Jaana Koistinen

Toxic significance of planar aromatic compounds in Baltic ecosystem — New studies on extremely toxic coplanar PCBs

Abstract Baltic salmon and white-tailed eagle samples have been analyzed for organochlorine compounds including polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, polychlorinated naphtalenes and toxic coplanar PCBs. In salmon, PCB and DDT residue contents were 0.2-0.3 ug/g in fresh muscle. Chlordanes, toxaphene, hexachlorobenzene, α-hexachlorocyclohexane and γ-hexachlorcyclohexane were found at 1 – 10 ng/g levels. Significant dioxin type of toxins found were only 2,3,7,8-tetrachlorodibenzofuran (45–81 pg/g) and 3,3′,4,4′-tetrachlorobiphenyl (638–1120 pg/g). Polychloronaphtalene contents in all salmon and eagle samples were of the same order of magnitude ranging from 4 to 85 ng/g. The highest chlorohydrocarbon contents in eagle samples were for PCB 462 ug/g, sum of the DDT residues 42 ug/g, chlordanes 5.7 ug/g and HCB 1.6 ug/g. In contrary, toxaphene, α-hexachlorocyclohexane and γ-hexachlorocyclohexane were not detected in eagles. Levels of polychlorodibenzo-p-dioxins, polychlorodibenzofurans and coplanar PCBs were highest ever reported in wildlife in adult eagle samples, in liver of a juvenile eagle and in eagle egg from South Finland ranging from 1 to 13 ng/g for PCDD/Fs and from 18 to 229 ng/g for coplanar PCBs. Calculation of the TCDD-equivalents of the contents gave that dioxin toxicity load comes in great excess from the coplanar PCBs, especially from 3,3′,4,4′,5-pentachlorobiphenyl.

PCDEs, PCBs, PCDDs AND PCDFs in black guillemots and white-tailed sea eagles from the Baltic Sea

Abstract Concentrations and patterns of several chloro compounds including polychlorinated dibenzo p-dioxins (PCDD), dibenzofurans (PCDF), biphenyls (PCB) and diphenyl ethers (PCDE) were determined in black guillemots ( Cepphus grylle L.) and white-tailed sea-eagles ( Hallaeetus albicilla L.) from the Baltic Sea environment. Three breast muscles of eagles were analyzed and had different concentrations and patterns of the studied compounds, whereas the three guillemot eggs were found to have more similar levels and patterns. The concentrations of individual PCDE congeners varied from

Bone-related effects of contaminants in seals may be associated with vitamin D and thyroid hormones†

The high levels of polychlorinated biphenyls (PCBs) and DDT in gray seal (Halichoerus grypus) and ringed seal (Phoca hispida botnica) in the Baltic Sea have been associated with pathological disruptions, including bone lesions and reproductive failures. The underlying environmental and toxicological mechanisms leading to these pathological changes are not yet fully understood. The present study investigated the relationship between the individual contaminant load and bone- and thyroid-related effects in adult gray seals (n=30) and ringed seals (n=46) in the highly contaminated Baltic Sea and in reference areas (Sable Island, Canada, and Svalbard, Norway). In the gray seals, multivariate and correlation analyses revealed a clear relationship between circulating 1,25-dihydroxyvitamin D(3) (1,25(OH)(2)D), calcium, phosphate, and thyroid hormone (TH) levels and hepatic PCB and DDT load, which suggests contaminant-mediated disruption of the bone and thyroid homeostasis. Contaminants may depress 1,25(OH)(2)D levels or lead to hyperthyroidism, which may cause bone resorption. In the ringed seals, associations between circulating 1,25(OH)(2)D, THs, and hepatic contaminants were less prominent. These results suggest that bone lesions observed in the Baltic gray seals may be associated with contaminant-mediated vitamin D and thyroid disruption.

Residues of planar polychloroaromatic compounds in Baltic fish and seal

Abstract Polychlorinated dibenzo-p-dioxins, dibenzofurans, coplanar PCBs and other dioxin-type of toxins have been analyzed in Baltic salmon, cod, ringed seal and grey seal and in Arctic cod.

Polychlorinated diphenyl ethers, dibenzo-p-dioxins, dibenzofurans and biphenyls in seals and sediment from the gulf of finland

Polychlorinated diphenyl ethers (PCDEs), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were analyzed in seals from the Gulf of Finland and in sediments from the Gulf of Finland and near Gotland. The sediments included one surface core from both sampling sites. The seal material consisted of 14 ringed seals and 6 grey seals that all were found dead and examined for pathology. The main aims were to scrutinize levels and patterns of PCDEs for the first time in seals from the Baltic Sea and to estimate whether chlorinated compounds mentioned have an influence on an exceptional high mortality that occurred among ringed seals in the Gulf of Finland in late 1991. The concentrations of 50 congeners of tetra- through deca-CDEs analyzed ranged from < 0.3 to 62 ng/g lipid weight (lw) in seal blubber, but in the sediments PCDEs were non-detectable (tetra- through hepta-CDEs < 0.1 ng/g dry weight (dw)). In ringed seals with good nutritional status, the concentrations of almost all PCDE congeners were greater in two adult females than in specimens of younger age groups. The concentrations of PCDDs and PCDFs as TCDD-equivalents exceeded those of the coplanar (non-ortho) PCBs in sediments, whereas non- and monoortho PCBs constituted greater toxic loads as those calculated for PCDDs and PCDFs in seals. However, the levels revealed do not explain the high mortality of ringed seals.

Dioxins and other planar polychloroaromatic compounds in Baltic, Finnish and Arctic Fish samples

Abstract Polychloroaromatic compounds were analyzed with GC/MS in Baltic salmon, cod liver fat from the Arctic coast of Norway (Vestertana) and fish from Lake Kernaala in South Finland. Total PCBs in salmon and in cod liver fat were at backround levels (140–270 and 700–900 ng/g, respectively). Fish in Kernaala were heavily polluted by PCB (6000–14000 ng/g). PCDDs and PCDFs in the present samples were below 5 pg/g except 2,3,7,8-tetra-CDF, which was found 5–9 pg/g in Kernaala fish. In salmon, five different polychlorinated diphenyl ethers were found 5–19 pg/g, polychloronaphthalenes 0.1–12 ng/g and heptachlorofluorenones 0.1–7 ng/g. The extremely toxic coplanar PCBs were found in all samples: 3,3′,4,4′-tetra-CB 70–900 pg/g and 3,3′,4,4′,5-penta-CB 30–300 pg/g.

Synthesis, structure verification, and chromatographic relative retention times for polychlorinated diphenyl ethers.

Fifty-four polychlorinated diphenyl ether (PCDEs) congeners were synthesized, and their structures were confirmed by mass spectrometry and proton magnetic resonance spectroscopy. The gas chromatographic relative retention times (RRT) for the PCDEs were determined relative to a reference standard, [ 13 C-3,3,4,4]-tetrachlorobiphenyl (PCB 77) on the fused silica capillary columns of SE-54 and OV-1701. The retention times for PCDEs increased with the increasing number of vicinal chlorines within a series of isomers. The chlorine substitution patterns of PCDEs were used to develop a method for predicting RRTs for congeners that were not synthesized

Lipid-Filled semipermeable membrane devices and mussels as samplers of organochlorine compounds in lake water.

Semipermeable membrane sampling devices (SPMDs) and caged lake mussels (Anodonta piscinalis) were simultaneously deployed at four lake watercourse sites in Central Finland four weeks in August 1992. This study was part of the regular annual monitoring of the organochlorine compounds (OCC) in pulp-mill recipient watercourses of Finland with bivalves. Chlorohydrocarbons (CHCs), chlorophenol compounds (PCPs), chloroanisoles (PCAs) and chloroveratroles (PCVs) were analyzed from lipid extract of mussels and from the synthetic triolein lipid of the SPMDs. Hexane-diethyl ether (9:1, v/v) dialysis using polyethylene membrane was applied in dean up of the SPMD lipids and, for comparison, to six sets of the mussel fat. Dialysis recovered CHCs but not PCPs from the mussel fat. CHCs, PCPs, PCAs and PCVs were all recovered in dialysis of the SPMD lipid. Handling of SPMDs in the transport and deployment operations caused significant OCC contamination for the blank SPMDs. Similar trends were revealed in the OCC profiles for mussels ans SPMDs. An exception was the lack of PCPs appearing in SPMDs that did appear in mussels and in a complementary manner the appearance of the PCAs and PCVs in SPMDs.

Bioaccumulation of dioxins, coplanar PCBs, PCDEs, HxCNs, R-PCNs, R-PCPHs and R-PCBBs in fish from a pulp-mill recipient watercourse

Abstract Pike, perch and lake bream from the river Kymijoki were analyzed by gas chromatography/mass spectrometry (GC/MS) for toxic polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), hexachlorinated naphthalenes (HxCNs), non-ortho substituted polychlorinated biphenyls (coplanar PCBs) and alkylchloroaromatics of pulp mill origin. In most fish, the only congener of PCDD/PCDFs found was 2,3,7,8-TeCDF (

Mussel incubation method for monitoring organochlorine pollutants in watercourses. Four-year application in Finland

Abstract Four week incubation of mussels followed with analyses has been developed to a sensitive method for monitoring chlorohydrocarbons, chlorophenols and aromatic chloroethers in watercourses. During four-year application at the Kymijoki river basin in Central and Southern Finland a decreasing trend of chlorophenol pollution, appearance of chlorocymenes, -cymenenes, other chlorohydrocarbons from pulp bleaching and bioaccumulation of chloroanisoles and -veratroles were shown. A continuing local PCB pollution was found and place of its origin traced. Use of combined samples in analysis to improve the economy of monitoring was applied successfully. Toxaphene components and toxic PCDD and PCDF congeners were absent in mussels incubated very near to the effluent pipe of activated sludge treatment plant of a kraft pulp mill.