Concentrations and loads of PCBs Concentrations and loads of PCBs and OC pesticides in the urbanized and OC pesticides in the urbanized Guadalupe River watershedGuadalupe River watershed

Presented to:Presented to:RMP Sources, Pathways, and Loadings RMP Sources, Pathways, and Loadings WorkgroupWorkgroup

May 22, 2007May 22, 2007

Jon LeatherbarrowJon LeatherbarrowSan Francisco Estuary Institute, Oakland, CASan Francisco Estuary Institute, Oakland, CAUC Davis, Civil & Environmental Engineering, Davis, UC Davis, Civil & Environmental Engineering, Davis, CACA

Item #2

PCB and OCP use in urban areasPCB and OCP use in urban areas

ChemicaChemicall

Initial UsesInitial Uses Restrictions in Restrictions in the 1970sthe 1970s

Continued or Continued or Recent Urban Recent Urban UseUse

PCBsPCBs

(1929-79)(1929-79)Electrical and Electrical and industrial uses; industrial uses; consumer productsconsumer products

1979: ban on 1979: ban on production and production and useuse

Continued enclosed Continued enclosed applications; applications;

DDTDDT

(1939-73)(1939-73)Agriculture, Agriculture, mosquito, pest mosquito, pest control for control for res/com/forestres/com/forest

1973: ban, except 1973: ban, except emergency uses; emergency uses; still used outside still used outside of U.S.of U.S.

No significant useNo significant use

ChlordaneChlordane

(1948-90s)(1948-90s)Agriculture, lawns, Agriculture, lawns, gardens; termitesgardens; termites

1978: ban on use 1978: ban on use for food and for food and above ground above ground appl.appl.

Post-1983: sub-Post-1983: sub-surface structural surface structural termite cont.; termite cont.; cancelled 1988cancelled 1988

DieldrinDieldrin

(1948-87)(1948-87)Agriculture, soils, Agriculture, soils, wood preservative, wood preservative, moth-proofing, moth-proofing, termitestermites

1970s: ban on use 1970s: ban on use for food and for food and above ground above ground appl.appl.

Post-1974: sub-Post-1974: sub-surface structural surface structural termite cont.; termite cont.; cancelled 1987cancelled 1987

HCHsHCHs

(1940s-(1940s-Present)Present)

Agriculture, garden, Agriculture, garden, farms, xmas trees, farms, xmas trees, etc.etc.

1976: ban on 1976: ban on production and production and use of technical-use of technical-HCHHCH

Post-1977: lindane Post-1977: lindane ((-HCH) use for seed -HCH) use for seed treatment & treatment & ornamentalsornamentals

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Areas of heaviest use of PCBs; contaminated areas; continued use and accidental release;

Areas of most recent widespread use of many OCPs (e.g., chlordane, dieldrin, HCHs); direct application, release

Development and disturbance of former agricultural lands; post World War II and Silicon Valley “boom” in the 1960s

Persistence in watershed soils and aquatic sediments due to chemical and physical stability;

Continuing local, regional, and global impacts from cycling of contaminant residues through non-point source pollution pathways (i.e., runoff, atmospheric)

Legacy contamination in urban Legacy contamination in urban environmentenvironment

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Sample collection: PCBs (n=72, WY2003-06) OCPs: DDT, HCHs (n=44 WY2003-04)

dieldrin, chlordane Grab samples (WY2003) D-96 sampler (WY2004-06)

Sample analysis Laboratory: Axys Analytical Services,

Ltd. Sidney, BC Method: HRGC/HRMS, EPA 1668A

Guadalupe River monitoring Guadalupe River monitoring approachapproach

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Guadalupe River monitoring resultsGuadalupe River monitoring resultsParameterParameter nn FWMCFWMC

(ng/L)(ng/L)RangeRange

(ng/L)(ng/L)CompositionComposition

40 40 PCBsPCBs 7272 4141 0.73 – 1670.73 – 167 ≥ ≥ 5-Cls (88 ± 5-Cls (88 ± 6%)6%)

6 6 DDTDDT 4444 2727 0.52 – 710.52 – 71 p,p’-DDE (40 ± p,p’-DDE (40 ± 6%)6%)

p,p’-DDT (28 ± p,p’-DDT (28 ± 7%)7%)

p,p’-DDD (20 ± p,p’-DDD (20 ± 8%)8%)

7 7 ChlordaneChlordane 4444 2424 0.63 – 640.63 – 64 -chlor (29 ± -chlor (29 ± 2%) 2%)

-chlor (28 ± -chlor (28 ± 2%) 2%)

t-non (20 ± t-non (20 ± 8%)8%)

DieldrinDieldrin 4444 2.22.2 0.19 – 6.00.19 – 6.0

4 4 HCHsHCHs 2424 0.330.33 0.10 – 1.30.10 – 1.3 -HCH (49 ± -HCH (49 ± 10%)10%)

-HCH (25 ± -HCH (25 ± 9%)9%)

-HCH (20 ± -HCH (20 ± 8%)8%)

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Regression: contaminants on SSCRegression: contaminants on SSC

0 200 400 600 800 1000 1200

Tot

al P

CB

s (p

g/L)

0

50000

100000

150000

200000

0 200 400 600 800 1000 1200

Tot

al D

DT

(pg

/L)

0

10000

20000

30000

40000

50000

60000

70000

SSC (mg/L)

0 200 400 600 800 1000 1200

TC

HLO

R (

pg/L

)

0

10000

20000

30000

40000

50000

60000

70000

SSC (mg/L)

0 200 400 600 800 1000 1200

diel

drin

(pg

/L)

0

2000

4000

6000

8000

Rising stage ●

Δ

Falling stage

Base flow ■

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Annual loading (***preliminary***)Annual loading (***preliminary***)

Load in Load in Grams/YrGrams/Yr

WY2003

WY2004

WY2005

WY2006

AVG (±

STDEV)

PCBsPCBs 930 730 620 1,360 910(± 330)

DDTDDT 800 620 560 1,230 800(± 300)

ChlorChlor 650 510 410 900 620(± 210)

DieldrinDieldrin 70 50 50 110 70(± 28)

Top 7 days (%)

62-70% 67-74% 42-47% 35-42%

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Watershed yields: Penta-PCBsWatershed yields: Penta-PCBsD

arb

yC

oop

erA

naco

stia

, NW

Ana

cost

ia, N

EM

antu

aP

enns

auke

nF

rank

ford

Gua

dalu

pe

Big

Tim

ber

Poq

uess

ing

Sch

uyk

illA

llow

ays

Sus

que

hann

aC

hes

ter

Cro

ssw

icks

Ra

ccoo

nP

enny

pack

Sal

emD

ela

war

eR

anc

oca

sS

usq

ueha

nna

Ch

irstin

aS

acra

men

toN

ers

ham

iny

Bra

ndy

win

e

0

1

2

3

4

5

6

Pen

ta-C

Bs

(ng

/m2/

day

)

Estimates from Fikslin and Suk (2003); Foster et al. (2000a,b); Ko and Baker (2004); Leatherbarrow et al. (2005)

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Da

rby

Co

oper

Ana

cost

ia, N

WA

naco

stia

, NE

Man

tua

Pen

nsau

ken

Fra

nkfo

rdG

uada

lup

eB

ig T

imbe

rP

oque

ssin

gS

chu

ykill

Allo

way

sS

usq

ueha

nna

Ch

este

rC

ross

wic

ksR

acc

oon

Pen

nypa

ckS

alem

De

law

are

Ra

nco

cas

Sus

que

hann

aC

hirs

tina

Sac

ram

ento

Ne

rsh

amin

yB

ran

dyw

ine

0

1

2

3

4

5

6

Pen

ta-C

Bs

(ng

/m2/

day

)

Watershed yields: Penta-PCBsWatershed yields: Penta-PCBs

Rowe et al. (2007) estimate that highlighted watershed yields reported in Delaware River TMDL are atmospherically driven

Item #2

Watershed yields*: PesticidesWatershed yields*: PesticidesG

uada

lupe

(03

-06)

Ana

cost

iaN

W (

95-9

6)

Nan

ticok

e (9

7-9

8)

Ana

cost

iaN

E (

95

-96

)S

usqu

eha

nna

(94

-95)

Che

ster

ville

(97

-98)

Sac

ram

en

to (

02-

03

)0

2

4

6

8

10

Sus

queh

ann

a (9

2-9

3)

Ana

cost

iaN

W (

95-9

6)

Gua

dalu

pe (

03-0

6)

Ana

cost

iaN

E (

95

-96

)

Sus

queh

ann

a (9

4-9

5)

Sac

ram

en

to (

02-

03

)

0

0.5

1

1.5

2A

naco

stia

NW

(95

-96)

Ana

cost

iaN

E (

95

-96

)G

uada

lupe

(03

-06)

Sus

queh

ann

a (9

2-9

3)S

usqu

eha

nna

(94

-95)

Nan

ticok

e (9

7-9

8)

Che

ster

ville

(97

-98)

Sac

ram

en

to (

02-

03

)

0

10

20

30

40

Sum of chlordane compounds

Dieldrin

Sum of p,p’-isomers of DDE, DDD, DDT

*All yields in ng/m2/day;

Estimates from Foster et al. (2000); Foster et al. (2003); Leatherbarrow et al. (2005)

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Potential sources: PCB congenersPotential sources: PCB congeners

PC

B 0

08

PC

B 0

18

PC

B 0

28

PC

B 0

31

PC

B 0

33

PC

B 0

44

PC

B 0

49

PC

B 0

52

PC

B 0

56

PC

B 0

60

PC

B 0

66

PC

B 0

70

PC

B 0

87

PC

B 0

95

PC

B 0

99

PC

B 1

01

PC

B 1

05

PC

B 1

10

PC

B 1

18

PC

B 1

28

PC

B 1

32

PC

B 1

38

PC

B 1

41

PC

B 1

49

PC

B 1

51

PC

B 1

53

PC

B 1

56

PC

B 1

58

PC

B 1

70

PC

B 1

74

PC

B 1

77

PC

B 1

80

PC

B 1

83

PC

B 1

87

PC

B 1

94

PC

B 1

95

PC

B 2

01

PC

B 2

03

PC

B (

pg/L

)

0

5000

100000

1000

2000P

CB

008

PC

B 0

18

PC

B 0

28

PC

B 0

31

PC

B 0

33

PC

B 0

44

PC

B 0

49

PC

B 0

52

PC

B 0

56

PC

B 0

60

PC

B 0

66

PC

B 0

70

PC

B 0

87

PC

B 0

95

PC

B 0

99

PC

B 1

01

PC

B 1

05

PC

B 1

10

PC

B 1

18

PC

B 1

28

PC

B 1

32

PC

B 1

38

PC

B 1

41

PC

B 1

49

PC

B 1

51

PC

B 1

53

PC

B 1

56

PC

B 1

58

PC

B 1

70

PC

B 1

74

PC

B 1

77

PC

B 1

80

PC

B 1

83

PC

B 1

87

PC

B 1

94

PC

B 1

95

PC

B 2

01

PC

B 2

03

0

1000

2000

PC

B 0

08

PC

B 0

18

PC

B 0

28

PC

B 0

31

PC

B 0

33

PC

B 0

44

PC

B 0

49

PC

B 0

52

PC

B 0

56

PC

B 0

60

PC

B 0

66

PC

B 0

70

PC

B 0

87

PC

B 0

95

PC

B 0

99

PC

B 1

01

PC

B 1

05

PC

B 1

10

PC

B 1

18

PC

B 1

28

PC

B 1

32

PC

B 1

38

PC

B 1

41

PC

B 1

49

PC

B 1

51

PC

B 1

53

PC

B 1

56

PC

B 1

58

PC

B 1

70

PC

B 1

74

PC

B 1

77

PC

B 1

80

PC

B 1

83

PC

B 1

87

PC

B 1

94

PC

B 1

95

PC

B 2

01

PC

B 2

03

PC

B (

%)

0

5

10

15

0

5

10

15

12/16/02 19:55 (GR24)

10/26/04 5:50 (GR310)

10/26/04 7:50 (GR311)

Aroclor 1260

Aroclor 1254

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Potential sources: PCB congenersPotential sources: PCB congenersR

atio

of

GR

311:

310

0.0

0.5

1.0

1.5

PC

B (

%)

02468

1012

PC

B 0

08

PC

B 0

18

PC

B 0

28

PC

B 0

31

PC

B 0

33

PC

B 0

44

PC

B 0

49

PC

B 0

52

PC

B 0

56

PC

B 0

60

PC

B 0

66

PC

B 0

70

PC

B 0

87

PC

B 0

95

PC

B 0

99

PC

B 1

01

PC

B 1

05

PC

B 1

10

PC

B 1

18

PC

B 1

28

PC

B 1

32

PC

B 1

38

PC

B 1

41

PC

B 1

49

PC

B 1

51

PC

B 1

53

PC

B 1

56

PC

B 1

58

PC

B 1

70

PC

B 1

74

PC

B 1

77

PC

B 1

80

PC

B 1

83

PC

B 1

87

PC

B 1

94

PC

B 1

95

PC

B 2

01

PC

B 2

03

PC

B (

%)

0

2

4

6

8

10

Aroclor 1016

Aroclor 1242

Ratio of GR311:GR310

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Watershed processing of PCBsWatershed processing of PCBs

Discharge (m3/s)

0 20 40 60 80 100 120 140 160 180

Pe

rce

nta

ge

of T

PC

Bs

(%)

10

15

20

25

30

35

40

Penta-PCBs ▼ Hepta-PCBs □

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Watershed processing of DDTWatershed processing of DDT

Discharge (m3/s)

0 20 40 60 80 100 120 140 160 180

Pe

rce

nta

ge

of T

DD

T (

%)

0

10

20

30

40

50

p,p’-DDT ▼ p,p’-DDD □

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Diffuse source distribution in the watershed: Positive linear relationships of contaminants with SSC; Relatively constant PCB congener profile;

Gradient in contamination from urban to non-urban areas: Differences in rising and falling stage regressions indicates

high SSC-based concentrations likely emanating from lower urban areas compared to upper non-urban areas;

Periodic inputs of PCBs from unique sources: Anomalous profiles in some samples; Atmospheric inputs likely discernable in evolving profile

patterns;

Relatively unweathered sources of pesticides: High percentage of parent DDT material at high flows; Similar increase in technical mixture profiles in other OCPs;

Implications of findings: sourcesImplications of findings: sources

Item #2

Watershed yields consistent with contaminated urban areas: PCB yields above expected yields from atmospheric deposition;

Urban influence evident compared to other land uses: Comparison of watershed yields indicates high potential source

density in urban areas compared to non-urban areas;

Urban runoff contributes to impairment of SF Bay: Mass budget models indicate loading of PCBs and OCPs on the

order of 10 kg/yr could significantly delay water quality improvement;

PCB TMDL loading target for urban runoff = 2 kg/yr Loads of 0.5-1 kg/yr from Guadalupe, combined with other

tributaries, are expected to contribute to prolonged impairment of water quality.

Implications of findings: loadingsImplications of findings: loadings

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Modeling Hydrologic routing: where is the water coming from? Sediment transport: where is the sediment coming from? Contaminant transport: link evolving contaminant profiles to

sources of water and sediment.

Treatment options Source reconnaissance Structural treatment device placement and optimization

Information gathering on other tributaries Monitoring other selected tributaries Extrapolation/modeling methods

Information needsInformation needs

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