0000000000033456
AUTHOR
Jaana Koistinen
Model compound synthesis for the structure determination of new unknown planar aromatic compounds originating from pulp mill
Abstract Several model compounds have been synthesized for verification of the structures of new unknown planar aromatic compounds (UPACs) observed in high-resolution gas chromatography/low-resolution mass spectrometry analyses of the polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in pulp mill products, effluents, sediments and mussels. The mass spectra of synthetic alkyl polychlorodibenzofurans (C6-PCDFs) were different, but those of alkyl polychlorobibenzyls (C5-PCBBs) were very similar compared to the spectra of UPACs.
Alkyl polychlorobibenzyls and planar aromatic chlorocompounds in pulp mill products, effluents, sludges and exposed biota
Abstract Aromatic chlorocompounds which interfere in GC/MS analysis of dioxins were studied in samples from three different pulp mills and in fish and mussels exposed to pulp mill effluents. The major interfering compounds were chlorinated alkyl bibenzyls (R-PCBBs; R = C5-alkyl; P = 1–4). In pulp mill samples, levels of C5-PCBBs (10–120 ng/l in effluents, 5–33 ng/g in dried sludges) were orders of magnitude higher than the levels of toxic PCDDs and PCDFs. C5-PCBBs bioaccumulated slightly to the recipient fish (0–2 pg/g in fresh muscles) and to incubated mussels (3–26 ng/g in lipid). In mussels, significant levels (19–73 ng/g in lipid) of other than pulp mill originated toxic hepta- and octa…
Chlorinated and methylated dibenzothiophenes: Preparation of the model compounds and their analysis from some environmental samples
Abstract Polychlorinated and polymethylated dibenzothiophenes if occuring in the environment can cause environmental hazards and problems like chlorinated dibenzodioxins and dibenzofurans. Some chlorinated and methylated dibenzothiophenes have been synthesized to serve as model compounds in environmental and toxicological analysis. The synthesis mixtures and some environmental samples have been analyzed by high resolution GC/low resolution MS. This investigation showed that the concentrations of these compounds in environmental samples were below ppb level but it did not exclude the occurence of these compounds in our environment. More investigation is needed.
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…
Polychlorinated diphenyl ethers, dibenzo-p-dioxins and dibenzofurans in finnish human tissues compared to environmental samples
Finnish human samples from the Helsinki area and Arctic cod samples from Vestertana Fjord (Norway) were analyzed for polychlorinated diphenyl ethers (PCDE) and 2,3,7,8-chloro substituted dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). The PCDE, PCDD and PCDF contents in human and animal samples from Finland and elsewhere were briefly reviewed. PCDEs were non-detectable in human liver and testis, but some PCDE congeners were identified in human adipose tissue and fat of boiled Arctic cod liver composite. The contents of PCDEs in Finnish human samples were similar to those reported in the literature for human tissues from North America. The estimated concentrations of PCDEs 99, 147 + 153 (…
Bioaccumulation, bioavailability and environmental fate of chlorophenol impurities, polychlorinated hydroxydiphenylethers and their methoxy analogues.
The bioaccumulation potential and environmental fate of polychlorinated hydroxydiphenyl ethers (HO-PCDEs; polychlorinated phenoxyphenols, PCPP), the major impurities of chlorophenol formulations and their methoxy analogues (MeO-PCDEs; polychlorinated methoxyanisoles, PCPAs) were investigated. Oligochaete worms (Lumbriculus variegatus) exposed to sediment spiked with a model substance of one HO-hexaCDE (4'-HO-PCDE 161) or its methoxy analogue (4'-MeO-PCDE 161) clearly accumulated the test compounds revealing the potential for environmental risk of HO-PCDEs and MeO-PCDEs. The HO-PCDE tested has earlier been reported as an abundant component in a Finnish chlorophenol formulation (Ky-5) and its…
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 (
Substituted Dibenzothiophenes I: Synthesis, Chromatography, Mass Spectrometry and Structure Elucidation by1H NMR Spectroscopy
Abstract Some polychlorinated and polymethylated dibenzothiophenes have been synthesized to serve as model compounds in environmental analysis. In order to obtain pure isomers, the synthesis mixtures have been fractionated with reversed-phase high performance liquid chromatography. In spite of a high sensitivity, mass spectrometry does not provide any reliable way to determine the precise structures of different isomers. Therefore, 1H NMR spectroscopy has been utilized as an aid in their analysis. The structures for two isomeric tetramethyldibenzothiophenes could be suggested on the basis of their 1H NMR spectra. Also some proposals for possible structures of two isomeric trimethyldibenzoth…
Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry
Abstract Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo- p -dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between
Tetra- and pentachlorodibenzothiophenes are formed in waste combustion
Abstract Two different waste combustion samples have been analyzed for tetra- and pentachlorodibenzothiophenes. HRGC/HRMS with a resolution of 20 000 was used for identification. By resolution of 10 000 chlorinated dibenzo-p-dioxins and some unknown compounds gave GC/SIM peaks at the exact masses of the chlorinated dibenzothiophenes. These peaks were no more present by resolution 20 000. Several tetra- and pentachlorodibenzothiophenes were found in both samples. In the other one of the samples the concentrations were seemingly high although exact quantitative determination could not be done.
Induction of erod activity in HEPA-1 mouse hepatoma cells and estrogenicity in mcf-7 human breast cancer cells by extracts of pulp mill effluents, sludge, and sediment exposed to effluents
Extracts of effluents and sludges from the primary and secondary clarifiers of an activated sludge treatment plant at a Finnish bleached kraft pulp and paper mill were analyzed in two cell bioassays. Total dioxin-like activities were determined by measuring the induction of ethoxyresorufin-O-deethylase (EROD) activity in Hepa-1 mouse hepatoma cells. Estrogenicity was studied by measuring luciferase activity in MCF-7 ERE-luc, which are MCF-7 human breast cancer cells stably transfected with an estrogen-responsive element linked to a luciferase promoter. Sediments collected near the pulp mill and from other sites in Lake Saimaa as well as fillets of whitefish exposed to effluents were examine…
High-resolution gas chromatographic-mass spectrometric determination of neutral chlorinated aromatic sulphur compounds in stack gas samples
Abstract Four stack gas samples from waste incineration were analysed by high-resolution GC-MS for neutral chlorinated aromatic sulphur compounds such as polychlorinated dibenzothiophenes, thianthrenes and diphenyl sulphides. Samples were analysed tentatively also for some methylated derivatives of these compounds. The stack gas samples had earlier been found to contain some tri- and tetrachlorodiphenyl sulphides. Two of the stack gas samples contained tetra- and pentachlorodibenzothiophenes. One sample was strongly suspected to contain some tri- and tetrachlorothianthrenes in low concentrations. No methylated derivatives of these compounds could be found. Polychlorothianthrenes, some polyc…
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 ring…
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.
Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds
Abstract Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (
Estimation of the environmental hazard of organochlorines in pulp mill biosludge used as soil fertilizer
Abstract Contents of total organic chlorine and polychlorinated phenols, guaiacols, catechols, benzenes, cymenes, cymenenes, naphthalenes, toxic dibenzodioxins, toxic dibenzofurans, toxic PCB congener 77, alkylated dibenzofurans, alkylated bibenzyls and alkylated phenanthrenes in spent biosludges from activated sludge treatment plants of chlorobleaching kraft pulp mills are reported. Some estimations of hazard caused by these organochlorines to humans and wildlife from the use of biosludge as soil fertilizer are constructed and discussed.
Ethoxyresorufin-O-deethylase induction potency of polychlorinated diphenyl ethers in H4IIE rat hepatoma cells
Polychlorinated diphenyl ethers (PCDEs) are structurally similar to polychlorinated biphenyls (PCBs), and some PCDE congeners have been reported to cause toxic responses similar to those caused by some of the non-ortho-substituted PCBs, which are mediated by the aryl hydrocarbon receptor (AhR). Twenty-nine PCDEs were tested for their potency as AhR agonists relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) by measuring their ability to induce the cytochrome P-450 1A1-associated enzyme activity, ethoxyresorufin-O-deethylase (EROD), in the H4IIE rat hepatoma cell bioassay. All PCDE congeners tested were found to be inactive as EROD inducers except for PCDE 156, which was a weak E…
Chlorophenanthrenes, alkylchlorophenanthrenes and alkylchloronaphthalenes in kraft pulp mill products and discharges
Abstract Chlorinated phenanthrenes (PCPHs; P=1–5), alkylphenanthrenes (C4-PCPHs; P=1–3), dimethylnaphthalenes (C2-PCNs; P=1–4) and trimethylnaphthalenes (C3-PCNs; P=1–2) were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) in pulp, effluent and biosludge of two kraft pulp mills (mills 1 and 2). These compounds were indicated to be formed in the manufacture of both bleached hardwood and softwood kraft pulp. Different compound groups dominated in mill 1 samples compared to mill 2 samples. Differences between birch and pine pulp from mill 1 were observed for all substance groups but in mill 2 pulp only for PCPHs. The highest concentrations of PCPHs …
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
Biomagnification of organohalogens in Atlantic salmon (Salmo salar) from its main prey species in three areas of the Baltic Sea
Abstract Factors affecting the biomagnification of organohalogens in Baltic salmon from sprat, herring and three-spined stickleback were assessed in three feeding areas. Second sea-year salmon contained (in fresh weight of whole fish) 79–250 ng g− 1 polychlorinated biphenyls (ΣPCB), 0.9–2.7 pg g− 1 dibenzo-p-dioxins (ΣPCDD), 8–19 pg g− 1 dibenzofurans (ΣPCDF), 96–246 pg g− 1 coplanar PCBs, 2.4–3.6 ng g− 1 polybrominated diphenylethers (ΣPBDE), and 39–136 ng g− 1 Σindicator PCB6. The EU limits for WHO toxic equivalent concentrations in fish feed were already exceeded in one-year-old sprat and herring and were exceeded many-fold in older age groups. The differences in the biomagnification rat…
Identification of lipophilic pollutants discharged from a Finnish pulp and paper mill.
Lipophilic organic compounds originating from kraft pulping and papermaking were identified by straight gas chromatography/mass spectrometry (GC/MS) analyses. Samples analyzed included a primary clarifier effluent (PE) and a secondary clarifier effluent (SE) from the activated sludge treatment plant of a Finnish ECF-bleached (Elementally Chlorine Free) kraft pulp and paper mill. Liquid-liquid extraction composition of PE was compared with solid phase extraction (SPE) and dialysis of a semipermeable membrane device (SPMD) exposed to PE. Dichloromethane extracts of particulate material isolated from PE, sludges from both the primary and secondary clarifier, a sediment collected in the vicinit…