7/8/2013

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The Long‐Term Impact ofMetal Smelting Operations on

Arsenic Availability in Urban Lakes of the South‐Central Puget Sound Region

Jim Gawel, Ph.D.

University of Washington Tacoma

Environmental Science and Studies

Research Team

• UWT Undergraduates: Lindsay Tuttle, Sarah Burdick, Michelle Miller, Jessica Asplund, Shawna Peterson, Kara Ziegler and Alexandra Ehle

• Bellarmine High School: Amanda Tollefson and Brian Rurik

• UW Seattle Faculty: Becca Neumann

Importance of Urban Lakes

• Human population concentrated in urban areas; already 50% or greater worldwide

• Urban poor rely on local, inexpensive recreational water resources

• Some rely on water sources for cultural ties and diet augmentation

• Urban waters serve as critical habitat for multiple species

Urbanization & Arsenic Pollution

• Lake sediments act as As reservoirs after external source removal

• If remobilized periodically As may migrate to surface sediments

• Cultural eutrophication can exacerbate As release from sediments

• Other anthropogenic inputs may affect As mobility (e.g. road salt, nitrate and phosphate)

Major Sources of Arsenic in Lakes

• Herbicide applications in lakes• Fruit orchard insecticides

[Paris Green ‐ 3Cu(AsO2)2.Cu(C2H3O2)2]

• Chemical manufacture• Timber treatment [CCA]• Mine tailings and drainage• Smelting

– Air emissions– Slag disposal

ASARCO

• 1890 Lead smelting begins

• 1905 Conversion to copper smelter

• 1912 Arsenic recovery begun in Tacoma

• 1917 Tall stack constructed (700 ft asl) + electrostatic precipitators

• 1970 Meteorological Curtailment Program

• 1986 All smelting operations cease

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Ongoing Study Breakdown

• Spatial distribution of As and Pb in lake sediments

• Temporal distribution in sediments

• Arsenic mobility and release to water column

• Chemical, biological, and physical controls on As mobility, bioavailability and toxicity

Lakes Sampled

Wind Patterns

American LakeSpanaway Lake

Steilacoom Lake

Snake LakeSurprise Lake

Fivemile LakeLake KillarneyLake Geneva

North Lake

Steel Lake

Lake Fenwick

Angle Lake

Bay Lake

Crescent Lake

Horseshoe LakeWye Lake

Wicks Lake

Long Lake

-

Lake Meridian

ASARCO

0.9 to 3.9 knots

4.0 to 6.9 knots

7.0 to 10.9 knots

11.0 to 16.9 knots

Lakes sampled

American LakeSpanaway Lake

Steilacoom Lake

Snake LakeSurprise Lake

Fivemile LakeLake KillarneyLake Geneva

North Lake

Steel Lake

Lake Fenwick

Angle Lake

Bay Lake

Crescent Lake

Horseshoe LakeWye Lake

Wicks Lake

Long Lake

-

Lake Meridian

ASARCO

0.9 to 3.9 knots

4.0 to 6.9 knots

7.0 to 10.9 knots

11.0 to 16.9 knots

Lakes sampled

Bonney LakeBonney LakeBonney LakeBonney Lake

Lake TappsLake TappsLake TappsLake Tapps

Dolloff Lake

Bow Lake

Waughop Lake

Wapato Lake

http://www.ecy.wa.gov/PROGRAMS/tcp/area_wide/AW/Toolbox_chap2_figures/Tier2Maps.pdf

WA Dept. of Ecology. 2002. King County mainland soil study.

Angle Lake

Steel Lake

Lake Meridian

Lake Killarney

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Lakes within predicted deposition zone significantly higher in As and Pb

As vs. Pb in Surface Sediments

0

20

40

60

80

100

120

140

160

0 100 200 300 400 500 600

average Pb conc (ppm)

ave

rag

e A

s c

on

c (p

pm

)

Crescent

Killarney

Fenwick

Meridian

Fivemile

Long (Kitsap)

Spanaway

Geneva

Horseshoe

Bay

Angle

Wye

Wicks

Surprise

Steel

Snake

Steilacoom

Two Different Sources?

R2 = 0.8932

R2 = 0.69780

20

40

60

80

100

120

140

0 100 200 300 400 500 600

Average Concentrations of Pb in ppm

Av

era

ge

Co

nc

en

tra

tio

n o

f A

s in

pp

m

•1:1 As:Pb ratio may be fingerprint of ASARCO slag/emissions (Mariner et al. 1997)

As in Sediment Cores

•Significant correlation between As and Pb in all cores except Brook and Spanaway

0

5

10

15

20

25

30

35

40

45

50

0 20 40 60 80 100

As (mg/kg dry sediment)D

ep

th in

co

re (

cm)

Fivemile Lake

Lake Geneva

Steel Lake

Spanaw ay Lake

Bonney Lake

0

10

20

30

40

50

60

70

0 50 100 150 200 250

As (mg/kg dry sediment)

De

pth

in c

ore

(cm

)

Angle Lake

North Lake

Lake Meridian

Lake Killarney

Killarney AmericanAngle

WaughopBonnie Dolloff

Sediment Summary

• Surface sediments in 10 of 12 lakes in deposition zone exceed probable effects concentration of 33 ppm As and 128 ppm Pb– PEC = “above which harmful effects are likely to be observed” (MacDonald et al. 2000)

• Lake Killarney and Angle Lake show highest sediment concentrations at sediment surface– Ongoing inputs?

– Vertical migration?

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Sediment/Water Transfer

p < 0.01

•Similar ratio seen in Lake Washington by Peterson and Carpenter (1986)•Similar ratio in suite of lakes in Massachusetts by Lattanzi et al. (2007)

Basic Red/Ox Chemistry

AsO43- [As(+V)]

(arsenate)

AsO33- [As(+III)]

(arsenite)

Fe(OH)3(s) [Fe(+III)]

Fe2+ [Fe(+II)]

SO42- [S(+VI)]

HS- [S(-II)]

Effect of Eh and pH on As/Fe/S

• Primary inorganic forms:

– arsenate [As(V):H2AsO4‐]

– arsenite [As(III): H3AsO4]

• As(V) binds readily to Fe(III)‐oxides and may precipitate

• As(III) is more soluble and toxic

• As(III) may bind to S(‐II) and Fe(II) and precipitate

Daus et al. (2002), ∑As=∑S=∑Fe=10−6 M

Arsenic Remobilization

Thermocline: barrier to mixing oxygen

As As As As As

SEDIMENTS

O2

O2

O2

O2

O2

O2

As

AsAs

As

As

Organic Matter + O2 = CO2 +H2O

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

Lake Meridian Angle Lake North Lake Lake KillarneyTemperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

08-19-200409-01-200409-15-2004

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-28-200408-19-200409-01-200409-15-2004

Te

mp

e ra

ture

DO (mg/L)

0 2 4 6 8 10 12

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

DO (mg/L)

0 2 4 6 8 10 12

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

DO (mg/L)

0 2 4 6 8 10 12

Dep

th (

m)

0

5

10

15

20

08-19-200409-01-200409-15-2004D

isso

lved

Oxy

gen

DO (mg/L)

0 2 4 6 8 10 12

De

pth

(m

)

0

5

10

15

20

07-28-200408-19-200409-01-200409-15-2004

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-08-200407-21-200408-10-200408-27-200409-08-200409-28-2004

Lake Meridian Angle Lake North Lake Lake KillarneyTemperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

08-19-200409-01-200409-15-2004

Temperature (°C)

5 10 15 20 25 30

Dep

th (

m)

0

5

10

15

20

07-28-200408-19-200409-01-200409-15-2004

Te

mp

e ra

ture

To

tal A

rsen

ic

Average Total Arsenic Conc. (ppb)

0 10 20 30 40

De

pth

(m

)

0

5

10

15

20

07-21-200408-10-200408-27-200409-08-200409-28-2004

Average Total Arsenic Conc. (ppb)

0 10 20 30 40

De

pth

(m

)

0

5

10

15

20

07-21-200408-10-200408-27-200409-08-200409-28-2004

Average Total Arsenic Conc. (ppb)

0 10 20 30 40

De

pth

(m

)

0

5

10

15

20

08-19-200409-01-200409-15-2004

Average Total Arsenic Conc. (ppb)

0 10 20 30 40

De

pth

(m

)

0

5

10

15

20

07-28-200408-19-200409-15-2004

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Total Dissolved As (ppb)

0 20 40 60 80 100D

ep

th (

m)

0

5

10

15

20

25

30

SteilacoomAmericanBonneyTappsMeridianNorthSteelKillarneyGenevaFivemileAngleSpanaway

Killarney

Steel

North

Angle

Average Arsenic Concentration (ppb)

0 10 20 30 40 50

Sul

fide

Con

cent

ratio

n (

mg

S2

- /L)

0.0

0.2

0.4

0.6

0.8

Meridian, Angle, and NorthKillarney

Average Arsenic Concentration (ppb)

0 10 20 30 40 50

Iron

Con

cent

ratio

n (m

g F

e/L)

0

2

4

6

8

Meridian, Angle, and NorthKillarney

As:Fe:S in Select Lakes

•Generally dissolved As, Fe, and S increase proportionately under reducing conditions•Killarney does not match that pattern, why?

DO vs PO4 in Select Lakes

•PO4 still elevated in Killarney in the presence of high DO•Highest PO4 when near bottom water goes anoxic (calm, warm weather)

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

0 2 4 6 8 10 12

Dissolved PO4(µM)

Dissolved Oxygen (mg/L)

Meridian, Angle, North

Killarney

Filtered vs. Unfiltered

Dissolved Arsenic Speciation

0

2

4

6

8

10

12

14

0% 20% 40% 60% 80% 100%

% of total (IC-ICP-MS)

De

pth

(m

)

As(III)

As(V)

Other

Angle Lake

0

2

4

6

8

10

12

14

0% 20% 40% 60% 80% 100%

% of total (IC-ICP-MS)

De

pth

(m

)

As(III)

As(V)

Other

Steel Lake

0

2

4

6

8

10

12

14

0% 20% 40% 60% 80% 100%

% of total (IC-ICP-MS)

De

pth

(m

)

As(III)

As(V)

Other

North Lake

0

2

4

6

8

10

12

14

0% 20% 40% 60% 80% 100%

% of total (IC-ICP-MS)

De

pth

(m

)

As(III)

As(V)

Other

Lake Killarney

•Analysis by Applied Speciation Inc.•Highly mobile As(V) in these lakes in general, with only North Lake having As(III)

Proposed Model for As Mobilityin Presence of Oxygen

Current hypothesis:(1) Microbially available orgC for reductive dissolution of arsenic‐bearing sediments(2) NOM and/or phosphate to keep arsenic from sorbing to settling particles(3) Shallow water column that resists stratification 

7/8/2013

6

Wa

pa

to L

ake

Dep

th (

me

ters

)

Lak

e D

ollo

ff

Dep

th (

met

ers

)

Temperature ºC Dissolved OxygenArsenic in Water (ppb)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

10 12 14 16 18 20 22 24

06/21/07

08/16/07

Secchi depth

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 2 4 6 8 10 12 14

06/21/07

08/16/07

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 2 4 6 8 10 12 14 16

As Filtered06/21/07As Unfiltered06/21/07As Filtered08/16/07As Unfiltered08/16/07

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

10 12 14 16 18 20 22 24

07/05/07

08/30/07

Secchi depth

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0 2 4 6 8 10 12 14

07/05/07

08/30/07

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0 2 4 6 8 10 12 14 16

As Filtered07/05/07As Unfiltered07/05/07As Filtered08/30/07As Unfiltered08/30/07 Total As (unfiltere d) nM

0 50 100 1 50 200 250

0

2

4

6

8

10

6/22/98

7/6/98

7/30/988/17/98

9/17/98

10 /6/98 10 /27/98

To tal As (unfilte red) nM

0 2 0 40 60 80 100

4/14 /99

5/3/99

5 /19 /996/2/99

6 /25 /99

Not Just in Washington

North Basin – Spy Pond, MA (Senn et al. 2007)

Questions to Address in Research

• What is the mix of water quality parameters to measure to predict As mobility in urban lakes?

• Does the presence of high levels of dissolved As in surface waters increase biotic uptake by phytoplankton, zooplankton, and fish?

• Would fish bioaccumulation become an issue under these conditions?

• How might this be important to freshwater sediment criteria development?

0.0E+00

2.0E‐10

4.0E‐10

6.0E‐10

8.0E‐10

1.0E‐09

1.2E‐09

Angle Killarney North Steel Wapato

mol PC(n=2)/ug chl‐a

(n=1)

ND

Bioindicators of Metal Toxicity

Acknowledgements

• Funded by:

– UWT Environmental Sciences Program

– UWT Founders Endowment

– UWT Chancellor’s Fund for Research

• As speciation provided by Applied Speciation, Inc., Tukwila, WA, at major discount

To All My UW Tacoma and BellarmineResearchers!

7/8/2013

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Links page

• Dr. Jim Gawel (jimgawel@uw.edu) 

• Environmental Sciences and Studies at University of Washington Tacoma:http://www.tacoma.uw.edu/interdisciplinary‐arts‐sciences/courses/environmental‐studies

• University of Washington Superfund Research Program:http://depts.washington.edu/sfund/

• US EPA Region 10:http://www.epa.gov/aboutepa/region10.html

• Dr. Bruce Duncan, Regional Science Liaison, US EPA Region 10(duncan.bruce@epa.gov)

• Superfund Research Program‐ National Institute of Environmental Health Sciences(NIEHS)http://www.niehs.nih.gov/research/supported/srp/