atmospheric aerosols from mining operations in hayden and dewey-humboldt, az eric a. betterton 1,2 ;...

Atmospheric Aerosols from Mining Atmospheric Aerosols from Mining Operations in Hayden and Dewey-Operations in Hayden and Dewey-

Humboldt, AZHumboldt, AZEric A. BettertonEric A. Betterton1,21,2; Janae L. Csavina; Janae L. Csavina11; Jason P. Field; Jason P. Field33; Andrea ; Andrea

C. LandázuriC. Landázuri11; ; Omar Felix VillarOmar Felix Villar11; Kyle P. Rine; Kyle P. Rine22; A. Eduardo Sáez; A. Eduardo Sáez11; Jana ; Jana

PencePence22; Homa Shayan; Homa Shayan11;; Mike StovernMike Stovern11 ; MacKenzie Russell ; MacKenzie Russell11Supported by NIEHS Superfund Basic Research ProgramSupported by NIEHS Superfund Basic Research Program

Betterton, EPA Dec. 8, 2011 11

Hayden slag pour

Hayden smelter stack

Dewey-Humboldt tailings

Poisoned PlacesPoisoned PlacesToxic Air, Neglected CommunitiesToxic Air, Neglected Communities

NPR News Investigations – November 17, 2011NPR News Investigations – November 17, 2011

Betterton, EPA NARPM May 2011Betterton, EPA NARPM May 2011 22

“The Environmental Protection Agency has taken tough enforcement action against a copper smelter in Arizona that has drawn complaints about toxic pollution for years.

The unpublicized "finding of violation" issued against the Asarco copper smelter in Hayden, Ariz., claims the company has been continuously emitting illegal amounts of lead, arsenic and eight other dangerous compounds for six years.”

EPA Takes Action Against Toxic Arizona Copper Plant

“A haze can be seen at night hovering over the Asarco copper smelter, which turns copper ore into nearly pure copper bars.”

http://www.npr.org/blogs/thetwo-way/2011/11/17/142439081/epa-takes-action-against-toxic-arizona-copper-plant

Effects of dust/aerosolsEffects of dust/aerosols

Public healthPublic health Public safetyPublic safety

Role of Particle Role of Particle DiameterDiameter Global vs. regional Global vs. regional

transporttransport Respiratory Respiratory

depositiondeposition Associated Associated

contaminantscontaminants VisibilityVisibility

Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 33

I-10 between PHX and TUS October 4, 2011. Wind gusts 30 to 50+ mph

View of dust storm from Kitt peak, looking north, 3pm

Mining Operations & Mining Operations & Particle Size Particle Size

Crushing, Grinding, Mine Crushing, Grinding, Mine Tailings ManagementTailings Management Coarse >2.5 Coarse >2.5 μμm m

(mechanical action)(mechanical action) Smelting, RefiningSmelting, Refining

Ultra-fine <0.1 Ultra-fine <0.1 μμm m ((gas to particle gas to particle conversion)conversion)

Accumulation 0.1-2.5 Accumulation 0.1-2.5 μμm m (coagulation of ultrafine (coagulation of ultrafine and condensation growthand condensation growth))

(Seinfeld and Pandis 1998)


Arizona Field SitesArizona Field Sites

Contaminated SitesContaminated Sites Iron King (Humboldt-Dewey) Iron King (Humboldt-Dewey)

- Inactive smelter; now a - Inactive smelter; now a Superfund site (arsenic, lead Superfund site (arsenic, lead contaminated tailings) contaminated tailings)

Hayden & Winkelman Hayden & Winkelman (ASARCO) (ASARCO) - active copper mine - active copper mine with smelter (arsenic, lead with smelter (arsenic, lead contaminated soil; airborne lead contaminated soil; airborne lead ) )

Comparison SitesComparison Sites Mount Lemmon Mount Lemmon -- Remote Remote

backgroundbackground TucsonTucson - Urban - Urban Green ValleyGreen Valley - Active copper - Active copper

mine; “clean” tailingsmine; “clean” tailings Wilcox PlayaWilcox Playa - Natural dust - Natural dust

sourcesource


Sampling TechniquesSampling Techniques MOUDI (Micro-Orifice Uniform

Deposit Impactor) 10 aerosol size fractions on separate

stages Cut-point diameters of 18, 10, 5.6,

3.2, 1.8, 1.0, 0.56, 0.32, 0.18 µm, 0.1 and 0.056 µm

30 L/min flow rate SMPS (Scanning Mobility SMPS (Scanning Mobility

Particle Sizer™) Particle Sizer™) Number concentration from 1 to 10Number concentration from 1 to 1088

particles/cmparticles/cm33

Dp from 2.5 nm to 1.0 µmDp from 2.5 nm to 1.0 µm TSP (Total Suspended TSP (Total Suspended

Particulate)Particulate) High volume sampler (14 ftHigh volume sampler (14 ft33/min)/min) Mass concentration for ambient Mass concentration for ambient

particulate particulate 24 hour sampling period24 hour sampling period

Weather StationWeather Station Wind speed/direction, temperature, Wind speed/direction, temperature,

relative humidityrelative humidity Dust Flux MonitorsDust Flux Monitors

Optical PM-10 measurementsOptical PM-10 measurements


Hayden MOUDI Hayden MOUDI Measurement Verification (ng Measurement Verification (ng

mm-3-3))

0.01

0.1

1

10

100

As Cd Pb

Ave

rage

Con

cen

trat

ion

(n

g m

-3)

PM <9.9 (MOUDI)PM 10 (Actual)TSP (MOUDI)TSP (Actual)


Hayden MOUDI Hayden MOUDI 2009 Annual Average (ng m2009 Annual Average (ng m-3-3))

0

2

4

6

8

10

12

189.96.23.11.81.00.550.320.180.10.054AF

Cutpoint Diameter (mm)

Ave

rage

Pb

Con

cent

rati

on (

ng m

-3)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ave

rage

Con

cent

rati

on (

ng m

-3)

Pb

Cd

As

Bimodal size Bimodal size distribution distribution


Hayden smelter building

Hayden slag pour

96-h sample96-h sample

Hayden Hayden MOUDI MOUDI 2009 2009

Seasonal Seasonal Average (ng Average (ng

mm-3-3)) MOUDI results for Pb, Cd, MOUDI results for Pb, Cd, and As with monthly and As with monthly averages.averages.

Majority of metals in fine Majority of metals in fine size fraction.size fraction.

Higher mixing height Higher mixing height occurs in summer months.occurs in summer months.

Smelter shutdown periods Smelter shutdown periods apparentapparent


Hayden – NW “smelter”Hayden – NW “smelter”


Figure 1. July 28, 2010 MOUDI ON (Programmed 300°-360°)

Hayden - July 28

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

189.96.23.11.810.550.320.180.10.054AF


Ave

rage

As

& C

d C

once

ntr

atio

n (

ng

m-3

)

0

2

4

6

8

10

12

Ave

rage

Pb

Con

cen

trat

ion

(n

g m

-3)

As

Cd

Pb

Hayden – NE “background”Hayden – NE “background”


Figure 1. November 16, 2010 MOUDI ON (Programmed 30°- 160°)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

189.96.23.11.810.550.320.180.10.054AF


Ave

rage

As

& C

d C

once

ntr

atio

n (

ng

m-3

)

0

2

4

6

8

10

12

Ave

rage

Pb

Con

cen

trat

ion

(n

g m

-3)

As

Cd

Pb

Scanning Electron Scanning Electron MicroscopyMicroscopy

(fine fraction)(fine fraction)

•Spherical nature of the arsenic- and lead-containing particles.•Lead particle shows direct evidence of coagulation with a smaller spherical particle.•Angular nature of the arsenic-free particles.


0.5 µm

Hayden Source ApportionmentHayden Source ApportionmentSEM with EDSSEM with EDS

Particles Containing Lead and Arsenic Particles Containing Lead and Arsenic

Weight % C-K O-K Al-K S-K Fe-K Zn-K Zr-L Pb-L Base(13)_pt1 7.47 20.72 54.87 2.06 0.54 1.53 1.93 10.88

Weight % Error (+/- 1 Sigma) C-K O-K Al-K S-K Fe-K Zn-K Zr-L Pb-L Base(13)_pt1 +/-1.85 +/-0.52 +/-0.19 +/-0.29 +/-0.10 +/-0.22 +/-0.22 +/-1.00

C-K O-K Al-K Si-K S-K Cl-K Fe-K Cu-K As-K Pt-L Base(11)_pt1 10.83 22.27 52.12 1.12 0.56 0.24 0.24 9.31 2.32 0.99

Weight % Error (+/- 1 Sigma) C-K O-K Al-K Si-K S-K Cl-K Fe-K Cu-K As-K Pt-L Base(11)_pt1 +/-1.02 +/-0.29 +/-0.18 +/-0.10 +/-0.06 +/-0.02 +/-0.03 +/-0.18 +/-0.31 +/-0.25

Energy-dispersive X-ray microanalysis imagery with SEM of MOUDI samples collected at Hayden showing the existence of arsenic- and lead-containing particles. The elemental analysis is for the areas targeted with a square on each particle.


Hayden Enrichment Factors Hayden Enrichment Factors Smelter Off as BaselineSmelter Off as Baseline

EF = [Cn(SmelterON)/Cref(SmelterON)]/[Bn(SmelterOFF)/Bref(SmelterOFF)]

n = As, Pb, Cd. ref = Sc

0.0

0.1

1.0

10.0

100.0

1000.0

>9.93.1-9.91 - 3.1<1

PMx (mm)

En

irch

men

t F

acto

r

As Cd Pb

Betterton, EPA Dec. 8, 201114

Lead stable isotopesLead stable isotopesin atmospheric aerosolsin atmospheric aerosols

Mukai et al., 2001

1515Betterton, EPA Dec. 8, 2011

Fractions for Pb Isotope Fractions for Pb Isotope AnalysisAnalysis

0

2

4

6

8

10

12

189.96.23.11.81.00.550.320.180.10.054AF


Ave

rage

Pb

Con

cen

trat

ion

(n

g m

-3)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5A

vera

ge A

s an

d C

d C

once

ntr

atio

n (

ng

m-3

)

Pb

Cd

As

1616Betterton, EPA Dec. 8, 2011

Lead Isotopes in Coarse and Lead Isotopes in Coarse and Fine FractionsFine Fractions

Ratios Ratios between the between the three stable three stable Pb isotopes Pb isotopes are often ore are often ore specific.specific.•Used to date Used to date ore formationore formation• Fingerprint Fingerprint anthropogenic anthropogenic Pb Pb


Lead isotope ratios for two sampling periods at Lead isotope ratios for two sampling periods at Hayden (MOUDI not programmed)Hayden (MOUDI not programmed)

Tucson Pb IsotopesTucson Pb IsotopesMOUDI not programmed

1818


Iron King TSP and SoilIron King TSP and Soil

1919

Hayden

Iron King

Tucson


DustTrack Optical Particle DustTrack Optical Particle MonitorMonitor

TSI DustTrak Aerosol Monitor•Particle concentrations corresponding to PM10, PM2.5, PM1.0 •Rapid response, portable, battery-operated

Comparison of Arizona Road Dust (A1) mass concentration measured by the DUSTTRAK DRX and the TEOM with a PM10 impactor.


Iron KingIron KingDust Flux and WindsDust Flux and Winds

Dust Flux towers installed Dust Flux towers installed at Iron King at Iron King Support model Support model

development development Track effects of Track effects of

phytoremediation. phytoremediation. Passive samplers also Passive samplers also

installed - help characterize installed - help characterize horizontal flux.horizontal flux.


Iron KingIron KingDust Flux MonitorsDust Flux Monitors

Two 10-m dust flux Two 10-m dust flux towerstowers

PM10, PM2.5, PM1.0PM10, PM2.5, PM1.0 Passive dust samplersPassive dust samplers Meteorological stationsMeteorological stations 3-D winds3-D winds


1

10

100

1000

10000

As Cd Pb

Ave

rage

Con

cent

rati

on (

ppm

)

Hayden

Iron King

Tucson

Green Valley

Wilcox

Iron King TSPIron King TSP


Iron KingIron King3-D Winds3-D Winds


3-D Ultrasonic anemometer

Sample 3-D winds from Iron King tailings November, 2011

Wind Erosion ModelingWind Erosion Modeling

Saltating sand dune particles in wind tunnel

Mass flux:

• Creep (rolling): 800-2000 mm Dp

• Saltation (hopping): 100-800 mm Dp

• Suspension (wind blown dust): <100 mm Dp

Kon et al., Int. J. Min. Reclamation & Env. 21, 198 (2007)

Greeley-Iversen erosion threshold curve

Kansas State University Kansas State University http://www.weru.ksu.edu/new_weru/multimedia/movies/dust003.mpghttp://www.weru.ksu.edu/new_weru/multimedia/movies/dust003.mpg


Wind Vectors - IK tailingsWind Vectors - IK tailings FLUENT FLUENT

Betterton, EPA Dec. 8, 2011 26

m/s

Iron KingIron KingArbitrary concentration (0 - 100 scale), 30 min after surface Arbitrary concentration (0 - 100 scale), 30 min after surface

ejection from IK tailing w/ Google earth overlayejection from IK tailing w/ Google earth overlay


Weather Research and Weather Research and Forecast Model (WRF)Forecast Model (WRF)

10-meter wind forecast on Google Earth


Weather Research and Weather Research and Forecast Model (WRF)Forecast Model (WRF)

WRF 10-meter wind forecast for Phoenix area: 6 pm, July 5, 2011(initialized 5 am)


Phoenix dust storm: 8 pm, July 5, 2011

Iron King Dust TrackIron King Dust Track


0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

1 2 3 4 5 6

PM

x C

onc

(mg/

m3 )

PM1

PM2.5

PM4

PM10

TSP

No Vegetation - Control

Dense Vegetation

Partial Vegetation

Avg. Wind Direction

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Sparse Vegetation Dense Vegetation Control

Per

cen

t D

ecre

ase

in P

Mx

PM1

PM2.5

PM4

PM10

TSP

Iron King PhytoremediationIron King Phytoremediation


Questions?Questions?


Phoenix, Arizona, July 6, 2011 2009-2011Janae Csavina, Jason Field, Mark P. Taylor, Song Gao, Andrea Landazuri, Eric A. Betterton, A. Eduardo Sáez , A Review on the Importance of Metals and Metalloids in Atmospheric Dust and Aerosol from Mining Operations, ready for submission to Sci. Total Environ. (2011).

Eric A. Betterton, Janae Csavina, Jason Field, Omar Ignacio Felix Villar, Andrea Landázuri, Kyle Rine, A. Eduardo Sáez, Jana Pence, Homa Shayan, MacKenzie Russell, Metal and Metalloid Contaminants in Airborne Dust Associated with Mining Operations, accepted AGU Fall Meeting, 5-9 December, San Francisco (2011).

Csavina, J., A. Landázuri, A. Wonaschütz, K. Rine, P. Rheinheimer, B. Barbaris, W. Conant, A.E. Sáez and E.A. Betterton, Metal and Metalloid Contaminants in Atmospheric Aerosols from Mining Operations, Water, Air, and Soil Pollution, 221, 145-157 (2011).

SEMSEM

3434

1 2

3Weight Percentage

Sample

Cu As Pb

1 27.59

X0 X0

2 29.60

X0 23.39

3 13.76

2.30

0.97


Green ValleyGreen Valley


atmospheric aerosols from mining operations in hayden and dewey-humboldt, az eric a. betterton 1,2 ;...

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