gmu chemistry & biochemistry pcbs and pahs in the anacostia river: sampling, concentrations and...

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Chemistry & Biochemistry

PCBs and PAHs in the PCBs and PAHs in the Anacostia River: Sampling, Anacostia River: Sampling,

Concentrations and Transport Concentrations and Transport in 2004-2005in 2004-2005

Gregory D. Foster & Phillip R. McEachernDepartment of Chemistry & Biochemistry

George Mason UniversityFairfax, VA

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Comparison of tPCB concentrations in sediments

Highest levels occur in •Anacostia River •Baltimore Harbor

Data compiled by J Baker (CBL)

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Study ObjectivesStudy Objectives

• Develop automated sampling techniques to accurately measure concentrations of PCBs and PAHs in the Anacostia River and refine annual load estimates

• Identify mode of PCB/PAH transport in AR and develop correlations with hydrology

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12

USGS Gauging Stations1. NE Branchsfc ar: 186 km2

Qavg:1.2x108 m3/y

2. NW Branchsfc ar: 126 km2

Qavg:7.0X107 m3/y

Watershed is ~50% urban land use

~80% urbanized in lower portion

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PCB Geochemistry: Dissolved and Particle Phases

Geosolids: Alumino- silicate clay particles in water (TSM)

•PCBs are concentrated in geosolids through sorption

Sorbed PCB (Cp ng/L)Dissolved PCB (Cw ng/L)

€

KdLkg

⎛

⎝ ⎜

⎞

⎠ ⎟=CsCw

ng / kgng / L

⎛

⎝ ⎜

⎞

⎠ ⎟

Kd =Cp

Cw [TSM]

€

Cp = Cs[TSM]

ng / L = (ng / kg)(kg / L){ }

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min10 20 30 40 50 60 70

counts

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Time, min

Res

po

nse

GC-ECD Chromatogram of PCBsGC-ECD Chromatogram of PCBs56 single component peaks (HP-1, 30 m)16 multiple component (2+) peaks88 congeners in 72 peaks•Congener No. (e.g., 119)•tPCBs = sum of mass•Homologue groups•LOD ~0.1 ng/L

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10.0015.0020.0025.0030.0035.000

100000

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Time-->

AbundanceTIC: W3SFDSC1.D

Flu

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Phe

nant

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Ant

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Flu

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Ben

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Chr

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Ben

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Ben

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Ben

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Inde

no(c

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Ben

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eryl

ene

Dib

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nthr

acen

e

Time

Inte

nsi

tyGC/MS TIC Chromatogram Anacostia River Sediments

Foster et al. (2000) Appl Geochem, 15,901

16 Priority Pollutant PAHsLOD ~ 0.5 ng/L

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Automated River Sampling

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NE Branch of the Anacostia River

How do you sample a river?

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River sampling was initiated whenrain gauge >0.15-0.25 in/hr

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0

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Arbitrary Time Intervals

Discharge (cfs)

NE Branch 25 June 2004

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1 16 31 46 61 76


Discharge (cfs)

NE Branch 22 July 2004

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1 16 31 46 61 76 91 106 121


Discharge (cfs)

NE Branch 27 May 2004

0

50

100

150

200

250

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1 51 101 151 201 251 301


Discharge (cfs)

NE Branch 26 April 2004

Examples of Sampled Hydrographs

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0

1

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7

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23 Jun 04 14 Jul 04 11 Jan 05 8 Feb 05 mean+sd

[TSM] mg/L NE

FultzIsco

Ho: samplers equal (TSM)p>0.05 (accept)paired t test

TSM: Fultz v. Isco Sampling NE Branch

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0

5

10

15

20

25

30


[TSM] mg/L NW

FultzIsco

TSM: Fultz v. Isco Sampling NW Branch

NA

Ho: samplers equal (TSM)p>0.05 (accept)paired t test

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0

0.2

0.4

0.6

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23 Jun 04 14 Jul 04 18 Aug 04 7 Dec 04 mean+sd

[tPCBs] ng/L D+P

FultzIsco

Ho: samplers equal (D+P)p>0.05 (accept)paired t test

PCBs: Fultz v. Isco Sampling - D+P NE Branch

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0.0

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[tPCBs] ng/L D+P

FultzIsco

PCBs: Fultz v. Isco Sampling - D+P NW Branch


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0

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[tPAHs] ng/L D+P

FultzIsco

PAHs: Fultz v. Isco Sampling - D+P NE Branch


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0

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400

500

600


[tPAHs] ng/L D+P

FultzIsco Ho: samplers equal (part)

p>0.05 (accept)paired t test

PAHs: Fultz v. Isco Sampling - D+P NW Branch

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PCBs & PAHs in Anacostia River Water

NE & NW Branches

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2.571.090.550.494.130.830.340.93

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base diss base part storm diss storm part

Median [tPCBs] in ng/L

NE BranchNW Branch

Summary of tPCB Concentrations

Ho: base and storm flow [tPCBs] are equalp<0.05 (reject)

Median Concentrationsrange (min-max)

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22 Apr 0427 May 0424 Jun 0415 Jul 048 Dec 0412 Jan 059 Feb -5

16 Jun 0521 Sep 0524 Apr 046 May 0416 May 0428 May 04

8 Jul 049 Sep 0420 Aug 0514 Apr 0427 Apr 043 May 046 Jun 04

12 Jun 0418 Jun 0426 Jun 0423 Jul 0412 Aug 0424 Dec 0415 Jan 059 Jul 059 Aug 058 Oct 05

Sampling Date for NE Branch

[tPCBs] ng/L

ParticleDissolved

Base Flow11 to 115 cfs

Storm Flow140 to 4,320 cfs

>0.25 in/hr38 to 119 cfs

NE Br Base- and Storm Flow tPCBs

%particle %dissolved

47%53%


65%35%


72%23%

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22 Apr 0427 May

24 Jun 0415 Jul 0412 Jan 059 Feb 0516 Jun 0521 Sep 059 Sep 0416 Jul 0514 Apr 0424 Apr 048 May 0412 Jun 0418 Jun 0426 Jun 048 Jul 0423 Jul 0413 Aug 0429 Sep 044 Dec 0424 Dec 0415 Jan 0524 Mar 05

3 Apr 0521 May9 Jul 058 Oct 05

Sampling Date

[tPCBs] ng/L

particledissolved

Base Flow6.7 - 46 cfs

Storm Flow61 - 3,810 cfs

>0.25 in hr20 - 28 cfs


18%

82%


60%40%


91%

9%

NW tPCBs

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0 20 40 60 80 100

18, 1574709599

77, 136153, 132

31, 285247

44, 376684

119110138

187, 183203, 196

332264

60, 56929787

151135105,

4282

149, 118141128177

156, 171157, 202

199170

8091

179137174

49158126185190189207146168205

86, 81195206114208194

166, 178167191201115120123198180169209

90, 101

Detection Frequency (D+P) NE Branch

61% (54) of PCB congeners detected in >80% of NE samples

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0

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base storm

% Major PCBs/tPCBs (wt/wt)

± 12% ± 12%

>85% of tPCB Mass Associated 54 Major Congeners

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PCB Homologue Distribution NE Branch

0 10 20 30 40 50

3

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7

8

9

10

Homologue Group

Median % Relative Abundance

particledissolved

Dissolved: 4>5>6>3>7>8>9>10Particle: 5>4>6>7>8>3>9>10

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PCB Homologue Distribution NW Branch

0 10 20 30 40 50

3

4

5

6

7

8

9

10

Homologue Group

% Relative Abundance

ParticleDissolved

Dissolved: 4,5>3>6>7>8>9>10Particle: 4>5>6>3>7>8>9>10

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0

5

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trichlorotetrachloropentachlorohexachloroheptachloro

octachlorononachlorodecachloro

NE Branch124212541260

Aroclor Homologue Profiles v. NE Branch

% R

el A

bund

ance

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LBD Hickey Watts Clay St PEPCO WNY

diss + part [tPCBs] ng/L

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[TSM], mg/L

tPCBs, ng/L

TSM, mg/L

Median [tPCBs], ng/L LBD 12 Hickey 11 Watts 6 Clay St. 22 PEPCO 23WNY 10

Diss + Part tPCB Concentrations (m/V)

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718

1496731

846

631526

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base diss base part storm diss storm part

Median [tPAHs] ng/L

NE BranchNW Branch

Summary of tPAH Concentrations

Ho: base and storm flow [tPAHs] are equalp<0.05 (reject)

Median Concentrationsrange (min-max)

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0

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4/21/20046/23/200412/7/20042/8/20059/20/20054/13/20044/26/20045/5/20045/27/20046/11/20046/25/20047/22/20049/8/20041/14/20058/8/200510/7/2005

[tPAHs] ng/L NE

ParticleDissolved

%dis %part

13%87%

%dis %part

55%45%

Base Flow

Storm Flow

NE Br Base- and Storm Flow tPAHs

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ConclusionsConclusions

• Particles in storm flows represent greatest PCB/PAH inputs

• PCBs/PAHs in dissolved phase of river water are relatively constant among flow regimes

• PCB/PAH hotspots are likely derived from storm flow inputs near outfalls and up small tribs in urbanized subsheds

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AcknowledgementsAcknowledgements

Technical: David Velinsky, Hyun-Min Hwang, Cherie Miller, Tom Huff

Students: Eldon Roberts, Robert Allen, Phil McEachern

Collaborators: OWML, Appl Environ, USGS, MWCOG, MDE

Sponsors: CBPO/EPA, AWTA, MWCOG, Jeffress Mem Trust, MDE

gmu chemistry & biochemistry pcbs and pahs in the anacostia river: sampling, concentrations and...

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