NSLS-II User Workshop, July 2007

NSLS-II Environmental Sciences Breakout Session

Antonio Lanzirotti (U. Chicago) Welcoming Remarks

Review of NSLS Molecular Environmental Sciences statistics. How are MES researchers utilizing the NSLS.

Overview of U.Chicago CARS MES research and future directions (10 minutes)

Richard Reeder (Stony Brook U.) EnviroSync MES community efforts

Overview of Stony Brook MES synchrotron research and future directions

(10 minutes)

Jeff Fitts (BNL Env. Sciences) BNL EnviroSuite initiative (10 minutes)

Satish Myneni (Princeton U.) Overview of Princeton U. Molecular Environmental Chemistry synchrotron research and future directions

(10 minutes)

Matt Ginder-Vogel (U. Delaware) Overview of U. Delaware Environmental Soil Chemistry synchrotron research and future directions

(10 minutes)

Unscheduled Presentations Open Presentations by Attendees (15 minutes)

NSLS-II Techincal Review Brief Overview of proposed capabilities of NSLS-II. Impact for the MES community

(10 minutes)

Open Discussion What are the requirements of the community for continued high quality MES research at NSLS-II?What new research that will be made possible by NSLS-II?Of the techniques potentially available at NSLS-II, which are the highest priorities? What is the preferred mode of access for the community? Dedicated beamlines? General User access only? How should planning/design/proposal writing/operations teams be organized/supported? What existing equipment is likely to be transferable?

(30 minutes)

Closeout Recommendations of the community to NSLS-II (15 minutes)

NSLS-II User Workshop, July 2007

NSLS-II User Workshop, July 2007

NSLS MES Publications 1998-2007 % by Technique

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

Hard X-RayMicroprobe

Soft TransmissionX-Ray Microscopy

X-Ray AbsorptionSpectroscopy

Infra-RedMicrospectroscopy

X-Ray Diffraction

% o

f P

ub

lica

tio

ns

NSLS-II User Workshop, July 2007

Total Publications for NSLS% of NSLS MES Publications

by Beamline 1998-2007

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20.0

25.0

30.0

35.0

40.0

Beamline Port

% o

f to

tal M

ES

Pu

bs

Hard X-Ray MicroprobeSoft Transmission X-Ray MicroscopyX-Ray Absorption SpectroscopyInfra-Red MicrospectroscopyX-Ray Diffraction

NSLS-II User Workshop, July 2007

% Oversubscription by TechniqueCycle 2, FY 2007, January through April 2007

0.0

50.0

100.0

150.0

200.0

250.0

Hard X-RayMicroprobe

Soft TransmissionX-Ray Microscopy

X-Ray AbsorptionSpectroscopy

Infra-RedMicrospectroscopy

X-Ray Diffraction

% O

ve

rsu

bs

cri

pti

on

2

2

8

56

NSLS-II User Workshop, July 2007

NSLS-II Workshop DeliverablesNSLS-II Workshop Deliverables

• What are the key scientific drivers? What experiments will NSLS-II enable that are not presently possible?

• What technical capabilities will these require? (Beamlines, endstations, undulators…)

• Estimate of community size. • What detector requirements does this field have? Do these

require R+D?• What software and computing infrastructure requirements are

there? (Control, data acquisition, analysis)• Any particular accelerator requirements?• Any particular conventional facility requirements?

Report Summarizing what was learned will be sent to DOE by COB August 5th.

NSLS-II User Workshop, July 2007

Why an X-ray microprobe: Distinct advantages over many analytical techniques by allowing analyses to be done in-situ and/or in-vivo, for example being the ability to determine chemical speciation of a wide variety of toxic elements in moist soils and biological specimens with little or no chemical pretreatment, low detection limits, and minimal beam interaction.

Multiple Complimentary TechniquesµXRF and elemental mapping: Spot XRF analyses of trace element composition.µXAFS: Spot XANES and EXAFS determinations of oxidation state and speciation.µXRD: In-situ phase identification and correlation with elemental and speciation information.Fluorescence Microtomography: Internal 2D and 3D elemental imaging.

Synchrotron Hard X-Ray Microprobe in Environmental SciencesSynchrotron Hard X-Ray Microprobe in Environmental Sciences

Two KB-Mirror Based X-Ray Microprobes

Beam

LineSource

Beam Size

(µm)Flux @ 10 keV

(ph/s)µXRF µXANES µEXAFS fCMT

NSLS

X26A

Bending Magnet

(2.8 GeV)5-8 2 x 108 1 ppm 10-100 ppm 1000 ppm -1 % 10-100 ppm

APS

13-ID

Undulator(7 GeV)

1 4 x 1011 100 ppb 1-10 ppm 100-1000 ppm 1-100 ppm

NSLS-II User Workshop, July 2007

X-ray optic Diffractive Optics Reflective Optics Refractive Optics

Numerical aperture

High NA possible Limited NA Limited NA

Resolution limit

< 1 nm? − KB: ~ 16 nm

− Wolter:~3nm

CRL: ~ 20 nm

A-CRL: ~ 2 nm

Efficiency 20% - 30% (60%-80%)

70% - 90% 20% - 30%

Chromaticity f ~ 1/λ Non-chromatic f ~ 1/λ2

Features • Monochromatic beam

• On-axis geometry

• Any x-ray energy

• White (pink) beam (non-ML)

• Grazing inc. geometry

• Any x-ray energy

• KB: working distance!

• Monochromatic beam

• On-axis geometry

• Limited energy range

• Long lenses

Limitations •(High aspect ratio/tilt)

•Positioning-alignment

Figure errors Small working distance at high resolution

Modified from Jörg Maser, 2006

X-ray Focusing and Imaging – Current State of the Art

NSLS-II User Workshop, July 2007

State of the art in x-ray imaging and focusing (2D focus):• Refractive Optics: δ ~ 50 nm (E = 21 keV) (Schroer, APL, 2005)• Reflective Optics: δ ~ 40 nm (E ~ 15 keV) (Mimura, JJAP 2005)• Diffractive Optics: δ ~ 15 nm, (E = 0.8 keV) (Chao, Nature, 2005)

What is the ultimate resolution limit for x-ray focusing?• Diffractive optics: ~ 1 nm (Kang, 2006); Å feasible?• Reflective Optics: ~ 16 nm (KB), 3 nm (Wolter) (non-ML)• Refractive Optics: ~ 2 nm (β = 0, Schroer, 2005)

X-ray Focusing and Imaging – Current State of the Art

NSLS-II User Workshop, July 2007

Combined capabilities for small spot size, achromatic focusing, large gain and long working distance.

Achromatic focusing - focus/beam position is retained during an energy scan

Large gain - gains of > 105 achievable, high elemental sensitivity

Long working distance - simplifies use of detectors, optical viewing systems, special sample chambers, etc.

Disadvantage - beam sizes ~ 0.1 micrometer currently unachievable for hard x-rays

Advantages of KB MicrofocusingAdvantages of KB Microfocusing

KB Microfocusing System Designed by P. Eng (U. Chicago)

NSLS-II User Workshop, July 2007

KB Optics NSLS Bend (X26A)

f1 9 m source to optic distance

f2 (H) 0.075 m optic to sample distance

f2 (V) 0.2 m optic to sample distance

m(H) 120 horizontal demag

m(V) 45 vertical demag

x 0.000464 m horizontal source size

y 0.00009 m vertical source size

S' (H) 5.16E-05 m source size

S' (V) 0.00001 m source size'T 1.00E-06 radians 1.00E-07 radians total angular RMS deviation from perfect ellipse

D(H) 1.000752 1.00001 deviation from perfect in horizontal

D(V) 1.019804 1.0002 deviation from perfect in vertical

FWHM(H) 9.09 microns 9.09 microns

FWHM(V) 4.79 microns 4.70 micronsagrees with observations. Also, the mirror imperfections are negligible compared to the angular source size

NSLS-II User Workshop, July 2007

KB Optics NSLS-II Hard X-Ray Undulator (U19)

f1 40 m source to optic distance          

f2 (H) 0.075 m optic to sample distance  

f2 (V) 0.2 m optic to sample distance  

m(H) 533.3333 horizontal demag  

m(V) 200 vertical demag  

x 0.000028 m horizontal source size  

y 2.6E-06 m vertical source size  

S' (H) 7E-07 m source size  

S' (V) 6.5E-08 m source size  'T 1.00E-06 radians 1.00E-07 radians total angular RMS deviation from perfect ellipse

   

D(H) 3.027089 1.04002 deviation from perfect in horizontal  

D(V) 30.78548 3.23534 deviation from perfect in vertical  

   

FWHM(H) 0.37microns 0.13 microns  

FWHM(V) 0.94microns 0.10 microns  

both vertical and horizontal are improved with better mirrors and benders;  close to linear esp. vertical. Improve deviation by factor of 3 and beam gets smaller by ~ that amount  

NSLS-II User Workshop, July 2007

KB Optics NSLS-II Three Pole Wiggler

f1 40 m source to optic distance          

f2 (H) 0.075 m optic to sample distance  

f2 (V) 0.2 m optic to sample distance  

m(H) 533.3333 horizontal demag  

m(V) 200 vertical demag  

x 0.000136 m horizontal source size  

y 1.57E-05 m vertical source size  

S' (H) 3.4E-06 m source size  

S' (V) 3.93E-07 m source size  'T 1.00E-06 radians 1.00E-07 radians total angular RMS deviation from perfect ellipse

   

D(H) 1.160181 1.00173deviation from perfect in horizontal  

D(V) 5.192739 1.12234 deviation from perfect in vertical  

   

FWHM(H) 0.70 microns 0.60 microns  FWHM(V) 0.96 microns 0.21 microns            

NSLS-II User Workshop, July 2007

Zone plate based HXR µprobeZone plate based HXR µprobe

An example is beamline 2ID-D at the APS

•100 nm-width tin oxide nanobelt

NSLS-II User Workshop, July 2007

NSLS II Sources

NSLS-II User Workshop, July 2007

NSLS II Sources

NSLS-II User Workshop, July 2007

Technique: X-ray Micro- Fluorescence, Spectroscopy, DiffractionResearchers:H. Jamieson, S. Walker, C. Andrade, (Queen’s University, Canada), A. Lanzirotti and S. Sutton (U. Chicago, CARS)Publication: Walker, S.R., Jamieson, H.E., Lanzirotti, A. and Andrade, C.F. (2005) Determining arsenic speciation in iron oxides: Application of synchrotron micro-XRD and micro-XANES at the grain scale. Canadian Mineralogist, v. 43, p. 1205-1224

Synchrotron-based µ-XRF mapping, µ-XANES and µ-XRD of arsenic-rich gold mine tailings and lacustrine sediments from Yellowknife

Bay, Canada

Characterize As bearing solids in roaster residue and roaster-derived iron oxides in a subareal weathered tailings horizon

Oxidation state and bonding mechanisms at the scale of individual particle (µ-XANES).

Phase identification (µ-XRD) of individual grains. Objective is to distinguish hematite (-Fe2O3) and maghemite (-Fe2O3).

Chemical mapping of individual grains (µ-XRF).

Understand bioavailability, predict long-term stability, design remediation to ensure As immobility.

Field of view 0.16mm x 0.10mm

Complex zoning at micron scales

hematite (-Fe2O3) and maghemite (-Fe2O3)

NSLS-II User Workshop, July 2007

Synchrotron-based µ-XRF mapping, µ-XANES and µ-XRD of arsenic-rich gold mine tailings and lacustrine sediments from Yellowknife

Bay, Canada

•H. Jamieson, S. Walker, C. Andrade, (Queen’s University, Canada), A. Lanzirotti and S. Sutton (U. Chicago, CARS)

Characterize As bearing solids in roaster residue and roaster-derived iron oxides in a subareal weathered tailings horizon

Oxidation state and bonding mechanisms at the scale of individual particle (µ-XANES).

Phase identification (µ-XRD) of individual grains. Objective is to distinguish hematite (-Fe2O3) and maghemite (-Fe2O3).

Chemical mapping of individual grains (µ-XRF).

Understand bioavailability, predict long-term stability, design remediation to ensure As immobility.

NSLS-II User Workshop, July 2007

Influence of Plutonium Oxidation State on Long-Term Transport Influence of Plutonium Oxidation State on Long-Term Transport through a Subsurface Sedimentthrough a Subsurface Sediment

Pu(IV) and Pu(VI) were placed in Savannah River Site lysimeters (1980) exposed to natural weather conditions, with the intent of evaluating the long-term environmental fate of Pu.

Pu in the Pu(VI)-amended Pu in the Pu(VI)-amended lysimeter traveled ~10 times lysimeter traveled ~10 times faster (12.5 cm yr-1) than the faster (12.5 cm yr-1) than the Pu(IV)-amended lysimeter (1.1 Pu(IV)-amended lysimeter (1.1 cm yr-1)cm yr-1)

MicroXANES showed Pu oxidation state was IV in IV-amended system (undetectable oxidized species)Yucca Mtn Tuff soak experiment

Optical ImageOptical Image

Pu “hot spots” located by Pu “hot spots” located by microXRF mappingmicroXRF mapping

Pu L MicroXANESPu L MicroXANES

•M. C. Duff, D. Kaplan, Savannah River National Laboratory (SRNL), B. Powell, Clemson U., A. Lanzirotti and S. Sutton (U. Chicago, CARS)

NSLS-II User Workshop, July 2007

0.1

1

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100

Ni Fe Cr Mn Cu Ga Ge Se Zn Br

Element (>volatility)

Ab

un

da

nc

e/C

I

IDPs

CI C2

C3

• Potentially most primitive solar system solids • Meteoritic material least altered by atmospheric entry • Hosts of interstellar grains

1 µm

• Total mass ~ 30 picogram (trillionths of a gram)

Interplanetary Dust ParticlesInterplanetary Dust Particles

NSLS-II User Workshop, July 2007

IDPs: Fluorescence MicrotomographyIDPs: Fluorescence Microtomography

• Are the volatile element enrichments indigenous or stratospheric contamination?

• Fluorescence tomography images show that volatile elements (Zn and Br) are not strongly surface-correlated, suggesting that these elements are primarily indigenous rather than from atmospheric contamination• Information on the host phases of trace elements (e.g., Zn, the first element lost during entry heating, is isolated in a few spots, probably ZnS identified by TEM in IDPs; Sr in carbonate)

10 m

Sutton, S.R., et al. (2000) Lunar Planet. Sci. XXXI,1857.

NSLS-II User Workshop, July 2007

Ionomics: the study of how genes regulate ions in cells.

Fe deficiency most common nutritional disorder in the world

2 billion (mainly in developing countries) are anemic

A number of the key genes involved in iron uptake in plants have been identified. Armed with this knowledge, it should now be possible to engineer or breed plants with improved iron uptake abilities and in more bioavailable forms.

Use synchrotron x-ray microprobe techniques to assign functions to metal homeostasis genes whose phenotypes could not be observed using volume-averaged metal analysis techniques

Genomics to Ionomics: Metal homeostatis in plantsGenomics to Ionomics: Metal homeostatis in plants

Technique: X-ray Fluorescence Computed Micro-TomographyResearchers:T. Punshon and M. L. Guerinot (Dartmouth U.), A. Lanzirotti (U. Chicago, CARS)Publication:S. Kim, T. Punshon, A. Lanzirotti, L. Li, J. Alonso,J. Ecker, J. Kaplan and M. L. Guerinot (2006) Localization of Iron in Arabidopsis Seed Requires the Vacuolar MembraneTransporter VIT1, Science.

Arabidopsis thaliana (Mouse-Eared Cress)genome sequenced (2000)

NSLS-II User Workshop, July 2007

Absorption Tomograms

cotyledonsradicle

seed coat

NSLS-II User Workshop, July 2007

Fluorescence TomogramsFluorescence Tomograms

Col-O atvit1-1

Fe Fe MnMn Zn Zn

• Synchrotron x-ray fluorescence microtomography shows that the majority of iron is preciselylocalized to the provascular strands of the embryo. This localization of iron is completelyabolished when the vacuolar iron uptake transporter VIT1 is disrupted, making vacuolesa promising target for increasing the iron content of seeds.