P. O'Keefe

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

Acute toxicity in guinea pigs and rabbits of soot from a polychlorinated biphenyl-containing transformer fire

Abstract A fire involving a polychlorinated biphenyl (PCB)-containing transformer extensively contaminated the State Office Building in Binghamton, New York, with a sootlike material containing 2,3,7,8-tetrachlorodibenzo- p -dioxin (2,3,7,8-TCDD), 2,3,7,8-tetrachlorodibenzofuran, and high concentrations of numerous other polychlorinated dibenzodioxins, dibenzofurans, and PCBs. The oral LD50s of the soot and of its benzene extract, each administered to female guinea pigs in 0.75% aqueous methyl cellulose, were 410 mg of soot/kg and 327 mg of soot equivalent/kg, respectively. Serum triglycerides were elevated in males at 100 and 500 mg/kg and in females at 500 mg/kg. Alkaline phosphatase was lowered in females at 500 mg/kg. Histopathology revealed dose-related pancreatic duct hyperplasia and salivary gland duct metaplasia in males. Body weight loss was observed in both sexes at 500 mg/kg. Thymus weight decreased in both sexes at 100 and 500 mg/kg, and kidney weights decreased in males at these doses. Dermal application of soot to rabbits for 24 hr caused no overt toxicity, although hepatic centrilobular hypertrophy was observed in both sexes. Similar application of soot extract caused a local serous inflammation in addition to the hepatic centrilobular hypertrophy. The oral LD50 for 2,3,7,8-TCDD in female guinea pigs was 19 μg/kg in aqueous methyl cellulose and 2.5 μg/kg in corn oil. We concluded that the soot matrix alters the dermal but not the oral toxicity of its components, that the toxic effects were consistent with those reported after exposure to dibenzodioxins and dibenzofurans, and the aqueous vehicle markedly diminished the acute toxicity of 2,3,7,8-TCDD relative to that in corn oil vehicle.

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.

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.

Polychlorinated dibenzofurans and dibenzo-p-dioxins in subsurface soil, superficial dust, and air extracts from a contaminated landfill

Extracts of soil, dust and air from a National Priorities List Landfill have been found to contain distinct profiles of polychlorinated biphenyls (PCBs). The different extracts show subtle differences in toxicities and the soil extract has been shown to cause both Ah receptor mediated effects and Ah receptor independent effects in immature female rats. Evidence of open burning at the site dictated quantitation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) for a more accurate tabulation of dioxin equivalencies. High volume air sampling on XAD-2 resin cartridges captured trace amounts of PCDFs and no detectable PCDDs. Acetone:Hexane (1:1) extracts of soil and dust contained 762 μg/ml and 250 μg/ml PCDFs, respectively, and less than 10% as much PCDD. Subsequent benzene:methylene chloride (1:1) extracts were enriched in coplanar compounds relative to total PCBs. PCDF:PCB ratios in all extracts were higher than in the rice oils contaminated with heated PCBs in the Yusho and Yu-Cheng incidents. No 2,3,7,8-TCDD was detected, and total PCB + PCDD + PCDF toxic equivalencies were dominated by the high proportions of PCDFs.

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.