By-side PCDD/Fs in technical PCB formulations of Kanechlor series.

The Japanese Kanechlor technical PCB formulations such as KC-300, KC-400, KC-500, KC-600 and KC-1000 have been examined for possible contamination with by-side PCDD/Fs. 75 PCDDs and 135 PCDF have been determined using isotope dilution, separation and enrichment on silica gel impregnated with activated carbon, and final HRGC/HRMS measurement. MonoCDDs to OCDD were absent in KC-300, KC-600 and KC-1000. Tetra- and PentaCDDs occurred at > 1 ng/g in KC-400 and KC-500. The Kanechlors were contaminated with nearly all 135 PCDFsw. In parallel with an increasing degree of chlorination of a particular Kanechlor formulation examined increased also the content of more chlorinated PCDFs. In term of total dioxin-like toxicity and TEQ loads the KC-500 contained highly toxic PCDD/Fs at 270 ng TEQ/g and followed by KC-400 with 269 ng TEQ/g, KC-600 with 188 ng TEQ/g, KC-1000 with 164 ng TEQ/g and KC-300 with 79 ng TEQ/g. From 99.5 to 100% of PCDD/Fs toxicity found in the Kanechlors was from PCDFs.

Survey of perfluorinated compounds (PFCs) in surface waters of Poland.

Perfluorochemicals (PFCs) are wide-spread contaminants on a global scale. There is an increasingly growing number of data on environmental occurrence, sources and risk of PFCs to humans and aquatic biota in highly industrialised countries but inadequate information exists for less industrialised regions. In the present study, concentrations and profiles of PFCs were examined in surface waters (rivers, lakes, streams, coastal region of the Baltic Sea) of Poland. PFOS was the dominant compound found in water at most of the sites surveyed and its concentration varied between < 0.5 and 150 ng/L and next was PFHxS with < 0.25 to 110 ng/L, while at much smaller concentration of < 0.5 to 18 ng/L occurred PFOA. The long-chain carboxylates (C11-C16) could be found only in water of a drainage ditch near to the Sarzyna site, i.e., PFUnDA occurred at 0.17 ng/L, PFTeDA of 0.06 ng/L, PFDoDA at 0.1 ng/L and PFHxDA at 0.12 ng/L. PFDA was found at several locations in the Gulf of Gdansk and its concentration varied between < 0.01 and 0.07 ng/L. The profile of PFCs in surface water at several sites of Poland with PFOS as a major compound, followed by PFOA is similar to that reported for other countries in Europe as well as for India, while this is different from that of Korea, Japan and the USA, where PFOA was the predominant contaminant.

Mercury bio-concentration potential of Larch Bolete, Suillus grevillei, mushroom.

Larch Bolete can be classified as a mushroom species accumulating Hg in the fruiting bodies. Our results did indicate diversity of Hg concentrations (p < 0.05), depending on a site of collection of Larch Bolete fruiting bodies as well as the lack of any statistically significant differences in soil mercury contamination among the examined sites. Values of 1.0 microg Hg/g dw for pool of caps and 2.0 microg/g dw for a single cap of Larch Bolete are suggested as threshold concentrations implying Hg baseline level, while greater value could imply contamination due to the site pollution.

Application and comparison of different chemometric approaches in QSPR modelling of supercooled liquid vapour pressures for chloronaphthalenes.

Molecular descriptors from calculations at the level of Density Functional Theory (B3LYP/6-311++G**) were effectively applied in QSPR estimation of supercooled liquid vapour pressures (P(L)) for individual chloronaphthalene congeners. The estimated values of log P(L) varied from 1.05 Pa to 5.6 x 10(-5) Pa, depending on the number of chlorine substituents present in the molecule and the substitution pattern. Comparison of the five chemometrical methods of modelling (approaches) led to the final conclusion, that the use of relatively simple PLS combined with one of the variable pre-selection algorithms (UVE or GA) seems to be the optimal choice in such computational studies for persistent organic pollutants. The best GA-PLS model was characterized by the value of root mean square error of prediction RMSEP = 0.108 logarithmic Pascal units.

Application of ICP sector field MS and principal component analysis for studying interdependences among 23 trace elements in Polish beers.

Twenty-three metallic elements, including almost all essential and toxic metals such as lead, cadmium, mercury, arsenic, silver, and thallium, have been quantified in 35 types of bottled and canned Polish beer by using double-focusing sector field inductively coupled plasma mass spectrometry (ICP-MS) with ultrasonic nebulization. The samples were digested using concentrated HNO3 in closed PTFE vessels and applying microwave energy under pressure. The means and medians of the concentrations of Rb, Mn, and Fe were on the order of 200 ng/mL; Cu, Zn, V, Cr, Sn, As, Pb, and Ni were detected at 1-5 ng/mL; Ag, Ga, Cd, Co, Cs, Hg, U, and Sb were found at < 1 ng/mL; and In, Tl, Bi, and Th were present at < 0.1 ng/mL. The concentrations of Hg, Cd, As, Pb, and Zn were 1-3 orders of magnitude lower than proposed tolerance limits. The interdependences among determined trace elements were examined using the principal component analysis (PCA) method. The PCA model explained 74% of the total variance. The metals tend to cluster together (As, Tl, Cs, Sn, Th, Bi, and Hg; Cd and Co; Cs and Cr; Fe and Zn; Mn and V).

Some toxic and essential trace metals in swine from northern Poland.

The concentrations of mercury, cadmium, lead, copper, manganese, zinc and iron have been determined in muscle (meat), liver and kidneys of swine slaughtered in the northern part of Poland between 1987 and 1991. The method of measurement was cold vapour flameless AAS for mercury and flame AAS for other trace metals. The concentrations of such toxic metals as mercury, lead and cadmium were relatively low or very low. The arithmetic mean weighted concentrations obtained related to fresh weight for muscle, liver and kidneys of swine were 1.9, 3.7 and 7.0 micrograms kg-1 for mercury, 5, 41 and 240 micrograms kg-1 for cadmium, 20, 94 and 120 micrograms kg-1 for lead, 1.1, 8.5 and 8.4 mg kg-1 for copper, 0.11, 1.3 and 1.3 mg kg-1 for manganese, 26, 50 and 30 mg kg-1 for zinc and 13, 54 and 63 mg kg-1 for iron, respectively. No definite time trends of mercury, cadmium and lead concentrations in swine muscle and edible organ meats during the period studied were observed, while for an essential trace metals analysed the values obtained seem to be typical. The results noted are reviewed and discussed with the data reported for muscle, liver and kidneys of swine in Poland from other studies.

Some toxic and essential trace metals in cattle from the northern part of Poland.

The concentrations of mercury, cadmium, lead, copper, manganese, zinc and iron have been determined in muscle (meat), liver and kidney of cattle slaughtered in the northern part of Poland between 1987 and 1991. The method of measurement was cold vapour flameless AAS for mercury and flame AAS for other metals. The arithmetic mean weighted concentrations obtained related to wet-weight for muscles, liver and kidneys of cattle were 1.2, 4.2 and 11 micrograms kg-1 for mercury; 6, 120 and 610 micrograms kg-1 for cadmium; 40, 160 and 210 micrograms kg-1 for lead; 1.2, 29 and 5.6 mg kg-1 for copper; 0.11, 1.8 and 0.93 mg kg-1 for manganese; 34, 43 and 22 mg kg-1 for zinc and 23, 44 and 72 mg kg-1 for iron, respectively. No clear trends with time of toxic trace metals have been found in bovine muscle and edible organs during the period studied. The results obtained are reviewed and discussed with the data reported for muscle, liver and kidneys of cattle in Poland from other studies.

Some toxic and trace metals in big game hunted in the northern part of Poland in 1987-1991.

Game animal meats (muscle, liver and kidneys) collected from different regions in northern part of Poland in 1987-1991 were analysed for mercury, cadmium, lead, copper, manganese, zinc and iron. Toxic mercury, cadmium and lead occurred in relatively low concentrations in muscle and organ meats, with the exception of lead in muscle and cadmium in kidneys, which were relatively more contaminated. The concentrations of essential trace metals in samples examined seemed to be natural. Roe-deer contained relatively higher concentrations of copper, both in liver and kidneys, than stag and wild boar, while stag had higher levels of manganese in muscle meat and organs. The weighted mean concentration ranges obtained related to wet-weight for muscle, liver and kidneys of wild boar, roe-deer and stage were 1.2-3.4, 7.3-15, and 24-54 micrograms/kg for mercury; 10-10, 110-210, and 1500-2100 micrograms/kg for cadmium; 86-160, 190-210, and 210-290 micrograms/kg for lead; 1.6 and 1.8, 4.5-28, and 5.4-12 mg/kg for copper; 0.24-0.83, 1.7-5.2, and 1.3-4.1 mg/kg for manganese; 32-37, 37-47, and 30-48 mg/kg for zinc; and 24-31, 40-54, and 67-83 mg/kg for iron, respectively. Single specimens of elk and aurochs were examined also. From the point of view of health, contamination of muscle with lead, as a result of shot pellet fragmentation, and of kidneys with cadmium from the contaminated environment, seemed to be of greatest concern. The values obtained were compared with the available literature data.

Polychlorinated naphthalenes: an environmental update.

Polychlorinated naphthalenes (PCNs; CNs) form a complex mixture of up to 75 congeners containing from one to eight chlorine atoms per naphthalene molecule. Chloronaphthalenes are widespread global environmental pollutants which accumulate in biota. All chloronaphthalenes are planar compounds and can contribute to the aryl hydrocarbon (Ah) receptor-mediated mechanism of toxicity with a combination of various 2,3,7,8-tetrachlorodibenzo-p-dioxin like toxic responses. There are three known main sources of environmental pollution with PCNs: technical PCN formulations, technical polychlorinated biphenyl formulations, and thermal and other processes in the presence of chlorine. The purpose of this paper is to briefly review the most recent data on environmental pollution, chemistry, analysis, sources, formation, persistence, toxicity and behavior of PCNs.

Trace metals in the bones of scaup ducks (Aythya marila L.) wintering in Gdansk Bay, Baltic Sea, 1982-83 and 1983-84.

The concentrations of Fe, Zn, Mn, Cu, Pb, Cd, Co, Ni, Cr and Ag in 88 samples of various bones and five samples of trachea prepared from scaup ducks (Aythya marila L.) have been determined. With the exception of lead, no significant sex-related differences were observed for the concentration of metals. However, there were significant differences in the concentrations of most metals for different bones.

The concentrations and bioconcentration factors of mercury in mushrooms from the Mierzeja Wislana sand-bar, northern Poland.

The total concentration of mercury was determined in 15 species of wild growing mushrooms, each represented by 15 specimens including underlying substrate, collected from the unpolluted area of the sand-bar Mierzeja Wislana in the northern part of Poland in 1993-1994. Mercury was measured by cold vapour atomic absorption spectrometry (CV-AAS) after wet digestion of the samples with concentrated nitric acid in a glass system. The mushroom species examined showed a wide range of mercury concentrations, i.e. from 5.6 +/- 2.1 micrograms/g dry wt. in Scleroderma citrinum to 1100 +/- 240 micrograms/g in the edible Macrolepiota procera. No bioconcentration of mercury was observed in Xerocomus badius, Paxilus involutus, Russula queletii and Lactarius rufus. In Hygrophorius aurantiaca, Armilariella mellea and Amanita vaginata the bioconcentration factor (BCF) values of mercury were close to one. Accumulation of mercury was slight in Oudemansiella platyphylla and Amanita citrica (BCF between 2.0 and 3.3 in the caps and 1.7 in the stalks) and high in Leccinum scabrurm, Amanita muscaria and Macrolepiota procera (BCFs between 11 and 35 in the caps and 6.7-18 in the stalks). In the whole fruiting body of Polyporus melanopsuss and Scleroderma citrinum the BCF values of mercury were 4.4 and 0.083, respectively. There was a high correlation between the concentrations of mercury in the caps and stalks of Macrolepiota procera and in the underlying substrate (P < 0.001), a slight correlation for Polyporus melanopsuss, and also for the caps of Leccinum scabrum, Oudemansiella platyphylla and Russula aeruginea and the stalks of Hygrophoropsis aurantiaca (P < 0.01) and L. scabrum (P < 0.05). For the other mushroom species investigated there was no correlation between mercury concentration in the fruiting bodies and underlying substrate.

Chlorinated hydrocarbons in diving ducks wintering in Gdansk Bay, Baltic Sea.

The levels of HCB, alpha-BHC, gamma-BHC, DDT (plus analogues), and PCB were determined in adipose fat from seven species of diving ducks at their winter quarters in the southern Baltic. PCB, epsilon DDT and HCB were detected in all samples. PCB's were highest followed by epsilon DDT and HCB. Residues of gamma-BHC were detected in only four of 129 samples examined, but, for all samples from the long-tailed duck, only levels of alpha-BHC were positive. Differences between HCB, epsilon DDT and PCB residue levels between males and females of the scaup-duck were statistically insignificant (P less than 0.01).

Investigations of trace metals in long-tailed duck (Clangula hyemalis L.) from the Gdansk Bay.

The determination of iron, zinc, manganese, copper, lead, cadmium, cobalt and nickel was carried out on liver, breast muscle, heart, stomach and feathers of 50 male and 40 female long-tailed ducks (Clangula hyemalis L.) staying in their winter quarters in Gdansk Bay during 1980-81. There were no significant differences in the concentration of metals between male and female long-tailed ducks. The correlation coefficients between the concentration of metals in the liver and breast muscle were determined.

Uranium and thorium content in long-tailed ducks (Clangula hyemalis L.).

Concentrations of uranium and thorium have been determined in liver, breast muscle, leg muscle, stomach and heart of long-tailed ducks wintering in Gdansk Bay during 1980-81. The highest concentration of uranium and thorium was found in stomach, and the lowest in breast muscle.

Most toxic and highly bioaccumulative PCB congeners in cod-liver oil of Baltic origin processed in Poland during the 1970s and 1980s, their TEQ-values and possible intake.

Five samples of cod-liver oil of Baltic origin, collected between 1971 and 1989, have been analysed for 15 selected polychlorinated biphenyl (PCB) congeners including the ten most toxic non-, mono-and di-ortho coplanar, IUPAC nos. 60, 77, 105, 118, 126, 138, 169 and 170 and another five highly bioaccumulative members (IUPAC nos. 28 + 32, 52, 101, 153 and 180). The method of measurement was capillary GC-MS. Cod-liver oils collected in 1971, 1975, 1980, 1985 and 1989 contained 3.0, 2.5, 6.7, 2.9 and 3.1 micrograms g-1 respectively, of selected PCBs (IUPAC nos. 28 + 32, 52, 101, 138, 153 and 180). The concentration of total PCBs in these oils were 8.0, 6.7, 17, 8.0 and 9.5 micrograms g-1, respectively for the years 1971-89, which indicates both persistency and steady state of these pollutants in the Baltic Sea. These cod-liver oils also showed high concentrations of the ten most toxic coplanar PCBs; their TEQ-values (Safe, 1990) were between 900 and 2300 micrograms g-1. 2,3', 4,4',5-pentachlorobiphenyl (IUPAC no. 118), 2,3,3', 4,4'-pentachlorobiphenyl (IUPAC no. 105) and 3,3',4,4',5-pentachlorobiphenyl (IUPAC no. 126) contributed most to the total TEQs of the ten coplanar members, occupying 47, 19 and 17%, respectively (totally 83%). A possible intake of these toxic PCBs from cod-liver oil by children or adults was estimated to be between 4.5 and 35 pg TEQ daily and for total PCBs between 34 and 260 micrograms daily.(ABSTRACT TRUNCATED AT 250 WORDS)

Mercury, lead, cadmium, manganese, copper, iron and zinc concentrations in poultry, rabbit and sheep from the northern part of Poland.

The concentrations of mercury, lead, cadmium, manganese, copper, iron and zinc have been determined in poultry, rabbit and sheep from the northern part of Poland between 1988 and 1991. The method of measurement was cold vapour flameless AAS for mercury and flame AAS for other trace metals. Rabbits contained somewhat higher concentrations of lead in liver and kidneys than other species examined and the same could be observed in the case of cadmium in organ meats of duck and geese with apparently higher contamination of the rabbit's kidneys. While for an essential trace metals the values obtained seem to be species/tissue specific and typical.

Congener-specific data of polychlorinated biphenyl residues in human adipose tissue in Poland.

Adipose tissue of inhabitants of the Gdansk city located at the southern coast of the Baltic Sea and of the province of Skierniewice of inland Poland have been investigated for congeners of polychlorinated biphenyls (PCBs) by the capillary GC-MS technique. PCB IUPAC No. 153 was a high contributor of the congener occupying 23% of the total PCB content, and together with No. 138 of 18% and No. 180 of 13% were the most prevalent members. Samples taken from Gdansk citizens in 1990 contained 1.5 +/- 1.3 micrograms/g of total PCBs on a fat weight basis while the citizens from the province of Skierniewice, sampled in 1979, contained 1.2 +/- 0.4 micrograms/g, which seemed to indicate a persistent PCB exposure in Poland. Among Gdansk citizens, randomly selected autopsy samples of liver cancer from dead persons contained 4.7 micrograms/g of PCBs, while in all other samples the level was between 0.75 and 1.9 micrograms/g of PCBs. TCDD TEQ of 13 detectable coplanar members of PCBs in adipose tissue of Gdansk, and Skierniewice inhabitants, was 210 and 190 pg/g on a lipid weight basis, respectively, including 45 and 59 pg/g of non-ortho, 142 and 110 pg/g of mono-ortho and 24 and 16 pg/g of di-ortho chlorobiphenyls. A fingerprint of chlorobiphenyl composition in the samples examined was virtually the same for human adipose tissue taken in 1990 from the coastal city of Gdansk and in 1979 from the inland province of Skierniewice, in spite of geographic variations and sampling intervals.

Polychlorinated biphenyl and organochlorine insecticide residues in human adipose tissue in Poland.

Concentrations of PCBs (polychlorinated biphenyls) and organochlorine insecticides such as DDT, HCHs (hexachlorocyclohexanes), HCB (hexachlorobenzene) and chlordanes were determined in human adipose fat from the provinces of Skierniewice and Gdansk in Poland collected during 1979 and 1990, respectively. The mean levels (microg g(-1) lipid weight basis) in Skierniewice and Gdansk were found to be 1.2+/-0.44 and 1.5+/-1.3 for PCBs, 25+/-16 and 15+/-13 for DDT, 0.53+/-0.17 and 0.25+/-0.09 for HCHs, 0.36+/-0.22 and 0.26+/-0.23 for HCB, and 0.11+/-0.08 and 0.07+/-0.04 for chlordanes, respectively. Very high concentrations of DDT were detected, with the maximum value as high as 52 microg g(-1) lipid weight in Skierniewice and 47 microg g(-1) lipid weight in Gdansk. PCB residues contained in the human fat from Polish cadavers are comparable to those of the levels reported for industrialized nations. It is appraised from the levels of DDT and PCBs in Poles' fat that the Polish environment is still experiencing both types of contamination, arising from agricultural and industrial activities. Contamination of humans by other organochlorine insecticides was relatively lower.

Concentrations and biomagnification of polychlorinated naphthalenes in black cormorants Phalacrocorax carbo sinensis from the Gulf of Gdansk, Baltic Sea.

Black cormorants, Phalacrocorax carbo sinensis (the breast muscles and liver) originating from the colony near Katy Rybackie on the south coast of the Gulf of Gdansk, Baltic Sea, were collected in 1992 and analysed for polychlorinated naphthalenes. PCNs were determined employing a multi-residue procedure including a non-destructive wide-bore open-tube extraction step, cleanup using semipermeable polyethylene membrane, HPLC fractionation of planar compounds on activated carbon column and final separation and identification and quantification with HRGC/HRMS. Tetra- to hepta-CNs were found in all samples examined, and penta- and next tetra-CNs were dominating homologue groups. Dominating members in the fingerprint of PCNs in black cormorants were 1,3,5,7-T4CN (no. 42); 1,2,3,5,7-/1,2,4,6,7-P5CN (no. 52/60); 1,2,4,6,8-P5CN (no. 61); 1,2,3,4,6,7-/1,2,3,5,6,7-H6CN (no. 66/67); 1,2,4,6-/1,2,4,7-/1,2,5,7-T4CN (no. 33/34); 1,2,4,5,7-P5CN (no. 58); and 1,2,4,7,8-P5CN (no. 62). When related to potential food items, black cormorants biomagnify in their body many PCNs and the congeners no. 42 and 66/67 show highest biomagnification factor (BMF) values.

Concentrations and spatial variations of cyclodienes and other organochlorines in herring and perch from the Baltic Sea.

Herring (Clupea harengus) and perch (Perca fluviatilis) were collected in the northern and southern Baltic Sea and analyzed for the presence of the cyclodiene pesticides chlordane (CHL), heptachlor, aldrin, dieldrin, endrin, isodrin, endosulfan and mirex, as well as other organochlorine contaminants, hexachlorocyclohexanes (HCHs), DDTs, hexachlorobenzene (HCBz) and polychlorinated biphenyls (PCBs) in order to investigate concentrations, accumulation and differences in geographical distribution. In the northern part of the Baltic Sea, Gulf of Bothnia, herring were collected at two pelagic stations, one in the Bothnian Bay (BB) and the other in the Bothnian Sea (BS), respectively; perch were collected at four coastal locations along the Swedish coast. All these locations were selected to represent background areas except one in the vicinity of an industrialised and contaminated area. Both specimens were also caught in the southern part of the Baltic Sea, in the Gulf of Gdansk (GG), Poland, a potentially highly polluted area. From the eight cyclodiene pesticides analyzed, three were detected in herring and perch samples, including 12 different CHL-related compounds, dieldrin and mirex. To our knowledge, it is the first time that mirex has been detected in samples from the Baltic Sea. Neither heptachlor, aldrin, endrin, isodrin nor endosulfan were found. However, HCHs, DDTs, HCBz and PCBs were found in every sample investigated, and the concentrations ranged e.g. for the cyclodiene chemicals dieldrin and CHL-related compounds from 30 to 170 ng/g lipid and for PCBs from 360 to 5400 ng/g lipid, both fish species included. Differences in contamination burden between the sites can be seen, e.g. for herring the BB and GG locals were similar, and generally lower than BS for all chemicals except that of DDT where GG was the highest. For the perch samples the industrialised location had markedly higher concentrations of HCBz and PCBs than the other locations. This species also identifies GG as the most DDT contaminated site among the three studied areas.