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 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 1668A PCDD/Fs – 17 congeners, USEPA Method 1613 Chlorinated 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.

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

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. PCBs in STP sludges mg/kg

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.

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

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 Hudson River at head of tide, Waterford, NY. Hudson River, mid-tidal, Kingston to Poughkeepsie Hudson River, lower tidal, Haverstraw Bay Effluents from 29 WPCFs New York Bight

Tetra- and Pentachlorobiphenylenes Tetra > penta Pre-dated 9/11 in sediments Very little is known about toxicity Weak evidence for a WTC impact?

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

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

Polybrominated Dioxins and Furans Expected pyrolysis products of PBDEs Tentative WHO TEFs* about the same as for PCDD/Fs Field and analytical methods are immature High method blanks and field blanks suggest: These are abundant chemicals and Procedures for ensuring cleanliness of PCB and PCDD/F are inadequate for the PBDD/Fs. *

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

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

Surface water samples show that PBDD/Fs are significant but are not correlated with PCDD/Fs. Post 9/11

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 Differences may be due to TOC. Congener abundance patterns were similar.

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.