atmospheric aerosols from mining operations in hayden and dewey-humboldt, az eric a. betterton 1,2 ;...
TRANSCRIPT
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.”
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)
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 44
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 55
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 66
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)
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 77
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 88
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 99
Hayden – NW “smelter”Hayden – NW “smelter”
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 1010
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
Cutpoint Diameter (mm)
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”
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 1111
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
Cutpoint Diameter (mm)
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.
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 1212
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.
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 1313
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
Cutpoint Diameter (mm)
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 1717
Lead isotope ratios for two sampling periods at Lead isotope ratios for two sampling periods at Hayden (MOUDI not programmed)Hayden (MOUDI not programmed)
Iron King TSP and SoilIron King TSP and Soil
1919
Hayden
Iron King
Tucson
Betterton, EPA Dec. 8, 2011
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.
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2020
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.
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2121
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2222
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 23
Iron KingIron King3-D Winds3-D Winds
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2424
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2525
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
Betterton, EPA Dec. 8, 201127
Weather Research and Weather Research and Forecast Model (WRF)Forecast Model (WRF)
10-meter wind forecast on Google Earth
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2828
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)
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 2929
Phoenix dust storm: 8 pm, July 5, 2011
Iron King Dust TrackIron King Dust Track
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 3030
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
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 31
Questions?Questions?
Betterton, EPA Dec. 8, 2011Betterton, EPA Dec. 8, 2011 3232
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
Betterton, EPA Dec. 8, 2011