David R. Hilker

Analysis of 2,3,7,8-Tetrachlorodibenzo-p-dioxin in Great Lakes fish

Abstract In fish samples from Lake Ontario and Lake Huron 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was found at concentrations from 2 to 162 pg/g (ppt) and from 2.5 to 29 ppt respectively. Fish from the other Great Lakes (Lake Superior, Lake Michigan and Lake Erie) generally had no detectable signals for TCDD although a few samples had

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. summation operatorPBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n=42) ranged from 80 to 25720 ng g(-1)lw, (overall mean 2403+/-5406 ng g(-1)lw). By age, mean summation operatorPBDE concentrations were: 3645+/-7388, 2945+/-5995, 1385+/-1265, and 326+/-193 ng g(-1)lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n=12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g(-1)lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.

Tetrachlorodibenzo-P-dioxins and tetrachlorodibenzofurans in Atlantic Coast striped bass and in selected Hudson River fish, waterfowl and sediments

In striped bass samples from the lower Hudson River and its estuary 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was found at concentrations from 16 to 120 pg/g (ppt). Striped bass from two other locations (Rhode Island coastal waters and Chesapeake Bay, Maryland) had <5 ppt, 2,3,7,8-TCDD. The contaminant, 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF), was found in striped bass from all three locations with concentrations varying from 6 ppt in Chesapeake Bay to 78 ppt in the Hudson River. Results from a limited number of non-migratory fish (carp and goldfish) and sediments suggest that the upper Hudson River is not a source for 2,3,7,8-TCDD/2,3,7,8-TCDF contamination of striped bass.

2,3,7,8-Tetrachlorodibenzo-p-dioxin in sediment samples from Love Canal storm sewers and creeks.

247-250. (44) Davis, E. M.; Bishop, J. R.; Guthrie, R. K.; Forthofer, R. Water Res. 1978, 12, 917-923. (45) Petrasek, A. C.; Wolf, H. W.; Esmond, S. E.; Andrews, D. C. “Ultraviolet Disinfection of Municipal Wastewater Effluents”; U S . Environmental Protection Agency: Cincinnati, OH, 1980; p 228 (EPA-600/2-80-102). (46) Portnoy, B. L.; Mackowiak, P. A.; Caraway, C. T.; Walker, J. A.; McKinley, T. W.; Klein, C. A. J. Am. Med. Assoc.

Measurement of PCDFS and PCDDS in air samples and lake sediments at several locations in upstate New York

Abstract To study atmospheric deposition, air samples from Niagara Falls and sediment core layers from Green Lake, NY were analyzed for PCDFs and PCDDs. The sediment results indicate that these compounds were present in 1860 and increase rapidly after 1923; however, preliminary data show a decline in PCDF concentrations in 1979–1984, the most recent sample analyzed.

Analysis for 2,3,7,8-tetrachlorodibenzofuran and 2,3,7,8-tetrachlorodibenzo-P-dioxin in a soot sample from a transformer explosion in Binghamton, New York

2,3,7,8-TCDF and 2,3,7,8-TCDD were found in a soot sample from a transformer explosion that occurred in an office building in Binghamton, New York. The isomer-specific analytical method was high-performance liquid chromatography, capillary gas chromatography and high-resolution mass spectrometry.

Ambient air and incinerator testing for chlorinated dibenzofurans and dioxins by low resolution mass spectrometry

Abstract Chlorinated dibenzofurans and dioxins were quantified in air samples collected every two weeks for six months at two locations in Niagara Falls, N.Y.

A survey of twenty community water systems in New York State for PCDDs and PCDFs

Abstract Two tetrachlorodibenzofurans (TCDFs) were found at concentrations of 1 part-per-quadrillion (ppq) in finished drinking water from one of 20 community water systems in New York State. A follow-up study also revealed that tetra- to octa-chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs) were present at part-per-trillion (ppt) to part-per-billion (ppb) concentrations in sediments taken from the same community water system and at ppq in raw water entering the plant.

Detection of sulfur analog of 2,3,7,8-TCDD in the environment

Abstract High-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) combined with a screening bioassay for dioxinlike activity was used to identify 2,3,7,8-tetrachlorothianthrene (2,3,7,8-TCTA), the sulfur analog of 2,3,7,8-tetrachlorodibenzo- p -dioxin (2,3,7,8-TCDD), in sediment from a sanitary sewer. The dioxinlike activity detected by the bioassay was considerably higher than could be accounted for by the 2,3,7,8-TCDD concentration as determined by HRGC/HRMS. Identification of a sediment component as 2,3,7,8-TCTA was confirmed by interpretation of its high-resolution mass spectrum and comparison of its mass spectrum and gas-chromatographic retention time with those of pure 2,3,7,8-TCTA. The sample was taken from a sanitary sewer near the chemical company which patented 2,3,7,8-TCTA. This combination of a screening bioassay with HRGC/HRMS can increase the likelihood of detecting and identifying compounds that are not targeted in a chemical analysis but may have important biologic activity.

Modification of a high-performance liquid chromatographic—gas chromatographic procedure for separation of the 22 tetrachlorodibenzo-p-dioxin isomers

Abstract A published method for separation of the 22 tetrachlorodibenzo- p -dioxin (TCDD) isomers by high-performance liquid chromatography (HPLC)—gas chromatography (GC) was modified to improve the recovery and chromatographic resolution of individual isomers. For the first step, reversed-phase HPLC, minor changes were made in column temperature (50 to 40°C, to prolong column life) and in injection solvent (chloroform to benzene, to avoid photodecomposition). For the second step, normal-phase HPLC, the silica gel columns were used in a less active state, and 0.4% toluene was added to the hexane eluent as a polar orgnaic modifier. Resolution of the 22 isomers was significantly improved by this change of solvent system, and recovery of subnanogram quantities of TCDDs from the silica gel columns was increased from 20 to 80%. For the final step a capillary GC column (OV-275) was used in place of a packed column.