the distribution of clay minerals in the different sample streams. Clay fractions (< 2 µm) were analysed by the calculated mineral reference intensities method (Moore and Reynolds, 1997), and the fines fraction by whole pattern fitting (RockJock; Eberl, 2003) and by Rietveld analysis (TOPAS; Bruker AXS, 2000). The results show that the kaolinite to illite ratio is higher in the supernatant when compared to the raw ore. This difference seems to be due to the higher affinity of the kaolinite particles for bitumen and non-polar solvents. Bruker AXS (2000): TOPAS V2.0: General profile and structure analysis software for

powder diffraction data. - User Manual, Bruker AXS, Karlsruhe, Germany. Eberl, D.D., (2003) User’s guide to RockJock – a program for determining quantitative

mineralogy from powder X-ray diffraction data. U.S. Geological Survey, Open-File Report 03-78.

Moore, D. M. and R. C. Reynolds, Jr. (1997) X-ray diffraction and the identification and analysis of clay minerals, 2nd Edition, Oxford University Press, USA, 378 p.

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RADIOGENIC ARGON AS AN INDICATOR OF MICA REMNANTS IN HYDROXY-INTERLAYERED VERMICULITE J. M. Wampler 1 and W. Crawford Elliott 2 1Department of Geosciences, Georgia State University, Atlanta, GA 30302, USA; [email protected] 2Department of Geosciences, Georgia State University, Atlanta, GA 30302, USA Kaolinite and hydroxy-interlayered vermiculite (HIV) are the predominant clay minerals in upland soils of the Savannah River Site (SRS) in the upper coastal plain of South Carolina. Potassium in the clay fractions of five soil samples averages 7 g/kg (standard deviation 1 g/kg), but there are no peaks for illite or K-feldspar in X-ray diffraction (XRD) patterns from oriented films of these clays. These observations are consistent with earlier findings that HIV in coastal plain soils of Alabama (Kirkland and Hajek, 1972) and Florida (Harris et al., 1992) contain substantial amounts of non-exchangeable potassium attributable to remnants of a mica precursor within HIV grains. We have measured argon isotopes and potassium in portions of B-horizon samples of the Fuquay and Orangeburg soil series at the SRS and in other portions of these samples after they had been leached with strong acid. Preliminary K-Ar age values for the Fuquay and Orangeburg samples are 340 million years and 440 million years respectively. Leaching portions of the samples for three hours with 10% nitric acid near 80°C removed some of the potassium from the soils but very little of the radiogenic argon. Preliminary K-Ar age values for the leached residues are 510 million years and 530 million years, respectively. Stronger leaching (three hours in 50% nitric acid near 100°C) removed a larger fraction of the potassium and some of the radiogenic argon from a portion of the Fuquay sample, leaving a residue with a preliminary K-Ar age value of 520 million years. We interpret these results as showing that most of the potassium in these soils is in remnants of mica derived from Paleozoic and Precambrian rocks of the Appalachian Mountain belt. Most (>70%) of the potassium in these soils is in the clay fraction, where HIV is the only 2:1 clay mineral evident by XRD, which indicates that the mica remnants are very small domains within clay-sized HIV particles. The presence of radiogenic argon in sufficient amount to give consistent K-Ar age values near 500 million years indicates that these domains have remained closed to chemical exchange throughout the extended period of chemical weathering that has converted muscovite-bearing Tertiary sands of the upper coastal plain into the HIV-bearing sandy soils of the present-day SRS. Harris, W.G., Morrone, A.A., and Coleman, S.E. (1992) Occluded mica in hydroxy-

interlayered vermiculite grains from a highly-weathered soil, Clays and Clay Minerals, 40, 32-39

Kirkland, D.L and Hajek, B.F. (1972) Formula derivation of Al-interlayered vermiculite in selected soil clays, Soil Science, 114, 317-322

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BEHAVIOR OF WATER MOLECULES IN MORDENITE SOLID SOLUTIONS Jie Wang and Philip S. Neuhoff Department of Geological Sciences, University of Florida, 241 Williamson Hall, Gainesville, FL 32611-2120, USA; [email protected] Mordenite is a common rock-forming zeolite with high ion-exchange capacity. Natural mordenite contains relatively large amount of water, up to 15% (Passaglia, 1975), and generally includes at least two extra framework cations in the crystal structure. Because the cations and water molecules are both located in the zeolitic channels, changes in cation content can influence the amount and site occupancies of water molecules in mordenite. A series of Na-K-mordenite solid solutions were generated by binary ion exchange between pure synthetic Na-mordenite and chloride solutions containing Na+ and K+ of different equivalent concentration ratios. The water contents of these solid solutions were measured by thermogravimetric analysis, and the results showed that the water content decreases with increasing mole fraction of K+ (XK+). Three energetically distinct water sites were observed in mordenite based on the differential scanning calorimetric (DSC) data: the lowest energetic site (W1) in which the water is similar in energy to water and very sensitive to the humidity change; the relatively higher energetic site (W2) with a corresponding peak in the DSC at ~ 60 °C and the water in this site is independent of the XK+; the highest energetic site (W3) which is affected by the variation of cation composition in the solid solutions. In comparison with the structure refinement study of the stepwise dehydration process in mordenite (Martucci et al., 2003), the water sites (C, D, G and H), in which water loss was observed at temperatures lower than 300 °C, correspond to W2 in this study; and the sites (B, J, and E), with dehydration above 300 °C, are similar to W3. The enthalpy of hydration (ΔHHyd) of mordenite at 25 °C was determined by the isothermal immersion technique. A linear relationship (with some uncertainty) was demonstrated between the ΔHHyd and XK+. ΔHHyd of mordenite becomes less exothermic with increasing XK+. Passaglia, E. (1975) The crystal chemistry of mordenites, Contributions to Mineralogy

and Petrology, 50, 65-77. Martucci, A., et al. (2003) In situ time resolved synchrotron powder diffraction study of

mordenite, European Journal of Mineralogy, 15, 485-493.

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THE SYNTHESIS OF AL-MCM-41 FROM VOLCLAY -A LOW-COST AL AND SI SOURCE M. Adjdir 1, T. Ali-Dahmane 2, F. Friedrich 1, T. Scherer 3 and P.G. Weidler 1

1Institute of Functional Interfaces, Division of Nanomineralogy, Forschungszentrum Karlsruhe GmbH, D-76021 Karlruhe, Germany; [email protected] 2Materials Chemical Laboratory, University of Oran BO: 31100 Oran Es-Sénia, Algeria. 3Institute for Nanotechnology Forschungszentrum Karlsruhe GmbH, D-76021 Karlsruhe, Germany The alkaline fusion of Volclay (a low-cost sodium exchanged smectite) was used as source to generate the Si and Al components which were effectively transformed into mesoporous Al-MCM-41 depending on hydrothermal condition. The Al-MCM-41 materials were investigated by powder X-ray diffraction (XRD), N2 adsorption–desorption measurement and both scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM). The Volclay which converted into a silicon and an aluminium source allowed the formation of well ordered mesoporous Al-MCM-41 materials with high aluminium content (roughly 3 times higher than a Al-MCM-41produced by a standard method), a high surface area (1060 m2/g), a pore volume of 0.77 cm3/g (for pore width < 7.1 nm) with an mono-modal pore distribution with a maximum in the mesoporous pore size of 3.8 nm in pore width.

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COMPLEX GENETIC EVOLUTION OF SURFACE COATINGS ON RESPIRABLE QUARTZ GRAINS CONTROLS CYTOTOXICITY IN THE LUNG Richard F. Wendlandt 1, Millicent P. Schmidt 1,2 and Wendy J. Harrison 1

1Dept. of Geology, Colorado School of Mines, Golden CO 80401 USA; [email protected] 2 Dept. of Geosciences, Stony Brook Univ., Stony Brook, NY 11790 Quartz grains in commercial bentonites are characterized by pervasive coatings of montmorillonite (up to 2 µm thick) that are resistant to removal by mechanical abrasion and chemical dissolution. These coatings modify the surface properties of respired quartz grains by sequestering the grain from contact with lung cells and fluids thereby affecting biodurability and potential cytotoxicity. To understand origins of these coatings, samples of volcanic ash with varying ages and degrees of glass alteration to montmorillonite were investigated. FE-SEM characterization of quartz grain separates from these ash units indicates the pervasive presence of volcanic glass related to the eruptive origin of these grains. As glass alteration progresses, quartz surfaces start to develop patches of montmorillonite that become continuous in extent on quartz grains in bentonites. Modified batch reaction experiments on SAz-2 and “western” montmorillonites conducted in simulated lung and lysosomal fluids (pH 7.40 and 4.55, respectively) yield dissolution rates based on BET surface areas and Si steady state release that range from 5.9x10-15 mol/m2/s in lung fluid to 1.5x10-14 mol/m2/s in lysosomal fluid. Biodurabilities calculated using a shrinking sphere model that accounts for complete dissolution of a 1 µm diameter montmorillonite particle range from 900 to 2300 years; thus, clay coatings on respired quartz grains can sequester the latter for periods well in excess of the human lifespan. By comparison, the particle lifetime of high silica volcanic glass (i.e., Bishop tuff, SiO2 = 72.62 wt%), calculated for complete dissolution of a 1 µm diameter sphere and using a dissolution rate determined at pH = 4.20 in HCl solution and based on BET surface areas (Wolff-Boenisch et al., 2004), is approximately 130 years. To constrain these widely ranging biodurabilities obtained for different dissolution environments, batch dissolution experiments on individual quartz grains from the Lava Creek (Yellowstone Caldera) and Bishop (Long Valley Caldera) Tuffs and “western” bentonite in lysosomal fluids were conducted for 30 days, followed by reaction for 60 additional days. Grain surfaces were characterized by FE-SEM prior to and following each batch experiment. We document complex surface properties on respirable quartz grains. Recognition of these properties is of critical importance in developing integrated and meaningful solutions to understanding pathogenic tendencies of quartz. Wolff-Boenisch et al. (2004) The dissolution rates of natural glasses as a function of their

composition at pH 4 and 10.6, and temperatures from 25 to 74oC. et al., Geochim. Cosmochim. Acta 68, 4843-4858.

149

MINERALOGICAL CHARACTERISATION OF NONTRONITE FOLLOWING INTERACTION WITH BACTERIA AND NITROBENZENE Maggie L. White, Claire I. Fialips and Dulce Perez Ferrandez

Newcastle University, School of Civil Engineering and Geosciences, Drummond building, Newcastle-Upon-Tyne NE1 7RU, United-Kingdom; [email protected] Clay minerals are widely used in environmental engineering applications due to their specific physical and chemical properties and their high abundance in soils in sediments. In working towards attaining ‘good status’ for all European groundwaters by 2015 (Water Framework Directive 2000/60/EU), a permeable Bio Fe-clay barrier is being developed which targets redox-sensitive organic groundwater contaminants. Currently Fe-smectites, such as nontronite, are not widely exploited in applied environmental fields. However, these clays may contain up to 20wt% of Fe2O3 as structural Fe(III) and if a suitable electron donor is available, the Fe(III) can be utilized by Fe-reducing bacteria as a terminal electron acceptor resulting in substantial Fe(III) reduction within the clay. Moreover, when reduced the overall reactivity of Fe-smectites changes, particularly where interactions with water and various organic compounds are involved. For instance, the presence of reduced Fe-smectites has been found to induce the degradation of certain subsurface organic contaminants commonly found in groundwaters as a result of agricultural and industrial activities, e.g. chlorinated aliphatics and nitroaromatic compounds. In the initial stages in the development of the Bio-Fe clay barrier, the iron-reducing bacterium Shewanella algae BrY was used to reduce structural Fe(III) in <2micron fractions of the Fe-rich smectite nontronite (NAu-2, 41.74wt% Fe2O3). S. algae BrY reduced structural Fe(III) within the nontronite to a maximum Fe(II)/Fe(II)+Fe(III) ratio of 0.34 in the presence and absence of the electron shuttle, AQDS (9, 10-anthraquinone-2, 6-disulfonic acid). Nitrobenzene was selected as the test redox-sensitive organic compound as it is a common subsurface contaminant and is of global ecotoxicological concern. To test the capability of the bio-reduced nontronite to transform nitrobenzene to aniline (the less toxic and more stable degradation product of nitrobenzene), nontronite suspensions with reduction levels of 20% and 30% were spiked with various concentrations of nitrobenzene and monitored for 5 days. Results showed that the most rapid transformation of nitrobenzene to aniline (100% recovery within 4 hours) occurred when reduced nontronite, S. algae BrY and AQDS were all present. Bio-reduced nontronite alone is also capable of degrading nitrobenzene but at a rate ~20 times slower than when AQDS is present. Bio-reduction level of nontronite was also found to affect nitrobenzene degradation rate: greater clay reduction levels were associated with the highest rates of nitrobenzene degradation. This is thought to be due to availability of active reducing sites. Preliminary IR studies show that nitrobenzene is incorporated into the nontronite interlayer following interaction and water content is reduced, although other structural and mineralogical changes associated with nontronite-nitrobenzene interaction have not been well characterized. Results to date will be presented.

150

MINERALOGICAL AND CHEMICAL COMPARISON OF ANTIBACTERIAL CLAYS Lynda B. Williams 1, Dennis D. Eberl 2, David M. Metge 2, Ronald W. Harvey 2

1Arizona State Univ., Tempe, AZ 85287-1404 USA; [email protected] 2U.S. Geological Survey, 3215 Marine St., Boulder CO 80303-1066 USA Medicinal and therapeutic uses of clay minerals have been documented based on the extraordinary absorptive/adsorptive properties of clay minerals and the health benefits recognized in aiding digestive processes or cleansing and protecting the skin. Kaolins adhere to the gastrointestinal mucosa as a protective coating, or absorb and rid the body of dissolved toxins, bacteria, and viruses. While the ability to absorb water and organic matter is a common attribute of many smectites, we have identified certain clays that do not physically adhere to bacteria, but are antibacterial against a broad spectrum of human pathogens including antibiotic resistant strains. Preliminary studies on three antibacterial clays led to the hypothesis that specific minerals within the clay samples inhibit growth of clinically relevant bacterial pathogens. The bactericide results from a chemical reaction, potentially buffered by the clay mineral surface, which may disrupt an essential physiological function. A comparison among the antibacterial clays shows: (1) Antibacterial clays are all different in their mineralogical makeup, but each contains a variety of smectite, which imparts an extensive surface area for biogeochemical interactions. (2) The three antibacterial clays tested contain minerals with reduced Fe and other transition metals that may play a role in the antibacterial process by producing reactive oxygen or nitrogen species that potentially degrade organic components critical to cell survival. (3) The antibacterial agent is soluble at extreme pH (<4 or >10) and low oxidation state. (4) There is no physical attraction of the clay to bacteria, and, without water, there is no antibacterial effect. Therefore the antibacterial mechanism involves solution components and chemical reactions affecting the cell wall or metabolic functions. (5) Aqueous clay leachates are antibacterial initially, but lose their effect on bacteria as the solution becomes oxidized. This points to an important role of the clay in buffering the solution chemistry to conditions that promote an antibacterial reaction. We hypothesize that reduced Fe or other transition metals are stabilized by the clay minerals that buffer the aqueous speciation of those elements involved in the antibacterial process.

151

QUANTIFYING CARBON FIXATION IN TRACE MINERALS FROM KIMBERLITE MINE TAILINGS Siobhan A. Wilson, Mati Raudsepp, and Gregory M. Dipple Mineral Deposit Research Unit, Department of Earth and Ocean Sciences, The University of British Columbia, 6339 Stores Road, Vancouver, British Columbia V6T 1Z4, Canada; [email protected] Mineral trapping of carbon dioxide (CO2) in mine tailings can occur at a scale that is significant relative to the greenhouse gas production of a mining operation. The presence of secondary carbonate minerals in mine tailings, even at trace abundances, can therefore represent substantial trapping of CO2. We have assessed the ability of three methods of quantitative X-ray diffraction to measure trace nesquehonite (MgCO3·3H2O) in samples of kimberlite mine tailings: the method of normalized reference intensity ratios (Chung, 1974), the internal standard method (Alexander and Klug, 1948), and the Rietveld method (Rietveld, 1969). Tests on synthetic mixtures made to resemble kimberlite tailings indicate that both the method of reference intensity ratios (RIR) and the Rietveld method can be used accurately to quantify nesquehonite to a lower limit of approximately 0.5 wt.% for conditions used in our laboratory. Below this value, estimates can be made to a limit of approximately 0.1 wt.% using a calibration curve according to the internal standard method. The RIR method becomes increasingly unreliable with decreasing abundance of nesquehonite, primarily as a result of an unpredictable decline in preferred orientation of crystallites. For Rietveld refinements, structureless pattern fitting was used to account for structural disorder in lizardite by considering it as an amorphous phase. Using this method, the presence of amorphous and/or nanocrystalline material in samples of synthetic kimberlite tailings resulted in overestimates of refined abundances for lizardite and underestimates for other phases. Relative errors on refined abundances for major and minor phases are typically in the range of 5 to 20 %. However, absolute errors are sufficiently small that estimates can be made for the amount of CO2 stored in nesquehonite using the RIR method or the Rietveld method for abundances ≥ 0.5 wt.% and a calibration curve for abundances < 0.5 wt.%. We have investigated the extent to which carbon is being mineralized in an active mine setting at the Diavik Diamond Mine, Northwest Territories, Canada. Rietveld refinement results and calibrated abundances for trace nesquehonite are used to estimate the amount of CO2 trapped in Diavik tailings. Alexander, L. and Klug, H.P. (1948) Basic aspects of X-ray absorption in quantitative

diffraction analysis of powder mixtures. Analytical Chemistry, 20, 886-889. Chung, F.H. (1974) Quantitative interpretation of X-ray diffraction patterns of mixtures.

II. Adiabatic principle of X-ray diffraction analysis of mixtures. Journal of Applied Crystallography, 7, 526-531.

Rietveld, H.M. (1969) A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 2, 65-71.

152

GEOLOGY AND MINERALOGY OF A SEPIOLITE-PALYGORSKITE DEPOSIT FROM SW ESKISEHIR (TURKEY) Mefail Yeniyol Department of Geology, 34850 Avcilar, Istanbul University, Istanbul, Turkey, [email protected] Several layered sepiolite deposits occur in the Eskişehir Neogene lacustrine basin. The present occurrence found in the SW Eskişehir contains both sepiolite and palygorskite in economical value. This occurrence was investigated in detail along two representative measured sections by XRD, SEM and chemical analysis. Sepiolite and palygorskite occur in a nearly 40 m thick sequence where dolomite and dolomitic marl beds are frequently represented. At the base of this section, Upper Miocene conglomerates occur in which well-known sepiolites of the meerschaum type quality are locally found throughout the Neogene basin. At the uppermost part of Upper Miocene, palygorskite occurs together with fine-grained detrital material. Lower Pliocene beds rest upon the Upper Miocene discordantly and beginning with an alternation of dolomite and dolomitic marls in which smectite and palygorskite or only smectite are the clay mineral constituents. In the middle part of the sequence, sepiolite is found as separate layers and occurs also in some layers together with palygorskite, in addition to alternating dolomite and dolomitic marls that also contain these phases. Dolomite makes up the upper part of the sequence and contains a few thin sepiolite-palygorskite intercalations. Along the sequences studied, the Mg-rich clay minerals and the mineral paragenesis occur in ascending order as: palygorskite, palygorskite + smectite, smectite, sepiolite and sepiolite + palygorskite in separate beds. Textural relationships observed by SEM revealed that the palygorskite that occurs at the top of Upper Miocene sequence was formed during diagenesis together with dolomite. In the Lower Pliocene sequence, palygorskite, sepiolite and smectite were formed by direct precipitation from solution in an alkaline lake environment. In addition, palygorskite was also formed by transformation from smectite.

153

MINERALOGICAL STUDY OF ISTANBUL SILE-UVEZLI CLAYS Yildiz Yildirim 1 and Gulseher Coban 2 1Kaleseramik Canakkale Kalebodur Seramik Sanayi A.S.- Physical & Chemical Laboratories ;17430 Can,Canakkale – TURKEY, [email protected] 2Kaleseramik Canakkale Kalebodur Seramik Sanayi A.S.– Technical Consultancy Unit ; 17430 Can, Canakkale – TURKEY The physical behavior or rheological properties of clays that come from the same region and that have almost identical chemical analyses may sometimes vary. Mineral groups of clays used in the ceramics industry must be analyzed properly to avoid potential problems during production. Industrial clay deposits of Sile Region constitute almost 60% of Turkey’s clay mines. The chemical composition of Sile Region clay is: 26 -32.7 % Al2O3 ; 15.5 – 57.5 % SiO2 and 1.8 -5.9 % Fe2O3. Kaolinite is the main clay mineral in the deposit. In addition, dioctahedral smectite, illite, K-feldspar, plagioclase, calcite, goethite, hematite and quartz have been identified. Trace minerals such as pyrite, anatase and organics are also present in the region. For this study, one of the Sile Region clays was selected and relevant methods of analysis were applied. Approximately 100 g of mineral sample was ground in a jar mill to obtain smaller chips of rock. Approximately 20 g of this material was dried at 60°C. The material also was treated by an ultrasonic probe for 10 min. Separation of different grain size fractions (<2µm and 2-16 µm) was obtained by the time of settling method based on the Stokes Law. The <2 µm fractions were separated by sedimentation, whereas the <0.2 µm fraction by timed centrifugation. Oriented XRD mounts were analyzed after air-drying and vapor solvation with ethylen-glycol at 60°C for 12h. For separating kaolinite and chlorite, oriented mounts were heat-treated. For the separation and quantification of ferrous minerals in the non-clay minerals fraction a sodium citrate buffer solution was used. Carbonate minerals were removed with some addition of acid. Quantitative analysis with the Rietveld method was applied to the non-clay fraction of the sample. Weight losses after each step were determined and the amounts of minerals were calculated from the weight losses. By using an internal standard addition method and the Rietveld method, the amounts of minerals were determined.

154

ELASTIC MODULI AND NANOHARDNESS OF TALC AND PYROPHYLITE Zhongxin Wei 1, Guoping Zhang 1, Ray E. Ferrell 2 and Stephen J. Guggenheim 3

1Department of Civil & Environmental Engineering, Louisiana State University, Baton Rouge, LA 70803, USA; [email protected] 2Department of Geology & Geophysics, Louisiana State University, Baton Rouge, LA 70803, USA 3Department of Earth & Environmental Sciences, University of Illinois at Chicago, Chicago, IL 60607, USA An accurate determination of the elastic modulus and hardness of a phyllosilicate mineral is important to understand seismological data. Many of the common phyllosilicates, however, are clay minerals, and many of these phases do not form in sufficient crystallite sizes to be readily tested by traditional mechanical testing techniques. A recently developed nanoindentation instrument provides a promising method to study the mechanical properties of small-sized materials, thin films, and coatings. We have used a nanoindenter on natural, well studied samples of a dioctahedral and a trioctahedral phyllosilicate with zero layer charge (and thus no cation occupancy between the 2:1 layers): talc, Mont Windara, Australia and pyrophyllite, Ibitiara, Bahia, Brazil. An MTS XP nanoindenter equipped with dynamic contact module (DCM) and continuous stiffness measurement (CSM) techniques was used to probe the mechanical properties of these minerals at very low indentation depth (< 200 nm). A sharp Berkovich indenter (tip radius < 20 nm) was used to indent the samples. A rigorous testing scheme was established to guarantee the accuracy and reliability of the results. For both minerals, the first discernable discontinuity on the load-displacement curves occurred at 13 nm, i.e., when the indenter penetrated about thirteen layers. The modulus E and hardness H perpendicular to the basal plane were determined by the analysis of the initial smooth part of the load-displacement curves (i.e., without visually discernable discontinuities). These values are: E = 26.8 GPa and H = 3.9 GPa for talc, and E = 19.6 GPa and H= 4.6 GPa for pyrophyllite. These much lower elastic moduli, when compared to muscovite where bare K cations occupy the interlayers with E = 79.3 GPa (Zhang et al., 2009) or 58.6 GPa (Vaughan and Guggenheim, 1986) indicate that the mechanical properties of 2:1 phyllosilicates are highly dependent upon the structure, particularly the interlayer species and the amount of layer charge. Furthermore, this study demonstrated that nanoindentation is capable of discerning the mechanical property changes resulting from even small structural variations in the phyllosilicate minerals. Zhang, G., Wei, Z., and Ferrell, R.E. (2009) Elastic modulus and hardness of muscovite

and rectorite determined by nanoindentation, Applied Clay Science, 43, 271-281. Vaughan, M.T. and Guggenheim, S. (1986) Elasticity of muscovite and its relationship to

crystal structure, Journal of Geophysical Research, 91, 4657-4664.

155

CLAY IN ENGINEERING AND ENVIRONMENT: APPLICATION AND TREATMENT IN ABADAN REFINERY S.R. Shadizadeh and Mansoor. Zoveidavianpoor Petroleum University of Technology, Abadan, Iran, [email protected] A rapidly expanding chemical and petroleum industry has been responsible for great improvements in the quality of urban areas in Iran over the last 100 years. The Abadan Refinery is located between the Arvandrud and Bahmanshir rivers in the highly populated Abadan city. These rivers supplies urban, industrial, and agricultural waters to Abadan city. During the war between Iran and Iraq, leakage of enormous volumes of oil and refined petroleum products from storage tanks and pipelines at the Abadan refinery to the surrounding environment occurred. Underground contamination resulting from that leakage is a serious and a growing environmental concern in Abadan city. In this work, twenty boreholes were investigated by considering petroleum leakage to the surrounding area during and after the war. Geological conditions, stratigraphy and petroleum contamination underlying the Abadan refinery was determined from cores during the drilling of the boreholes. Oil saturation of cores was defined for each borehole. Also, porosity, and density of the cores were measured in this project. Water table fluctuations were measured for a period of one year, to determine the underground water movement patterns at Abadan refinery and the connections with surrounded rivers. The results of sampling underground waters indicate that the contaminated oil was measureable in just two wells; No.3 and No.11. The extent of the petroleum contaminated underground layers was also determined in this study and the results show that the majority of existing petroleum in below-ground stratigraphy at Abadan refinery was absorbed by clay. The average depth of the contaminated units is from the surface to the depth of 4.5 meters. The underground water monitoring wells were completed in such a manner that they could form a unique control system at the Abadan refinery in the future.

156

AUTHOR INDEX

A Adegoroye .............................................................. 36, 47 Adjdir ................................................................... 34, 147 Ali-Dahmane ........................................................ 34, 147 Amonette ............................................................... 26, 48 Amouric ................................................................. 32, 73 Aronson ............................................................... 32, 115 Asgar-Deen .......................................................... 32, 115 Austin ..................................................................... 38, 49

B Baioumy ................................................................. 32, 88 Banaś ...................................................................... 32, 73 Bangira ................................................................... 28, 50 Barrientos Velazquez ........................... 27, 38, 51, 72, 75 Barton .................................................................. 29, 131 Beall ................................................................. 33, 52, 53 Benson ................................................................... 26, 85 Bhattacharyya ......................................................... 36, 76 Bish ........................................................................ 25, 62 Bishop ........................................................ 26, 27, 54, 77 Blum ....................................................................... 34, 55 Bobet .................................................................... 28, 105 Bobos ..................................................................... 31, 56 Boyd ....................................................... 37, 57, 103, 112 Bristow ..................................................... 28, 34, 58, 121 Brown ........................................................................... 81 Bulger ..................................................................... 35, 59

C Cervini-Silva ........................................................... 26, 60 Chen ....................................................................... 27, 61 Chipera ................................................................... 25, 62 Chorover .................................................. 37, 38, 84, 129 Christidis .......................................................... 25, 63, 64 Chrysochoou .......................................................... 30, 65 Clarke ................................................................... 28, 105 Clauer ............................................................... 32, 66, 67 Coban ................................................................... 34, 153 Constan .................................................................. 35, 68 Curtiss .................................................................... 31, 90 Cygan ...................................................................... 27, 69

D Day ................................................................... 28, 50, 70 DeArmitt ................................................................ 33, 71 Deng ........................................ 27, 28, 38, 50, 51, 72, 75 Derkowski .............................................................. 32, 73

Detellier .................................................................. 27, 74 Diaco ....................................................................... 27, 74 Ding ..................................................................... 37, 112 Dipple .................................................................. 30, 151 Dixon ................................................... 27, 38, 51, 72, 75 Donahoe ................................................................. 36, 76 Dong .......................................................... 26, 27, 54, 77 Dowd ...................................................................... 38, 49 Drits ..................................................................... 25, 114 Drnevich .............................................................. 28, 105 Duke ....................................................................... 28, 78 Dunn .................................................................... 37, 142

E Eberl ... 25, 30, 31, 34, 38, 55, 56, 64, 79, 92, 125, 132,

144, 150 Ece .......................................................................... 31, 80 Eisenhour ............................................................... 24, 81 Ekinci ...................................................................... 31, 80 Elliott .............................................................. 32, 82, 145 Elmore .................................................................... 32, 82 Engel ....................................................................... 32, 82 Esenli ...................................................................... 31, 80 Etika ........................................................... 34, 39, 94, 95 Etsell .................................................................... 36, 144

F Fabris ................................................................... 26, 122 Fenter ................................................................... 37, 111 Ferrandez ....................................................... 28, 83, 149 Ferrell ...................................... 25, 35, 37, 113, 143, 154 Fialips ............................................................. 28, 83, 149 Filewicz ................................................................ 37, 142 Fishman .................................................................. 34, 55 Friedrich .............................................................. 34, 147 Frommell ............................................................. 36, 133

G Gamboa .................................................................. 26, 93 Gao ......................................................................... 37, 84 Gardiner .............................................................. 38, 117 Gates ................................................................ 26, 85, 86 Gilg ............................................................. 32, 35, 87, 88 Glasmann ................................................................ 31, 89 Goetz ....................................................................... 31, 90 Goyne ..................................................................... 37, 91 Gräfe .................................................................... 28, 137 Grauch .................................................................... 30, 92 Greathouse ............................................................. 27, 69 Grubb...................................................................... 30, 65 Grunlan ............................. 26, 33, 34, 39, 93, 94, 95, 96

157

Guggenheim ......................................................... 35, 154 Guthrie ................................................................. 36, 133 Guven ..................................................................... 26, 97

H Haack ................................................................... 34, 101 Hallmark ................................................................ 28, 50 Harrison ............................................................... 38, 148 Harvey .................................................................. 38, 150 Hegner ................................................................... 32, 88 Helfrich .................................................................. 33, 98 Herbert ................................................................. 38, 117 Herpfer .................................................................. 31, 99 Hervig ................................................................... 32, 128 Hess ............................................................ 34, 39, 94, 95 Hill ......................................................................... 34, 55 Hillier ................................................................... 32, 115 Hines ...................................................................... 26, 85 Hinman ................................................................ 39, 135 Hochella ................................................................. 24, 42 Hölzl ....................................................................... 32, 88 Honty ..................................................................... 32, 67 Hooshiar .............................................................. 36, 144 Horner ......................................................................... 40 Howard ................................................................ 36, 133 Huff .......................................................... 25, 39, 63, 100 Hunter .................................................................. 34, 101

I Inanli .................................................................... 39, 100 Ives ....................................................................... 34, 126 Ivey ......................................................... 34, 36, 126, 144

J Jaisi ......................................................................... 27, 54 Jang ......................................................................... 26, 93 Jaynes ................................................................... 38, 102 Ji

Junfeng.............................................................. 27, 54 Shanshan .......................................................... 26, 77

Johnson ................................................................ 37, 142 Johnston ............................ 27, 28, 37, 57, 103, 104, 105

K Kacewicz............................................................... 37, 142 Kaur...................................................................... 28, 137 Kennedy

Brendan J. ....................................................... 28, 137 Martin J........................................................... 28, 121

Kibanova ................................................................ 26, 60 Kim ....................................................................... 27, 127 Kirst ...................................................................... 37, 113 Kleeberg ............................................................... 25, 106 Kleinmann ........................................................... 36, 133 Komadel ................................................. 26, 27, 107, 108

Kosel .................................................................... 29, 131 Kotler ................................................................... 39, 135 Kukkadapu ............................................................. 27, 54 Kyle ...................................................................... 39, 134

L Laird ......................................................... 37, 40, 57, 109 Lan ....................................................................... 33, 110 Lear ...................................................................... 26, 108 Lee ....................................................................... 37, 111 Lerch ....................................................................... 37, 91 Lerman ................................................................... 32, 66 Letaief ..................................................................... 27, 74 Lewis ....................................................................... 28, 78 Li

Hui ........................................................... 37, 57, 112 Yu-Chin ............................................................. 26, 93

Lin ........................................................................... 37, 91 Little ..................................................................... 38, 117 Liu

Lei ........................................................ 34, 39, 94, 95 Qi .................................................................. 36, 144

Loeppert ................................................................. 28, 50 Luo .......................................................................... 27, 75

M Madejova ............................................................. 27, 107 Marroquin-Cardona ..................................................... 51 Martin .................................................................. 34, 132 Masliyah .................................................................. 36, 47 Maurice .................................................. 29, 34, 101, 131 Mbamalu .............................................................. 37, 113 McCarty ................................................. 25, 37, 114, 142 Metge ................................................................... 38, 150 Meyer ................................................................... 32, 115 Miles .................................................................... 24, 116 Miller ................................................................... 38, 117 Mohtar ................................................................. 28, 105 Moll ......................................... 33, 38, 39, 118, 119, 120 Morrison .................................................. 28, 34, 58, 121 Murad .................................................................. 26, 122 Murray .................................................................... 30, 43

N Nadeau .................................... 32, 36, 39, 115, 123, 124 Nagy ..................................................................... 37, 111 Nenoff ..................................................................... 27, 69 Neuhoff ................................................................ 25, 146 Neupane ................................................................. 36, 76 Ngameni ................................................................. 27, 74 Nieto-Camacho ...................................................... 26, 60

O Ockwig .................................................................... 27, 69 Omotoso ........................... 25, 34, 36, 47, 125, 126, 144

158

P Palomino .............................................................. 27, 127 Park ...................................................................... 37, 111 Patra ..................................................................... 34, 101 Pauly ..................................................................... 32, 128 Pentrak ................................................................. 27, 107 Perdrial ................................................................. 38, 129 Pinnavaia .............................................................. 37, 103 Premachandra ...................................................... 27, 104 Priolo ...................................................................... 26, 93 Pruett .................................................................... 31, 130

Q Quicksall ................................................ 29, 34, 101, 131

R Rana ..................................................................... 37, 103 Rao ......................................................... 31, 36, 138, 139 Raudsepp ............................................................. 30, 151 Rawson ................................................................... 26, 93 Reid ...................................................................... 34, 132 Richards ............................................................... 32, 115 Richardson ........................................................... 39, 135 Riediger ................................................................ 32, 115 Rocholl ................................................................... 35, 87 Romanov .............................................................. 36, 133

S Sakharov............................................................... 25, 114 Santagata................................................. 27, 28, 104, 105 Scherer ................................................................. 34, 147 Schiffman ............................................................. 32, 128 Schmidt ................................................................ 38, 148 Schroeder ................................................. 38, 39, 49, 134 Schulz ..................................................................... 26, 93 Scott ...................................................................... 39, 135 Sellin ..................................................................... 36, 136 Shadizadeh ........................................................... 37, 155 Shiley ...................................................................... 31, 90 Singh ..................................................................... 28, 137 Sivachidambaram................................... 31, 36, 138, 139 Skiba ..................................................................... 27, 140 Soong.................................................................... 36, 133 Środoń...................................................... 27, 32, 73, 140 Stucki ..................................... 26, 28, 30, 44, 50, 70, 108 Sturchio ................................................................ 37, 111 Sucha ...................................................................... 32, 67

Szczerba ............................................................... 27, 140

T Takagi .................................................................. 24, 141 Taubald ................................................................... 32, 88 Teppen .................................................. 37, 57, 103, 112 Thomas

Andrew ........................................................... 37, 142 Christine ........................................................ 25, 143

Thompson ........................................................... 38, 129 Tonle ...................................................................... 27, 74

U Uhlik .............................................................. 36, 47, 144

W Wampler.............................................................. 32, 145 Wang

Cuiping .......................................................... 37, 112 Hejing ................................................................ 27, 61 Jie .................................................................. 25, 146

Warr ....................................................................... 32, 88 Wei ...................................................................... 35, 154 Weidler ................................................................ 34, 147 Wendlandt ........................................................... 38, 148 White ............................................................. 28, 83, 149 Williams.............................. 24, 32, 38, 45, 67, 128, 150 Wilson ................................................................. 30, 151 Wu .......................................................................... 37, 91

X Xu ........................................................................... 36, 47

Y Yang ........................................................................ 26, 77 Yeniyol ................................................................. 39, 152 Yildirim ................................................................ 34, 153

Z Zartman ............................................................... 38, 102 Zhang

Guoping ......................................................... 35, 154 Jing..................................................................... 26, 77 Xialin ................................................................. 27, 61

Zhuang .................................................................... 28, 83 Zoveidavianpoor .................................................. 37, 155

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