Lars-Owe Kjeller

Overview on environmental fate of chlorinated dioxins and dibenzofurans. Sources, levels and isomeric pattern in various matrices

Abstract Polychlorinated dioxins and dibenzofurans have been identified in technical products and pesticides, most of which are not very widely used today. Other sources are incinerators of various types like MSW incinerators, but also hazardous waste incinerators and industrial incinerators. PCDDs and PCDFs have also been identified in exhausts from cars running on leaded gasoline with halogenated additives. Background levels of PCDDs and PCDFs have been identified in fish and other aquatic organisms from the Great Lakes and the Baltic Sea, and also in human adipose tissue samples from USA, Canada, Sweden, Japan and Viet Nam as well as in samples of breast milk from Sweden, Denmark, West Germany, the Netherlands, Yugoslavia and Viet Nam. The isomeric pattern in all these biological samples is very similar.

Time trends in levels, patterns, and profiles for polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in a sediment core from the Baltic Proper

A rural laminated sediment core from the northwestern part of the Baltic Proper (station P18) was sliced into nine dated disks. (Average age : 1882, 1906, 1922, 1938, 1954, 1962, 1970, 1978, and 1985). Each disk was analyzed for tetra- to octachlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and seven congeners of chlorinated biphenyls (PCBs). Both PCDD/Fs and PCB were detected in small but significant levels during the period 1882-1962 (total PCDD/F 92-234 pg/g). The proposed sources are combustion of various natural items like coal, wood, and peat. Increased PCDD/F and PCB levels were found during the period 1970-1985 (total PCDD/Fs 520-1800 pg/g). The increased concentrations coincide with a change in PCDD/F congener profiles and isomeric patterns. Detailed examination of the profile and pattern demonstrates that chloroorganics, and among them pentachlorophenol (PCP), are the main contributors to PCDD/Fs. Polychlorinated alkyldibenzofurans (alkyl-PCDFs) were detected in the 1985 and 1978 disks, providing evidence of coastal transport and demonstrating the impact of pulp mill chlorine bleaching activities. The transport time for particulates with coastal origin is estimated to be in order of decades. This should be compared to the atmospheric input via dry and wet deposition, which is estimated to have a residence time in the water column of a maximum of 2 years. Degradation is assumed to be insignificant, but an estimate of minimum half-life times for PCDD/F in buried sediment is made.

Analyses of PCDDs and PCDFs in sludge and water samples

Abstract PCDDs and PCDFs have been identified in sludge samples from municipal water treatment plants and river water. The sampling technique and the analytical technique is discussed.

Levels, profile and pattern of PCDDs and PCDFs in samples related to the production and use of chlorine

Abstract Analyses of sludge from graphite electrodes used in the chloralkali process show total levels of PCDFs as high as 650000 pg/g sludge. The levels of tetra-, penta-and hexaCDFs were found to be approximately the same. The levels for the corresponding PCDDs were below the detection level. The dominating congeners within each group are the toxic 2,3,7,8-substituted PCDFs at levels of 340000 pg/g, This typical pattern, called the “chloralkali pattern” can also be found in soil samples taken at another chloralkali plant. The typical pattern can also be identified in a solution of ferric chloride. Traces of “chloralkali pattern” are identified in a sludge sample from the drinking water purification plant, the source for PCDFs in the sludge is unknown.

Levels and patterns of PCDD and PCDF contamination in fish, crabs, and lobsters from Newark Bay and the New York Bight

Abstract Samples of striped bass, crabs and lobsters were collected in Newark Bay and the New York Bight. The fish muscle and the hepatopancreas and meat from the crabs were subjected to congener specific analysis. All samples were found to be contaminated by 2,3,7,8-tetraCDD and a series of other highly hazardous 2,3,7,8-substituted congeners as well as less hazardous PCDDs and PCDFs. A value exceeding 6000 ppt wet tissue weight of 2,3,7,8-tetraCDD was found in a sample of crab hepatopancreas, which seems to be the highest value so far reported in a food product. The crab meat, on the other hand, contained only 100 ppt. In general the crustaceans contained many congeners, while the fish samples contained only 2,3,7,8-substituted compounds. An unknown compound, possibly a tetrachlorodibenzothiophene, was the dominating peak in most of the crustacean samples.

Patterns and sources of polychlorinated dibenzo-p-dioxins and dibenzofurans found in soil and sediment samples in Southern Mississippi

Using hierarchical cluster analysis and Principal Component Analysis (PCA), sediment and soil samples from the State of Mississippi were compared with the effluents of a pulp mill, a potential point source. Additionally, data of many known sources of PCDD/PCDF from the scientific literature were evaluated. Both methods were able to distinguish between different matrices with known PCDD/PCDF contamination (e.g. PCP, PCB, kraft pulp mill effluents). In some instances, a specific PCDD/PCDF source could be correlated to an environmental sample, e.g. the pattern of a U.S. brand of pentachlorophenate was found in sediment samples. None of the mathematical and statistical techniques could identify the pulp mill as the source of the PCDD/PCDF in the sediments and soils in the floodplain.

Levels of PCDDs and PCDFs in products and effluent from the Swedish pulp and paper industry and chloralkali process

Abstract Within the Swedish Dioxin Survey various samples from the pulp and paper industry and the chloralkali process have been analyzed by congener specific analytical methods. In addition to the generally discussed “bleaching pattern” of the tetrachlorinated congeners, these samples also contained higher chlorinated congeners like hexa-CDDs, hepta-CDFs, octa-CDD and octa-CDF. Consequently it is recommended that samples from the pulp industry should be analyzed for all PCDDs and PCDFs (tetra- through octa-). Counted as Nordic Toxic Equivalents (NTEQ), the recycled pulp samples had the highest contamination level followed by TMP, unbleached sulfite and bleached softwood and hardwood. In addition to the bleaching process, various chemicals used in the pulping, bleaching and wastewater treatment can contribute to the contamination.

Sampling and analysis of water and suspended particulate matter of the river Elbe for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs)

Abstract A sampling method for the determination of the particle-bound and dissolved PCDDs/Fs in the river Elbe is described. The suspended particulate matter (SPM) sample was taken by means of a centrifuge. For the water phase a sampling system with three modules was developed (FILAD I). The first two modules serve as filters, the third for solid/liquid-extraction. Samples were analysed by HRGC/HRMS for PCDDs/Fs. The concentrations of the dissolved PCDDs/Fs were in the fg/L range. Detection limit for dissolved PCDDs/Fs was 0,7 - 0,9 fg/L. Particulate organic carbon/water partition coefficients (Koc) were calculated. The results show that the analysis of particle-bound PCDDs/Fs alone would be sufficient to determine their concentration in the river Elbe. The differences in PCDD/F concentrations and in isomeric patterns of SPM between two sampling points, one upstream and the other downstream of the harbour of Hamburg, are discussed.

Polychlorierte Dibenzo-p-dioxine (PCDDs) und polychlorierte Dibenzofurane (PCDFs) in Sedimenten und Fischen aus dem Hamburger Hafen

Abstract In the paper we report on isomerspecific analyses of PCDDs and PCDFs in 25 samples of sediments and 15 samples of fish collected in the harbor of Hamburg, Federal Republik of Germany. 2,3,7,8-TCDD was identified and quantified in all samples. In the sediments point sources were identified where background levels were exceeded by a factor of 10–70. In the paper we discuss possible sources to the contamination. The levels in the fish samples were found to parallel the sediment levels.

Sources and Relative Importance of PCDD and PCDF Emissions

Polychlorinated dioxins (PCDD) and dibenzofurans (PCDF) have been identified in technical products and pesticides, most of which are not very widely used today. Other sources are incinerators of various types like MSW incinerators, hazardous waste incinerators and industrial incinerators. PCDDs and PCDFs have also been identified in exhausts from cars running on leaded gasoline with halogenated additives. Background levels of PCDDs and PCDFs have been identified in fish and other aquatic organisms from the Great Lakes and the Baltic Sea, and also in human adipose tissue samples from U.S.A., Canada, Sweden, Japan and Vietnam as well as in samples of breast milk from Sweden, Denmark, West Germany, the Netherlands, Yugoslavia and Vietnam. The isomeric pattern in all these biological samples is very similar. The relative importance of different sources to the general background is difficult to estimate although the contribution of direct inhalation from point sources like MSW incinerators is small.