R.E. Clement

Quantitative determination of organic priority pollutants in sewage sludge by GC/MS

Abstract An analytical method for the simultaneous determination of organochlorine pesticides, PCBs, PAHs, phthalates, chloroaromatics, phenolics, phenoxy acids and other base/neutral compounds in sewage sludge is described. Spiked sewage sludge samples were extracted with a mixture of dichloromethane/diethyl ether under basic and acidic conditions. The combined extracts were fractionated via gel permeation chromatography (GPC). Phthalates, recovered in the initial GPC fraction, were further cleaned up on a Florisil column and their presence confirmed by GC/MS. The target analytes, recovered in a separate GPC fraction, were treated with diazomethane and analyzed by GC/MS. Method performance based on the recoveries of target compounds from spiked sludge samples is discussed. Over 100 organic analytes can be determined in a single sludge sample by this method.

PCDD and PCDF in air, soil, vegetation and oily runoff from a tire fire

In early February 1990, vandals set fire to a used tire storage facility near Hagersville, Ontario, Canada, During the fire, the Ontario Ministry of Environment and Energy (MOEE) monitored the site and surrounding impact zone for numerous organic contaminants. Samples of air, soil, vegetation, runoff water, and oily residue were collected and analyzed for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). Air samples produced complex incineration patterns with a large number of isomers detected. Total toxicity equivalents (TEQ) at 1 km downwind of the fire were an order of magnitude higher than those at 3 km downwind. Soil samples collected during the fire did not show elevated PCDD or PCDF concentrations, however, low concentrations were detected in vegetation collected at 100 m and 200 m from the site. PCDD and PCDF concentrations in the foliage decreased with time but were still detectable for at least 200 days after the fire started. As the tires burned, water used to extinguish the fire caused runoff of oil and oily water. Unique patterns of PCDDs and PCDFs were detected in these samples.

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in wood burning stoves and fireplaces

Abstract Samples of bottom ash and chimney ash were collected from two wood burning stoves, one open fireplace, and from out-of-doors open-air burning. Although only untreated wood was burned, PCDD/PCDF was detected in all samples. Large differences in total PCDD/PCDF and relative congener amounts were observed between samples, although within-congener isomer patterns were very similar and in some cases resembled the patterns detected in municipal incinerator flyash. Acid treatment of the ash before extraction increased the amounts of PCDD/PCDF detected.

Comparison of instrumental methods for chlorinated dibenzo-p-dioxin (CDD) determination - interim results of a round-robin study involving GC-MS, MS-MS, and high resolution MS

Abstract A study was designed to determine the feasibility of using GC-MS-MS techniques for the determination of chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in difficult environmental samples with reduced cleanup. Three fish and three sediment extracts were provided to six different laboratories with GC-MS-MS capability for analysis. In addition, extracts were analysed by GC-low reduction MS (LRMS) and GC-high resolution MS (HRMS). At the time of this report, all participating GC-MS-MS laboratories had not completed their analysis of the supplied samples. All reporting laboratories found the analysis of these very complex samples difficult without extensive cleanup. GC-HRMS determination of some samples was possible with reduced cleanup compared to GC-LRMS.

Preliminary report: Dioxins and furans in prescribed burns

The Ontario Ministry of Environment (MOE) recently participated in a joint Canadian/U.S. program to monitor the behavior and environmental impact of prescribed fires. Air, soil and ash samples were collected at the burn sites and analyzed for chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF). Preliminary results indicated that larger air sample volumes were required.

Concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans in effluents and centrifuged particulates from Ontario pulp and paper mills

Abstract Chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) were determined in effluents and centrifuged particulates from nine pulp and paper mills situated in Ontario, Canada. The centrifuged particulates from all mills contained some CDD/CDF congeners, although they were not always detected in the corresponding effluents. The greatest concentrations of CDDs/CDFs were found in the effluents and particulates from the bleached kraft mills, where the tetrachlorinated CDDs/CDFs were the predominant congeners.

Comparison of high volume sampling techniques for dioxins and furans in ambient air

Abstract Spiking experiments were performed to determine the sampling efficiency of a modified high volume sampler equipped with a filter and polyurethane foam (PUF) plugs. Good surrogate recovery from both the PUF and filter was obtained and some breakthrough of the lower chlorinated congeners from the filter to the PUF was observed. A comparison of the MOE modified HiVol and a General Metal Works model PS-1 sampler was also made.

Levels of PCDD/PCDF and other chlorinated organics in municipal refuse

Abstract Representative samples of refuse were obtained from two municipal incinerators in Ontario. Analysis indicated that daily input levels of polychlorinated dibenzodioxins (PCDD) polychlorinated dibenzofurans (PCDF), polychlorinated biphenyls (PCB), chlorophenols (CP) and chlorobenzenes (CB) were significant (grams/day). Comparison of PCDD/PCDF congener distribution in stack emission samples to refuse extract samples showed absence of the lower chlorinated congeners in most cases. Only hepta and octachlorodioxin were detected. Total CP, CB and PCB were detected at much higher levels than total PCDD/PCDF.

Water round robin for parts-per-quadrillion determination of PCDDs and PCDFs

Abstract As a part of the provincial Municipal Industrial Strategy for Abatement (MISA), the Ontario Ministry of Environment (MOE) carried out a round robin study on four litre spiked water samples to determine interlaboratory precision, accuracy and achievable detection limits for chlorinated dibenzo-p-dioxins (CDD) and chlorinated dibenzofurans (CDF). The results from the six participating laboratories are presented.

Interlaboratory testing study on 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran isomer standard solutions

Abstract Carefully prepared isomer standard solutions of all 17 of the 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans and their corresponding crystalline materials were provided to nine environmental analytical laboratories for the purpose of performing a round robin study of the accuracy and reliability of the standard solutions. Consensus values were determined for each isomer. Good correlation was found between the target values and the consensus values.