Masahide Kawano

Bioconcentration and residue patterns of chlordane compounds in marine animals: invertebrates, fish, mammals, and seabirds.

The bioconcentration and compositional patterns of chlordane compounds (CHLs: cis-chlordane, transchlordane, cis-nonachlor, trans-nonachlor, and oxychlordane) were investigated in organisms from two marine ecosystems. The bioconcentration factors (BCF: concentration in organism/concentration in seawater) of CHLs in lower trophic organisms were in between the values obtained for HCHs (a-HCH, P-HCH, and yHCH) and DDTs (p,p’-DDE and p,p’-DDT). In the case of higher trophic organisms, the scatter in the biomagnification factors (BMF: concentration in organism/concentration in food) of CHLs was found to be wider than those observed for HCHs and DDTs. Also, there were remarkable differences in CHLs composition among higher trophic organisms. For example, the percent composition of oxychlordane, which is one of the persistent metabolites of CHLs in seabirds from both areas, was higher than those of marine mammals.

Global distribution and atmospheric transport of chlorinated hydrocarbons: HCH (BHC) isomers and DDT compounds in the Western Pacific, Eastern Indian and Antarctic Oceans

Concentrations of chlorinated hydrocarbons such as HCH isomers and DDT compounds were determined in air and surface water samples taken from the Western Pacific, Eastern Indian and Antarctic Oceans. The most interesting finding was their presence in measurable concentrations in the Antarctic Ocean. Chlorinated hydrocarbon pesticides are widely distributed in the open ocean environment over both the northern and southern hemispheres, and some characteristic distribution patterns of pesticide species in different oceanic regions were observed both in air and water samples. HCH residues found in the northern hemisphere were much higher in concentration than those in the southern hemisphere. On the other hand, higher concentrations of DDT residues were found in the tropical regions, but their levels were not so different between both the northern and southern hemispheres. HCH isomers found in the northern hemisphere had the following order of concentrations:α-HCH>γ HCH>β-HCH, while in the southern hemisphereγ-HCH was apparently dominant. DDT compound compositions were rather uniform in all the oceans surveyed, and more than 50% wasp,p′-DDT. These facts can be explained by the world wide situation regarding pesticide use and the physicochemical properties of the pesticides such as their vapor pressures and water solubilities. In addition, the meridional circulation of the atmosphere, particularly the mass flows of the Hadley and Ferrel cells in the troposphere, also contributes to the atmospheric transport and global distribution of these pesticides.

Isomer-Specific Determination and Toxic Evaluation of Polychlorinated Biphenyls, Polychlorinated/brominated Dibenzo-p-Dioxins and Dibenzofurans, Polybrominated Biphenyl Ethers, and Extractable Organic Halogen in Carp from the Buffalo River, New York.

Concentrations of PCB isomers, polychlorinated/brominated dibenzo-p-dioxins (PCDDs/PBDDs) and dibenzofurans (PCDFs/PBDFs), polybrominated biphenyl ethers (PBBEs), and total extractable organic halogen (EOX) were determined in carp (Cyprinus carpio) of three age classes collected from the Buffalo River, New York. Total PCBs concentrations exceeded the United States Food and Drug Administrations tolerable level of 2 μg/g (wet wt) in all the three age classes. Concentration ranges of total PCDDs and PCDFs were 27-146 and 22-99 pg/g, respectively. Among several of the 2,3,7,8-substituted isomers detected, OCDD and OCDF were the most predominantly noticed congeners. Noticeable concentrations of PBBEs were found with a major contribution from tetra-BBEs. Extractable organochlorines (EOCl) were the highest in the total EOX family followed by organobromines and organoiodines. The known organochlorines such as PCBs and DDT accounted for 13-58% of the EOCl, suggesting the presence of considerable levels of other unknown organochlorines. The 2,3,7,8-TCDD equivalents of coplanar PCBs, dioxins, and furans in carp muscle were between 45 and 108 pg/g, with 38-48% of the toxicity exerted by mono-ortho-PCBs. The estimated allowable consumption rates of carp based on the risk assessment method were much lowerthan the actual consumption values available for the Great Lakes states. Elevated concentrations of PCB isomers other than dioxins and furans suggest the need to protect humans from the consumption of PCB-contaminated carp from the Buffalo River.

Mercury in wild mushrooms and underlying soil substrate from Koszalin, North-central Poland

Concentrations of total mercury were determined by cold-vapour atomic absorption spectroscopy (CV-AAS) in 221 caps and 221 stalks of 15 species of wild growing higher fungi/mushrooms and 221 samples of corresponding soil substrate collected in 1997-98 in Manowo County, near the city of Koszalin in North-central Poland. Mean mercury concentrations in caps and stalks of the mushroom species examined and soils varied between 30+/-31 and 920+/-280, 17+/-11 and 560+/-220, and 10+/-9 and 170+/-110 ng/g dry matter, respectively. Cap to stalk mercury concentration quotients were from 1.0+/-0.4 in poison pax (Paxillus involutus) to 2.8+/-0.7 in slippery jack (Suillus luteus). Brown cort (Cortinarius malicorius), fly agaric (Amanita muscaria), orange-brown ringless amanita (A. fulva), red-aspen bolete (Leccinum rufum) and mutagen milk cap (Lactarius necator) contained the highest concentrations of mercury both in caps and stalks, and mean concentrations varied between 600+/-750 and 920+/-280 and 370+/-470 and 560+/-220 ng/g dry matter, respectively. An estimate of daily intake of mercury from mushroom consumption indicated that the flesh of edible species of mushrooms may not pose hazards to human health even at a maximum consumption rate of 28 g/day. However, it should be noted that mercury intake from other foods will augment the daily intake rates. Species such as the sickener (Russula emetica), Geranium-scented russula (R. fellea) and poison pax (P. involutus) did not concentrate mercury as evidenced from the bioconcentration factors (BCFs: concentrations in mushroom/concentration in soil substrate), which were less than 1. Similarly, red-hot milk cap (L. rufus), rickstone funnel cap (Clitocybe geotropa) and European cow bolete (S. bovinus) were observed to be weak accumulators of mercury. Fly agaric (A. muscaria) accumulated great concentrations of mercury with BCFs reaching 73+/-42 and 38+/-22 in caps and stalks, respectively. Mercury BCFs of between 4.0+/-2.3 and 23+/-25 (caps) and 2.6+/-1.9 and 14+/-12 (stalks) were noted for the other mushroom species. Relatively great concentrations of mercury in fly agaric (A. muscaria) were due to preferential uptake of this element by this species.

Total mercury in wild-grown higher mushrooms and underlying soil from Wdzydze Landscape Park, Northern Poland

Concentrations of mercury were determined in wild growing mushrooms (nine edible and 6 inedible species) and underlying soil (0–10 cm layer) substrate collected from Wdzydze Landscape Park in Northern Poland in 1995–1996. The analysis was performed using cold-vapour atomic absorption spectroscopy (CV–AAS) in 211 caps, 211 stalks and 211 soil samples. King Bolete (Boletus edulis), Cloudy Clitocybe (Lepista nebularis) and Orange Slime Court (Cortinarius mucosus) accumulated great concentrations of mercury and bioconcentration factors (BCF) of mercury in these species were between 560±510 and 180±160 in caps and between 310±190 and 77±64 in stalks. All other species examined, also accumulated mercury, but to lesser extent, with BCF values ranging from 3.9±2.1 to 69±12 in caps, and 1.0±0.4 and 38±7 in stalks. Cap to stalk concentration quotients for mercury were between 1.2±1.1 and 4.4±2.8. Mercury concentrations in underlying soil substrate were low between 2.7±1.2 and 37±5 ng/g dry weight, for 14 species, and 78±53 (18–170) ng/g dry weight for soil from which Sulfur Tuft (Hypoloma fasciculare) was collected. Among edible species, King Bolete showed a mean mercury concentration of up to 2600±2000 ng/g, dry weight, in caps and 1600±1200 ng/g in stalks. Mean mercury concentrations in other edible species were <400±200 in caps and <170±120 ng/g dry weight in stalks. Bare-toothed Brittle Gills (Russula vesca) had the lowest concentration of 45±26 ng/g and 30±18 ng/g dry weight, in caps and stalks, respectively. A statistically significant relationship was noted between mercury content in caps of Sandy Knight Cap (Tricholoma flavovirens; P<0.01), King Bolete (P<0.05) and soil mercury content, while a negative relationship was observed for Bay Bolete (Xerocomus badius; caps and stalks) and Sulfur Tuft (H. fasciculare; 0.01

Persistent organochlorine residues in soils from tropical and sub-tropical Asian Countries

Soil samples from paddy fields, uplands, and urban areas (gardens and roadsides) collected from Vietnam, Thailand, and Taiwan were analysed to determine the residual levels of persistent organochlorine compounds such as DDTs, HCHs, and PCBs. DDT concentration in soil samples from Vietnam were found to be highest, with a mean value of 110 ng g(-1), and were followed by those in Taiwanese soils with a mean value of 20 ng g(-1). HCH concentrations were highest in soil samples from Vietnam (a mean value of 4.8 ng g(-1)) and were followed by those from Taiwan (a mean value of 1.4 ng g(-1)). Concentrations of PCBs were found to be highest in Taiwanese soil samples, with a mean of 95 ng g(-1). Interestingly, relatively high concentrations of PCBs in rural cultivated-soil samples from Vietnam were recorded with a mean value of 25 ng g(-1), probably suggesting PCB release from different kinds of weapons used during the Second Indochina war. The lowest concentrations of DDTs, HCHs, and PCBs were obtained in soil samples from Thailand, with mean values of 8.3 ng g(-1), 0.4 ng g(-1), and 2.7 ng g(-1), respectively.

Content and bioconcentration of mercury in mushrooms from northern Poland.

Mercury (Hg) was quantified using cold vapour-atomic absorption spectrometry (CV-AAS) in the fruiting bodies of nine edible and five inedible mushrooms and in underlying soil substrate samples. In total, 404 samples comprising caps and stalks and 202 samples of soil substrate (0–10 cm layer) were collected in 1996 from Trójmiejski Landscape Park, northern Poland. Mean Hg concentrations in the soil substrate for different species varied between 10 ± 3 and 780 ± 500 ng g -1 dry wt (range 2.3–1700). Among edible mushroom species, Horse Mushroom (Agaricus arvensis), Brown Birch Scaber Stalk (Leccinum scabrum), Parasol Mushroom (Macrolepiota procera), King Bolete (Boletus edulis) and Yellow-cracking Bolete (Xerocomus subtomentosus) contained elevated concentrations of Hg ranging from 1600 ± 930 to 6800 ± 4000 ng g-1 dry wt in the caps. Concentrations of Hg in the stalks were 2.6 ± 1.1 to 1.7 ±1.0 times lower than those in the caps. Some mushroom species investigated had high Hg levels when compared with specimens collected from the background reference sites elsewhere (located far away from the big cities) in northern Poland. Bioconcentration factors of Hg in the caps of Horse Mushroom, Parasol Mushroom and Brown Birch Scaber Stalk were between 150 ± 58 and 230 ± 150 ng g-1 dry wt, respectively, and for inedible Pestle-shaged Puffball (Claviata excipulformis) was 960 ± 300 ng g-1 dry wt. Linear regression coefficients between Hg in caps and in stalks and Hg soil concentrations showed a positive relationship for A. arvensis and Horse mushroom (p < 0.05) and a negative correlation for the caps of Death Caps (Amanita phalloides) and Woolly Milk Cap (Lactarius torminosus) (p < 0.05), while for other species no clear trend was found.

Accumulation factors of mercury in mushrooms from Zaborski Landscape Park, Poland

Total mercury concentrations were determined by cold-vapour atomic absorption spectroscopy (CV-AAS) in 117 samples of caps, 117 of stalks and 47 of whole fruiting bodies of 13 species of wild mushrooms and in 164 underlying soil substrate collected from Zaborski Landscape Park during 1997 and 1998. The study area is a background, forested site with rural landscape and no known local sources of mercury emission. Mean mercury concentrations in mushrooms varied widely (range: 50 +/- 20 to 3700 +/- 1700 ng/g, dry matter) depending on the site and mushroom species investigated. However, mercury concentrations in soil samples varied less (range: 3.0 +/- 3.0 to 43 +/- 17 ng/g dry matter). Fruiting bodies of Common Puffball (Lycoperdon perlatum) and King Bolete (Boletus edulis) contained the greatest concentrations of mercury of 3700 +/- 1700 and 2600 +/- 1200 ng/g dry matter, respectively. A positive correlation existed between mercury concentrations in the caps of Slippery Jack (Suillus luteus) and Fly Agaric (Amanita muscaria) (p < 0.01) and mercury concentrations in corresponding soils. However, concentrations of mercury in The Sickener (Russula emetica) was negatively correlated with its soil substrate (p < 0.01). Bioconcentration factors (BCFs: concentrations ratios of mercury in mushroom to soil) of total mercury in whole fruiting bodies or caps were greatest for Common Puffball (L. perlatum), Larch Bolete (Suillus grevillei) and King Bolete (B. edulis) and varied between 130 +/- 78 and 160 +/- 120, while for the other species BCFs were between 4.0 +/- 6.0 and 61 +/- 20 in caps, and 4.4 +/- 3.1 and 70 +/- 68 in stalks. The concentration ratios of Hg in cap to stalk were from 1.1 +/- 0.5 for Poison Pax (Paxillus involutus) to 2.7 +/- 1.7 in Larch Bolete (S. grevillei).

Concentrations of Mercury in Wild Growing Higher Fungi and underlying Substrate near Lake Wdzydze, Poland

Fourteen species of wild growing mushrooms and surface (0–10 cm) soils were collected near Lake Wdzydze in the northern part of Poland in 1996–1997 to understand the status of mercury pollution. Concentrations of mercury in mushrooms varied between 100±30 and 2400±1900 ng g-1 dry matter in caps and 60±1 and 1300±1500 ng g-1 dry matter in stalks. Concentrations of mercury in underlying soil were between 30±1 and 140±120 ng g-1 dry matter (between 36±18 and 63±100 ng g-1 depending on the soil type). Bioconcentration factors (BCF: concentrations in mushroom/concentrationin soil) of total mercury were between 2.3±1.1 and 90±110 for caps, and between 2.1±1.0 and 53±56 for stalks. Scaly tooth (Sarcodon imbricatum) contained the greatest concentrations of mercury in the flesh. However, there was no significant relationship (p >: 0.05) between mercury content in the fruiting bodies of this speciesto soil mercury concentrations. A significant (p < 0.01) positive relationship between mercury content in caps to underlying soil was noted for European cow bolete (Suillus bovinus), while a negative relationship between mercury content in caps and stalks to underlying soil was observed for Sandy knight-cap (Tricholomaflavovirens), Shaggy scale-head (Pholiota squaroso-adiposa),Gypsy mushroom (Rozites caperata) and Pine spike cap (Chroogomphus rutilus).

Composition of chloronaphthalene congeners in technical chloronaphthalene formulations of the Halowax series

Abstract Normalised pattern (DB‐5 capillary column) of polychlorinated naphthalenes (PCNs; CNs) for all seven technical Halowax formulations and mass percent contribution (CN %) for an equivalent mixture of Halowax 1031, 1000, 1001, 1099, 1013, 1014 and 1051 (Equi‐Halowax) is presented. 2,3‐DiCN (PCN no. 10), 1,6,7‐and 2,3,6‐TrCNs (PCNs nos 25 and 26) and probably also 1,3,5‐TrCN (PCN no. 19), 1,3,6,7‐, 1,2,3,6‐and 1,2,3,8‐TeCN (PCNs nos. 44, 29 and 31), and 1,2,3,6,7,8‐HxCN (PCN no. 70) were absent in commercial PCNs formulations. The congeners such as 1,2,3‐TrCN (PCN no. 13), 1,3,8‐TrCN (PCN no. 22) and 1,2,3,6,7‐PeCN (PCN no. 54) were present in the mixtures at very low concentrations. The congeners most abundant in Halowax mixtures are usually chlorinated at α‐positions (1, 4, 5, 8‐positions) of the naphthalene nuclei. Because of some unresolved peaks observed on the chromatograms due to insufficient separation power of DB‐5, and also of many other liquid phases used in capillary gas Chromatographie separation of PCNs even when mass spectrometric detection was used, a perfect isomer and congener composition of PCN mixtures still has to be elucidated.