The Destruction of the World Trade Center and PCBs, PBDEs, PCDD/Fs, PBDD/Fs, and Chlorinated Biphenylenes in Water, Sediment, and Sewage Sludge Simon Litten,

The Destruction of the World Trade Center and PCBs, PBDEs, PCDD/Fs,

PBDD/Fs, and Chlorinated Biphenylenes in Water, Sediment, and Sewage Sludge

Simon Litten, NYSDEC

Dennis J. McChesney, USEPA, Region 2

M.C. Hamilton, Axys Analytical Services

Brian Fowler, Micromass, Canada, Victoria

Shortly after the destruction of the World Trade Center investigators from the USEPA Region 2 and the NYSDEC sampled run-off water and surface waters to determine if the calamity was affecting water quality in New York Harbor.

In the immediate aftermath of the event security was very tight and the extent of the infrastructure damage was unknown. EPA field teams reached Ground Zero on 9/14. NYSDEC had been conducting an extensive monitoring project for trace contaminants in the harbor since 1998.

WTC environmental samples were among the first packages to be shipped as air-courier services were re-established in the afternoon of 9/15.

Organic analytes were selected on the basis of on-going NY harbor work (PCBs, PCDD/Fs, PAHs, and chlorinated pesticides), recollection of the 1982 State Office Building fire in Binghamton, NY (chlorinated biphenylenes), current interests in brominated flame retardants (PBDEs), and research showing that pyrolyzation of PBDEs produces brominated dioxins and furans (PBDD/Fs).

PCBs – 209 congeners (157 domains), USPEA Method 1668APCDD/Fs – 17 congeners, USEPA Method 1613Chlorinated Biphenylenes – 2 homologues (tetra-, pentachlorobiphenylene, 1613 (modified)PBDEs – 44 congeners, 1668A (modified)PBDD/Fs – 12 congeners, 1613 (modified)

The World Trade Center complex was located near the south western tip of Manhattan. The labeled points are sites sampled by EPA on 9/20. On 9/14 EPA collected one run-off sample at the foot of Rector St. NYSDEC took sediment samples on 9/19 and on 10/5 collected a single large volume sample (570 L) on the western side of Manhattan. NYCDEP took sludge samples on 9/19 and 9/25 from NC STP.

On 9/14 USEPA sampled run-off at the foot of Rector St. This sample consisted of ash and dust being flushed off the street by a NYCDOS crew using water supplied by a NYFD fire boat. The site was re-visited on 9/20.

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

1-mono 2-di 3-tri 4-tetra 5-penta 6-Hexa 7-Hepta 8-Octa 9-Nona 10-Deca

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13 ng/L - ER SOUTH ST.17 ng/L - GW BRIDGE11 ng/L - HR NORTH7.8 ng/L - HR SOUTH11 ng/L - HR WEST96 ng/L - RECTOR ST, 9/2024,000 ng/L - RECTOR ST, 9/148,400 ng/L - RECTOR ST., 9/14

Plots of relative abundances of PCB homologues show that Rector St. run-off was consistent. Hudson River ambient samples taken on 9/20 showed a different pattern.

Hudson River, 9/20 Rector St. 9/14 and 9/20

Total PCB concentrations are shown in the legend

Large volume PCB samples collected in the lower Hudson R. off western Manhattan before and after 9/11 show no difference in concentration or relative homologue abundance.

10/5/01

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

1-mono 2-di 3-tri 4-tetra 5-penta 6-Hexa 7-Hepta 8-Octa 9-Nona 10-Deca

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12/17/98 - 15 ng/L

3/16/99 - 24 ng/L

8/12/99 - 9.9 ng/L

12/14/99 - 5.3 ng/L

12/14/99 - 7.0 ng/L

10/5/01 - 10 ng/L

Sludge samples from New York City treatment plants had been examined in February; samples from the STP receiving lower Manhattan wastes were taken on 9/25 and 9/19.

0 2,000 4,000 6,000 8,000 10,000 12,000 14,000

WI, North

HP#9

BB

HP#10

CI

RH

WI, South

NC, 9/19

NC, 9/25

26Ward

PR

ug/kg PCB

PCBs in STP sludgesmg/kg

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

2,3

,7,8

-TC

DD

1,2

,3,7

,8-P

eC

DD

1,2

,3,4

,7,8

-HxC

DD

1,2

,3,6

,7,8

-HxC

DD

1,2

,3,7

,8,9

-HxC

DD

1,2

,3,4

,6,7

,8-H

pC

DD

OC

DD

2,3

,7,8

-TC

DF

1,2

,3,7

,8-P

eC

DF

2,3

,4,7

,8-P

eC

DF

1,2

,3,4

,7,8

-HxC

DF

1,2

,3,6

,7,8

-HxC

DF

2,3

,4,6

,7,8

-HxC

DF

1,2

,3,7

,8,9

-HxC

DF

1,2

,3,4

,6,7

,8-H

pC

DF

1,2

,3,4

,7,8

,9-H

pC

DF

OC

DF

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9/14, 130 pg/L

9/20, 11 pg/L

PCDD/Fs measured from Rector St. run-off on 9/14 and 9/20 were mostly PeCDF.

Dioxin concentrations are multiplied by TEFs (NATO 1988) and BEFs in conformity to NYS WQS.

00.05

0.10.15

0.20.25

0.30.35

0.40.45

0.5

2,3

,7,8

-TC

DD

1,2

,3,7

,8-P

eC

DD

1,2

,3,4

,7,8

-HxC

DD

1,2

,3,6

,7,8

-HxC

DD

1,2

,3,7

,8,9

-HxC

DD

1,2

,3,4

,6,7

,8-H

pC

DD

OC

DD

2,3

,7,8

-TC

DF

1,2

,3,7

,8-P

eC

DF

2,3

,4,7

,8-P

eC

DF

1,2

,3,4

,7,8

-HxC

DF

1,2

,3,6

,7,8

-HxC

DF

2,3

,4,6

,7,8

-HxC

DF

1,2

,3,7

,8,9

-HxC

DF

1,2

,3,4

,6,7

,8-H

pC

DF

1,2

,3,4

,7,8

,9-H

pC

DF

OC

DF

TE

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Dust A06351 TEQ pg/g - 84




TEQ/BEQ adjusted data from lower Manhattan dust samples taken immediately after 9/11.

0

0.1

0.2

0.3

0.4

0.5

0.6

2,3

,7,8

-TC

DD

1,2

,3,7

,8-P

eC

DD

1,2

,3,4

,7,8

-HxC

DD

1,2

,3,6

,7,8

-HxC

DD

1,2

,3,7

,8,9

-HxC

DD

1,2

,3,4

,6,7

,8-H

pC

DD

OC

DD

2,3

,7,8

-TC

DF

1,2

,3,7

,8-P

eC

DF

2,3

,4,7

,8-P

eC

DF

1,2

,3,4

,7,8

-HxC

DF

1,2

,3,6

,7,8

-HxC

DF

2,3

,4,6

,7,8

-HxC

DF

1,2

,3,7

,8,9

-HxC

DF

1,2

,3,4

,6,7

,8-H

pC

DF

1,2

,3,4

,7,8

,9-H

pC

DF

OC

DF

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3/16/99 - 0.45 pg/L

8/12/99 - 0.15 pg/L

6/14/00 - 0.36 pg/L

10/5/01 - 0.34 pg/L

TEQ/BEQ adjusted dioxins from the lower Hudson River. PeCDF continues to be important, but so too is 2,3,7,8-TCDD. The post 9/11 sample is the same as the others.

Two PCDD/F congeners are of particular importance in NY Harbor, 2,3,7,8-TCDD, which seems to originate from the Passaic River, and 2,3,4,7,8-PeCDF, which was found in a creek impacted by wastes from a facility incinerating obsolete electronics. The relative importance of 2,3,4,7,8-PeCDF increases moving down the Hudson R. Potential precursors are incinerated PCBs, plastics, or resins. 2,3,4,7,8-PeCDF has a TEF of 0.5.

A Tale of Two Congeners

Dioxins/Furans in Suspended Solids

0.00

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0.40

0.50

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

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100 fg/L - Mar, 99

41 fg/L - Jul, 99

100 fg/L - Dec, 98

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

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4 fg/L - Jan, 99

2 fg/L - Feb, 99

0.00

0.20

0.40

0.60

0.80

1.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

Q,

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22000 fg/L - Jun, 99

730 fg/L - Nov, 98

2500 fg/L - Feb, 99

0.000.100.200.300.400.500.600.700.80

1 2 3 4 5 6 7 8 9 1011121314151617Congener number

TE

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1300 fg/L - Aug, 99

830 fg/L - Nov, 98660 fg/L - Jan, 99

0.00

0.20

0.40

0.60

0.80

1 2 3 4 5 6 7 8 9 10111213 14151617

Congener number

TE

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2100 fg/L - Jul, 99

920 fg/L - Nov, 98

600 fg/L - Feb, 99

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

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12000 fg/L - May, 98

0.00

0.05

0.10

0.15

0.20

0.25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

Q,

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680 fg/L - Mar, 99

200 fg/L - Aug, 99

480 fg/L - Dec, 98

0.000.050.100.150.200.250.300.350.40

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

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360 fg/L - Mar, 99270 fg/L - Mar, 99110 fg/L - Apr, 99130 fg/L - Apr, 99

Hudson River at head of tide, Waterford, NY.

0.00

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0.10

0.15

0.20

0.25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17Congener number

TE

Q,

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ab

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130 fg/L - May, 99

100 fg/L - Oct, 99

Hudson River, mid-tidal, Kingston to Poughkeepsie

Hudson River, lower tidal, Haverstraw Bay

Effluents from 29 WPCFs

New York Bight

0.00

0.05

0.10

0.15

0.20

0.25

0.30

1 2 3 4 5 6 7 8 9 1011121314151617Congener number

TE

Q, re

lati

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bu

nd

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420 fg/L - Jul, 99250 fg/L - Nov, 98310 fg/L - Feb, 99

0

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0.25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Congener number

TE

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Tetra- and Pentachlorobiphenylenes

Tetra > pentaPre-dated 9/11 in sedimentsVery little is known about toxicityWeak evidence for a WTC impact?

sample tetra penta unitsRector St., 9/14 5500 1010 pg/LRector St., 9/20 14 <0.1 pg/LNC Sludge, 9/19 28 4.3 ng/kgNC Sludge, 9/25 14 1.1 ng/kgWTC N 1.4 <0.1 pg/LWTC S 1.6 <0.1 pg/LWTC W 0.26 <0.1 pg/LWTC South St 0.2 <0.1 pg/LWTC GW Bridge <0.1 <0.1 pg/LArthur Kill Sediment, 1998 57 15 ng/kg

PBDEsOffice buildings contain brominated flame retardants in computers, furnishings, and upholstery. Little is know about toxicity and background concentrations of these chemicals.

0

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0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1-Mono 2-Di 3-Tri 4-Tetra 5-Penta 6-Hexa 7-Hepta 9-Nona 10-Deca

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590,000 ng/L, 9/14/01

220 ng/L, 9/20/01

Rector St. run-off contained high levels of deca-PBDE on 9/14

Relative abundances of PBDE homologues in harbor samples taken before and after 9/11 show similar patterns.

00.10.20.30.40.50.60.70.80.9

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Hudson R. South of Harlem R., 10/5/01, 2.4 ng/LUpper Bay, 3/18/99, 12 ng/LWTC GW Bridge, 9/20/01, 26 ng/L

Four other samples taken in the Hudson and East River on 9/20 had concentrations ranging from 1.1 to 2.6 ng/L. These samples had insufficient mass to distinguish them from the blanks.

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PIER 25, 9/18/01, 0.015 mg/kg

Arthur Kill, 1998, 0.076 mg/kg

PIER 6, 9/18/01, 0.077 mg/kg

NC Sludge, 9/25/01, 11 mg/kg

NC Sludge, 9/19/01, 18 mg/kg

PBDE concentrations in sediments taken adjacent to Ground Zero on 9/18 were similar with those from the Arthur Kill taken in 1998. NC sludge concentrations were much higher. All show dominance by the decabromo congener.

Polybrominated Dioxins and Furans

Expected pyrolysis products of PBDEsTentative WHO TEFs* about the same as for PCDD/FsField and analytical methods are immatureHigh method blanks and field blanks suggest:

These are abundant chemicals andProcedures for ensuring cleanliness of PCB and PCDD/F are inadequate for the PBDD/Fs.

* www.inchem.org/documents/ehc/ehc/ehc205.htm

0 500 1000 1500 2000 2500 3000 3500

RECTOR ST., 9/20/01

RECTOR ST., 9/14/01

TEQ in pg/L

PCDD/F

PBDD/F

PCDD/Fs and PBDD/Fs in Rector St. Run-off, 9/14 and 9/20

00.10.20.30.40.50.60.70.8

2,3,7,8-TBDF 1,2,3,7,8-PeBDF

2,3,4,7,8-PeBDF

1,2,3,4,7,8-HxBDF

1,2,3,4,6,7,8-HpBDF

OBDF

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RECTOR 9/14/01

RECTOR 9/20/01

0 100 200 300 400 500

NC SLUDGE, 9/25/01

NC SLUDGE, 9/19/01

ng/kg TEQ

PCDD/F

PBDD/F

PBDD/F concentrations were higher immediately after 9/11. No PBDD/F data are available from before 9/11.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

2,3,7,8-TBDF 1,2,3,7,8-PeBDF 2,3,4,7,8-PeBDF 1,2,3,4,7,8-HxBDF

1,2,3,4,6,7,8-HpBDF

OBDF

NC SLUDGE, 9/19/01

NC SLUDGE 9/25/01

0 0.5 1 1.5 2 2.5

UB, 8/11/99

HRSHR, 10/5/01

UB, 3/18/99

TAPPEN ZEE, 7/10/99

HRPOUGH, 3/1/99

HRSHR,3/16/99

HRPOUGH, 4/17/99

HRPOUGH, 4/17/99

pg/L TEQ

Conc PCDD, TEQ

Conc PBDD, TEQ

0 5 10 15 20 25 30 35

PASSAIC, 7/21/99

PASSAIC, 8/25/99

PASSAIC 10/18/00

TEQ, pg/L

Conc PCDD, TEQ

Conc PBDD, TEQ

Surface water samples show that PBDD/Fs are significant but are not correlated with PCDD/Fs.

Post 9/11

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

2,3,7,8-TBDF 1,2,3,7,8-PeBDF 2,3,4,7,8-PeBDF 1,2,3,4,7,8-HxBDF

1,2,3,4,6,7,8-HpBDF

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PIER 25, 9.6 ng/kg TEQ

PIER 6, 13 ng/kg TEQ

Sediments collected from piers adjacent to the WTC on 9/18/01 had PBDD/F concentrations less than those seen in archived sediments taken in the Arthur Kill in 1998. Differences may be due to TOC. Congener abundance patterns were similar.

73.6

0.052

1.01

2.14

0.184

85.8

0.14

5.5

3.19

0.355

0 10 20 30 40 50 60 70 80 90 100

brominated furan

brominated dioxin

chlorinatedbiphenylene

chlorinated furan

chlorinated dioxin

Thousands

pg/L

total tetra-

total penta-

Dioxin-Like Substances in 9/14 Rector St. Run-Off

Conclusions

• We see no evidence that the destruction of the World Trade Center impacted water quality in New York Harbor.

• PCBs, chlorinated dioxins, PAHs, and chlorinated pesticides had high concentrations in run-off but show no elevation in the harbor.

• Exotic chemicals were found at high concentrations in run-off from the site.

• These substances occurred in the harbor before 9/11. • While analytical methods and toxicology are immature,

the exotics may be important environmental pollutants.

Documents

The Destruction of the World Trade Center and PCBs, PBDEs, PCDD/Fs, PBDD/Fs, and Chlorinated Biphenylenes in Water, Sediment, and Sewage Sludge Simon Litten,