Studies on the distribution of beta- and gamma-isomers of hexachlorocyclohexane in rat tissues

A study of the comparative distribution pattern of beta- and gamma-isomers of hexachlorocyclohexane (HCH) in albino rat tissues as a function of duration of treatment at two dose levels revealed different accumulation patterns for the two isomers in tissues. In general, the accumulation pattern was found to be in the order: fat greater than kidney greater than lungs greater than liver greater than muscle greater than heart greater than spleen greater than brain greater than blood for beta-HCH and fat greater than brain greater than kidney greater than muscle greater than lungs greater than heart greater than spleen greater than liver greater than blood for gamma-HCH. The tissue accumulation of beta-isomer was always greater than that of gamma-isomer in any tissue except in brain. Brain beta-HCH residue levels were relatively lower than in many other tissues except blood, whereas brain gamma-HCH concentration was only next to fat. A higher dose or a longer period of treatment generally produced a more marked elevation of tissue residue levels in beta-HCH fed rats, but not in gamma-HCH treated animals.     

Insecticidal activity of different extracts from Scrophularia canina L. against Culex pipiens molestus Forskal (Diptera, Culicidae)

The insecticidal activity of different extracts (aqueous, methyl alcohol, hexane and petroleum ether) of the aerial part of Scrophularia canina against the second and fourth-instar larvae and adult females of Culex pipiens molestus was investigated. The larvicidal activity of all the extracts was tested in the dose range from 7.8 to 1000 ppm. The highest toxicity was exhibited by the petroleum ether extract against second-instar larvae (48 h LC?? = 23.5 ppm) and by the hexane extract against fourth-instar larvae (48 h LC?? = 23.6 ppm). Methyl alcohol and aqueous extracts did not show any larvicidal activity. Sub-lethal doses of petroleum ether and hexane extracts induced increasing mortalities during 13 days after treatment but did not affect the duration of larval and pupal stages. In persistence tests, the hexane extract retained a satisfactory larvicidal activity after a 10-day period of test solutions incubation. Topical treatment of adult females with doses from 0.25 to 8 μg per mg of female body weight of different extracts showed a similar toxicity for the hexane (24 h LD?? = 1.7 μg mg?1) and petroleum ether (24 h LD?? = 1.8 μg mg?1) extracts which were significantly more toxic than methyl alcohol extract (4.2 μg mg?1). Aqueous extract did not induce adult mortality. The marked mosquitocidal activity of petroleum ether and hexane extracts of the aerial part of S. canina against different life stages of C. pipiens molestus is promising to develop effective alternatives to synthetic insecticides.     

Seasonal impacts on beta-hexachlorocyclohexane concentration in soil solution

We analysed monthly the concentration of beta-hexachlorocyclohexane (beta-HCH), a hydrophobic organic contaminant, in aqueous saturation extracts of the topsoil from five differently contaminated sites. beta-HCH concentration in the aqueous soil extract shows a high seasonal variability. Concentrations differ up to 60-fold with peaks up to 2.24 microg l(-1). Higher beta-HCH concentrations were found in summer and autumn and accompanied by peaks in dissolved organic carbon concentration. This indicates the importance of dissolved organic matter for beta-HCH mobilization and the risks for groundwater pollution and plant uptake.     

Persistent organohalogen contaminants in plasma from groups of humans with different occupations in Bangladesh

The present study is aimed to assess persistent organic halogenated pollutants in humans living in Bangladesh. The results are compared to other similar studies in the region and globally. Human blood plasma were collected from groups of men and women with different occupations, i.e. being students, garment industry workers, employees at the Power Development Board (PDB), all groups in Dhaka, fishermen and fishermen wife's from Dhaka and another group from Barisal district. The plasma was analysed for hexachlorobenzene (HCB), the hexachlorocyclohexane isomers, alpha-HCH, beta-HCH, gamma-HCH and delta-HCH, the DDT group of chemicals, chlordane compounds, trans-chlordane, cis-chlordane, oxychlordane, trans-nonachlor, trans-heptachlorepoxide, methoxychlor and mirex. The most abundant contaminant, in all groups studied, p,p'-DDE is dominating, with p,p'-DDT/Sigma DDT ratios indicating recent and ongoing DDT exposure. Among the other pesticides analysed beta-HCH is the most abundant indicating the use of technical HCH products instead of Lindane (gamma-HCH). While the Sigma DDT is present in the low ppm range the beta-HCH is detected in up to approx. 400 ppb, lipid basis. The beta-HCH is most abundant in the groups of students. In contrast to the pesticides analysed very low concentrations of polychlorinated biphenyls (PCB) are present in all study groups, with e.g. CB-153 in the range of 5-30 ng g(-1) fat. The concentrations of the DDT group of chemical differ significantly between fishermen and fishermen's wives living and working in the Dhaka area versus those living and working in Barisal. Also, fishermen and their wives had significantly different concentrations of DDT compared to garment industry workers.     

Toxicity of technical X-factor to weanling rats. II. A subacute oral study

Eighty male weanling rats were fed dietary levels of Technical X-factor (beta-isomer free BHC, a by-product obtained during the separation of lindane from Tech. BHC) at dosages of 10,50,250,750,1500 and 3000 ppm for 90 days. No overt signs of toxicity or mortality were observed at any of the dietary levels. However, a significant reduction in food consumption and growth was evident beyond 750 ppm. Pronounced hepatomegaly observed at 1500 and 3000 ppm was associated with histological alterations such as cellular hypertrophy, cytoplasmic vacuolisation and focal necrosis. Adrenals showed cortical hypertrophy and highly vacuolated cytoplasm. Though a significant increase in the levels of SGOT was noted at 3000 ppm dosage, no appreciable changes were observed in the levels of SGPT and SLDH. Technical X-factor appeared to possess low chronic toxicity compared to Tech. BHC as evidenced by the various parameters studied. The observed low chronic toxicity of X-factor is probably due to the absence if beta-isomer and altered composition of delta and alpha isomers.     

Formation of mutagens by photolysis of amino acids in neutral aqueous solution containing nitrite or nitrate ion

Nine amino acids, i.e., alanine, threonine, cysteine, glutamic acid, arginine, proline, tryptophan, phenylalanine and tyrosine, were irradiated with UV light in water containing nitrite or nitrate ion under neutral conditions. The mutagenicities of the ether extracts and the residual water layers of the reaction mixtures were assayed with and without S-9 mix using $\text{Salmonella typhimurium}$ TA98 and TA100. Three aromatic amino acids, tryptophan, phenylalanine and tyrosine, were found to give direct-acting and frameshift mutagens by irradiation in aqueous nitrite solution. Among them, the ether extract of tryptophan exhibited the strongest mutagenicity toward TA98. In the case of irradiation in aqueous nitrate solution, only the ether extract of tryptophan exhibited weak mutagenicity toward TA98 without S-9 mix. The effects of nitrite concentration, irradiation time and pH on mutagen formation from tryptophan and some characteristics of the produced mutagens were examined.     

Mammalian toxicity of Technical X-factor I. An acute oral study

Intragastric administration of acute doses of Technical X-factor (beta-isomer free BHC, a byproduct obtained during separation of Lindane from Tech. BHC) carried in peanut oil elicited typical signs of central nervous system depression in adult rats. The computed oral LD50 values of X-factor were 4174 and 5673 mg/kg. body weight for male and female rats respectively indicating that its acute toxicity was of relatively low order compared to Tech. BHC. It is suggested that the low acute mammalian toxicity of X-factor could possibly be due to a direct antagonism of the delta isomer (present in larger proportion in X-factor) with the gamma isomer.     

Seasonal change of persistent organic pollutant concentrations in air at Niigata area,Japan

The concentrations of persistent organic pollutants (POPs), such as HCB, alpha-, beta-, gamma- and delta-HCH, trans- and cis-chlordane (t-CHL, c-CHL), DDE, DDD and DDT, in ambient air have been measured at five sampling points in Niigata area, Japan (Niigata, Maki, Tsubame, Jouzo and Yahiko) during the period from September 1999 to November 2001. HCB, alpha-HCH, t-CHL and c-CHL showed higher concentrations than the other chemicals in all locations. All the POPs except t-CHL and c-CHL collected at urban sites of the Niigata Plain was almost the same in their concentration levels. Higher concentrations of t-CHL and c-CHL in residential areas should be attributed to the past usage of the chemical as a termiticide. At Yahiko (remote site), most of the POPs showed lower concentrations than those measured at the other sampling sites, although alpha-HCH and gamma-HCH were comparable with the concentrations found at the other sampling sites. All POPs except alpha-HCH and gamma-HCH tend to decrease 41-80% in their concentrations from 2000 to 2001. The lower POPs concentrations in winter and the higher POPs concentrations in summer at every sampling point can be partly explained by temperature differences. Applying the equation of the logarithm of the POP partial pressure in air versus reciprocal temperature (lnPa=m/T+b) to our data, linear relations were observed. HCB gave a poor linearity and the smallest slope, while beta-HCH, t-CHL and c-CHL gave good linearities and large slopes in the equation. The results suggest that HCB level is influenced by not only the emission from terrestrial sources but the global-scale background pollution. A peculiar observation is that beta-HCH concentration measured in our study showed large temperature dependence, indicating there could be a source of contamination in the surrounding areas.     

The in vitro metabolism of lindane by an enzyme preparation from chicken liver.

The soluble fraction (105,000 x g, 30 min) of chicken liver homogenates contained an enzyme(s), probably a dehydrochlorinase(s), which metabolized lindane in vitro. The reaction was glutathione dependent and took place anaerobically. The enzyme(s) also metabolized the alpha- and delta-isomers but not the beta-isomer. About 66% of the in vitro metabolites were soluble in petroleum ether. From the ether-soluble fraction, o-, p- amd m-dichlorobenzene, 1,2,3- and 1,2,4-trichlorobenzene, gamma-2,3,4,5,6-pentachlorocyclohex-1-ene (gamma-PCCH), 2,3- and 2,4-dichlorophenol and 2,4,6-trichlorophenol were identified by comparison of mass spectra and gas chromatographic data with those of reference compounds. Seven additional metabolites were tentatively identified from their mass spectra data. These metabolites were: chlorobenzene, 2 isomers of trichlorocyclohexene, dichlorocyclohexadienetriol, chlorophenol, trichlorocyclohexenol and trichlorocyclohexanediol. The petroleum ether-extracted aqueous phase contained a number of unidentified conjugated metabolites. It was concluded that the metabolic pathway for lindane in the chicken is quite similar to that in the pheasant.     

Distribution of hexabromocyclododecane in Detroit River suspended sediments

The distribution of hexabromocyclododecane (HBCD) isomers (alpha, beta and gamma) was determined in Detroit River suspended sediments using liquid chromatography tandem mass spectrometry (LC/MS/MS). Individual isomers of HBCD were measured at concentrations ranging from <0.025 to 1.9 ng/g (dry wt.) for the alpha-isomer, <0.025 to 0.28 ng/g for the beta-isomer, and <0.025 to 2.3 ng/g for the gamma-isomer. Concentrations of total HBCD ranged from <0.075 to 3.7 ng/g. Roughly two-thirds of HBCD profiles in suspended sediments were dominated by the gamma-isomer, and were similar to profiles of commercial technical mixtures. Profiles in the remaining samples were dominated by the alpha-isomer. The beta-isomer was consistently detected at substantially lower levels than the other isomers; this isomer is a minor constituent in the commercial technical mixtures. Seasonal sampling showed significant shifts in the relative ratios of the HBCD isomers. The spatial distribution of HBCD in the Detroit River was similar to other persistent organic pollutants (e.g., PCBs), and showed a strong association with urban/industrial activities in the watershed. However, the highest HBCD concentrations (2.6-3.7 ng/g) were associated with areas of contemporary industrial activity, and were much lower than maximum concentrations of PCBs (2.2 microg/g) found in areas of the Detroit River associated with historical industrial activity.     

Interlaboratory comparison exercise for the analysis of PCDD/Fs in samples of digested sewage sludge

Five UK laboratories participated in a study designed to explore the principal sources of interlaboratory variation in the analysis of PCDD/Fs in sewage sludge. Samples of wet sludge, dry sludge, toluene extract of sludge and cleaned extract of sludge were prepared by an organising laboratory. The samples were analysed in duplicate by each laboratory along with a solution of PCDD/F standards and reference sediment. Mean coefficients of variation between laboratories were 45% for the wet sludge, 33% for the dry sludge, 32% for the extract of sludge, 36% for the cleaned extract of sludge, 32% for the reference sediment and 28% for the standard solution. The results were subjected to statistical analysis, which showed that there was no specific part of the analysis that introduced a dominant part of the variation. The spread of data generated from the analysis of wet sludge samples was not appreciably greater than the spread for the analysis of cleaned extracts. Thus the drying, extraction and clean up processes in the PCDD/F analysis of wet sludge did not have a dramatic effect on the interlaboratory variation.     

Persistent organic pollutants in moss as bioindicators of atmospheric pollution in Singapore

Moss samples were collected from the island of Singapore and analysed for a range of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Although all compounds analysed have been banned from use in Singapore, they were detected in all samples collected. Among the hexachlorocyclohexanes (HCH), beta-HCH was the most dominant isomer, while trans-chlorane was found to be the most dominant cyclodiene pesticide. High levels (79.12 ng g(-1)) of PCBs were detected in mosses collected from a nearby island due to active accumulation of pollutants associated with boat emissions. Significant spatial variations in the levels of organic pollutants in Singapore were largely absent, indicating that air masses moving over the island deposit OCPs and PCBs in a uniform pattern. A comparison of moss pollutant levels with available data from Czech Republic showed that dichlorodiphenyldichloroethylene (p,p'-DDE), dichlorodiphenyltrichloroethane (p,p'-DDT) and PCB levels in Singapore are the highest. The presence of these compounds suggests that they are still used in the region and are environmentally recalcitrant.     

Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary,Southeast China

Persistent organochlorine compounds were analyzed in surface water, porewater and surficial sediment samples from Minjiang River Estuary, which is the first large river in Fujian Province, Southeast of China. The total concentrations of 18 organochlorine pesticides were 214.4-1819, 4541-13,699 ng/l, 28.79-52.07 ng/g in surface water, porewater and sediments (dry weight) respectively, and those of 21 polychlorinated biphenyls (PCBs) in the three phases were: 203.9-2473, 3192-10,855 ng/l, 15.14-57.93 ng/g respectively. The results showed that the concentrations of these selected organochlorine pesticides and PCBs in porewater were higher than those in surface water. It may be due to the fact that these organic hydrophobic pollutants tend to stay in the sediments, and then re-suspend from the sedimentary phase to the upper water. We have analyzed the distribution characteristics of individual organochlorine pesticide components and PCBs, and found that alpha-HCH, DDE, Heptachlor, Endosulfan II, Methoxychlor were the most common organochlorine pesticides contaminants. Considering the groups of HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH) and DDTs (DDTs=DDT+DDD+DDE), the predominance of beta-HCH, DDE in all water, porewater and sediment samples was clearly observed. This observation suggested that beta-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD, of which DDE that was more un-degradable. The PCB congeners containing 3-6 chlorines had the great preponderance in the three phase. These results were compared with those present in other estuaries and harbors. A risk assessment was evaluated for the persistent organic pollutants in the Minjiang River Estuary.     

Investigation of organochlorine pesticides (OCPs) in mollusks collected from coastal sites along the Chinese Bohai Sea from 2002 to 2004

Mollusks living in seas can accumulate organochlorine pesticides (OCPs). The residue levels of selected OCPs: dichlorodiphenyltrichloroethane (p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD), hexachlorocyclohexanes (alpha-, beta-, gamma- and delta-HCH) in gastropod and bivalve species collected from ten coastal cites along the Chinese Bohai Sea were investigated from 2002 to 2004. The species included nine kinds of mollusks: Rapana venosa, Neverita didyma, Scapharca subcrenata, Mytilus edulis, Amusium, Crassostrea talienwhanensis, Meretix meretrix, Sinonovacula constricta, Ruditapes philippinarum, Mactra veneriformis. The results showed that OCPs widely existed in the mollusks organisms. p,p'-DDT, p,p'-DDE, beta-HCH were the major compounds. Statistical analysis (One-way ANOVA) showed that the contents of OCPs in these mollusks did not change obviously from 2002 to 2004. Principal component analysis (PCA) was also used for determining the polluting characters existing in this selected field.     

Temporal trends of organochlorines and mercury in seabird eggs from the Canadian Arctic, 1975-2003

Organochlorine pesticides, PCBs, total mercury and selenium were measured in eggs of thick-billed murres, northern fulmars and black-legged kittiwakes collected from Prince Leopold Island in the Canadian High Arctic between 1975 and 2003. The primary organochlorines found were SigmaPCB, p,p'-DDE, oxychlordane, and hexachlorobenzene (HCB). Most of organochlorines analyzed showed either significant declines or no significant change between 1975 and 2003 in all three species. However, significant increases were observed for SigmaHCH in the kittiwakes and fulmars, and beta-HCH in the murres and fulmars. Mercury increased significantly in eggs of murres and fulmars, whereas mercury in the kittiwakes did not change significantly over the study period. Statistical analyses included stable-nitrogen isotope ratios (delta(15)N) to control for any variation in trophic level over time. Although the contaminant concentrations reported in this study are below published threshold values, mercury and beta-HCH concentrations continue to increase suggesting that continued monitoring is warranted.     

Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.     

Urinary phenolics and glucuronides in hexachlorocyclohexane isomers fed rats

Rats fed with dietary beta- and gamma-isomers of hexachlorocyclohexane excreted higher amounts of phenolics and glucuronides in the urine as compared to controls. The excretion profile of urinary phenolics and glucuronides suggested a relatively higher turnover rate of the gamma-isomer in the body as compared to the beta-isomer. Excretion of ethereal sulfate was low in hexachlorocyclohexane fed animals.     

Control of common freshwater predatory fish, Channa punctatus, through Nerium indicum leaf extracts

The diethyl ether, chloroform, acetone and methanol extract of Nerium indicum leaf were evaluated for their piscicidal activity against common freshwater air breathing predatory fish Channa punctatus. The rank of order of toxicity (LC50) of the leaf extract was, diethyl ether extract (17.34 mg/l)>acetone (40.01 mg/l)>chloroform (40.61 mg/l)>and methanol (106.37 mg/l). There was a significant negative correlation between LC50 values and exposure periods. Thus increase in exposure period, LC50 decreases from 17.34 mg/l (24 h) to >13.58 mg/l (96 h) in the diethyl ether extract. Similar trends were also observed in acetone, chloroform and methanol extracts. Exposure of sub-lethal doses (40% and 80% of LC50) of the diethyl ether extract of N. indicum leaf (which has maximum piscicidal activity) for 24 or 96 h caused significant alteration in the level of total protein, total free amino acid, nucleic acid, glycogen, pyruvate, lactate and activity of enzyme protease, phosphatases, alanine aminotransferase, aspartate aminotransferase and acetylcholinesterase in liver and muscle tissue. The alterations in all the above biochemical parameters were significantly (P<0.05) time and dose dependent. There was a significant recovery in all the above biochemical parameters, in both liver and muscle tissues of fish after the seventh day of the withdrawal of treatment. Thus, the leaf extracts of N. indicum have potent piscicidal activity against fish C. punctatus and also significantly affect both aerobic and anaerobic pathway of respiration in fish.     

Distribution and fate of organochlorine pesticide residues in sediments from the selected rivers in Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from selected rivers in Taiwan was investigated to evaluate the pollution potentials and hazard in river sediments. Da-han River and Erh-jen River were selected as the target rivers due to their serious pollution. A total of 40 surface sediment samples were collected at five sampling stations along the rivers. Results showed that the concentrations of various pesticides in sediments were in the range of 0.57-14.1 ng/g for sigmaHCH, 0.05-0.15 ng/g for aldrin, 0.12-5.8 ng/g for dieldrin, 0.22-0.64 for endrin, 0.24-6.37 ng/g for endosulfan and 0.21-8.81 ng/g for EDDT (p,p'-DDD, p,p'-DDE, p,p'-DDT). Among the OCPs, sigmaHCH, endosulfan and sigmaDDT were the most dominant compounds in the river sediments. Endosulfan sulfate was the most frequent detected compound in the sediments from the selected rivers. Also, sigmaDDT, dieldrin and beta-HCH were in abundance. Different contamination patterns between the selected river sediments were also observed. Da-han River was mainly contaminated with endosulfan sulfate and sigmaDDT. Whereas the main pesticides in Erh-jen River were beta-HCH and sigmaDDT. Among the cyclodiene compounds, dieldrin was in abundance in most of the sediments. Moreover, the frequencies of detection of the metabolites were higher than those of parent compounds, depicting that the sediments have contaminated for a long time. The results obtained in this study showed that there still exist a variety of OCP residues in the river sediments in Taiwan.     

Temporal trend of bis(4-chlorophenyl) sulfone, methylsulfonyl-DDE and -PCBs in Baltic guillemot (Uria aalge) egg 1971-2001--a comparison to 4,4'-DDE and PCB trends

The dynamics of organohalogen contaminants and their metabolites are best studied over time by analysis of biota at high trophic levels. In this study, time trends, 1971-2001, of bis(4-chlorophenyl) sulfone (BCPS) and of methylsulfonyl-substituted metabolites of PCBs and 4,4'-DDE, were investigated in eggs of guillemot (Uria aalge) hatching in the Baltic Proper. Temporal trends of PCBs, trans-nonachlor, beta-HCH, 4,4'-DDT, and 4,4'-DDE were also assessed. Tris(4-chlorophenyl) methane (TCPMe), a 4,4'-DDT by-product, was detected in the eggs. The concentration of BCPS ranged between 2.6-0.76 microg/g on a lipid weight basis over the three decades and showed a significant 1.6% annual decrease. Three metabolites of PCBs, i.e. 3'-MeSO2-CB101, 4'-MeSO2-CB101 and 4-MeSO2-CB149, were quantified in all samples over time and showed an annual decrease of approximately 3% compared to MeSO2-DDE with a decrease of 8.9%. The methylsulfonyl-PCB and -DDE metabolites are eliminated more slowly than the persistent PCB congeners and 4,4'-DDE. Trans-nonachlor decreases by 16% compared to 19% and 9% for 4,4'-DDT and beta-HCH, respectively. The concentration of TCPMe in guillemot decreased by 8.2% per year. A linear relationship was found between TCPMe and 4,4'-DDE concentrations which supports the theory that TCPMe has an origin as a contaminant in commercial 4,4'-DDT products. The very slow decrease in BCPS concentrations is notable and remains to be explained. BCPS is still present at rather high concentrations in the guillemot eggs. The enantiomeric fraction varied between 0.27 and 0.67 which indicates less of a specific retention of the chiral MeSO2-PCBs in guillemot eggs than in grey seal tissues, for example. Independent of meta- or para-substitution of the sulfone group, the most accumulative atropisomer of each of four MeSO2-PCB pairs has been assigned an absolute R structure.