Distribution of hexachlorocyclohexane isomers in soil samples from a small scale industrial area of Lucknow, North India, associated with lindane production

Concentrations of hexachlorocyclohexane isomers (alpha-HCH, beta-HCH, gamma-HCH, and delta-HCH) were studied in soils samples collected from a small scale industrial unit of Lucknow associated with lindane production. All four isomers were detected from ten sites and the total HCH isomers in the analyzed samples varied from 53 to 99mgkg(-1). Cluster analysis was performed to group the soil sites in terms of their HCH contamination level. Low alpha/gamma HCH ratios were found and they indicate recent input of HCH. There is an urgent need for the on-site remediation of these contaminated sites in order to prevent the long-term environmental pollution.     

Polychlorinated organic compounds in the Arctic cod liver: trends and profiles

Polychlorinated organic compounds (POCs) have been measured in Arctic cod liver from Vestertana Fjord for a period of 1987-1998. Significant decrease was observed for DDD (p = 0.043), alpha-HCH (p = 0.001), and gamma-HCH (lindane; p = 0.001). Contents of DDE, 2,3,7,8-tetrachlorodibenzofuran, PCBs, chlordanes, chloronaphthalenes, hexachlorobenzene and polychlorodiphenyl ethers had no significant trend. Contents of three hexa- and two heptachlorodibenzofurans and octachlorodibenzofuran increased slightly from 1987 to 1994, but then at very high rate from 1994 to 1998. Trends of HCHs, profiles of PCBs and levels of chlordanes are in accordance with atmospheric long range transport. The hexa-, hepta- and octachlorodibenzofurans observed are major impurities in chlorophenol formulation Ky-5, which has been used as wood preservative and as fungicide/slimicide in industrial processes. Their profile in Vestertana cod was similar to that observed in Ky-5 contaminated fish.     

Air-sea gas exchange of HCHs and PCBs and enantiomers of alpha-HCH in the Kattegat Sea region

Concentrations and air-water gas exchange of polychlorinated biphenyls (PCBs) and hexachlorocyclohexanes (HCHs) were determined in nine paired air and water samples. The samples were collected monthly in the Kattegat Sea between December 1998 and November 1999. Average fugacity and flux values indicated that PCBs were oversaturated in the water, while HCHs were net deposited. Variations were large over the year, especially during spring and summer. Air parcel back trajectories suggested that air concentrations over the Kattegat Sea are largely dependent of air mass origin. Seasonal trends were detected for airborne HCHs and for PCBs in water. The air and water enantiomeric compositions of alpha-HCH indicated that a larger portion of alpha-HCH in air originated from the underlying water during summer than during winter.     

Long-term fate of three hexachlorocyclohexanes in the lower reach of Liao River basin: dynamic mass budgets and pathways

The Liao River Basin Multimedia Fate and Transport Model (LRBMFTM), a non-steady state multiple-segment river fugacity-based model, for describing the long-term fate of persistent organic pollutants (POPs) in Liao River basin environment, is used to illustrate a quantitative understanding of the behavior of alpha-, beta-, and gamma-hexachlorocyclohexane (HCH) in more detail in the lower reach of Liao River basin from 1952 to 2001. The major pathway of the three HCHs from the basin to the surrounding environment is the atmospheric advection. One of the major removing of HCHs from the basin is degradation, where 2388.5 ton of alpha-HCH, 405.6 ton of beta-HCH, 382.7 ton of gamma-HCH emitted into the basin have been degraded, especially in the soil of application regions. The main reservoir of the HCHs is the soil in the basin, where there is a positive correlation between the accumulated amount and emission. The model suggests that the mass fluxes of all processes show an obviously seasonal trend. After the use ban, HCHs evaporate from water bodies, soils, and vegetation, and are advected away in the atmosphere. It is believed that the model can provide a valuable understanding of the processes that determine the overall fate of HCHs in the basin.     

Organochlorine pesticides and metabolites in young leaves of Mangifera indica from sites near a point source in Coast region, Tanzania

Young leaves of Mangifera indica (mango tree) from nine sites were used as bioindicators of local atmospheric contamination by organochlorine pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. Sample extracts were analysed by GC-ECD and GC-MS. The concentrations ranged 2.7-649 ng g(-1)p,p'-DDT, below detection limit (bdl)-290 ng g(-1) o,p'-DDT, 0.4-13 ng g(-1) p,p'-DDE, bdl to 4 ng g(-1) o,p'-DDE, 1-231 ng g(-1) p,p'-DDD and 0.5-55 ng g(-1) o,p'-DDD. The concentrations of other compounds were up to 3.9 ng g(-1) pentachloroanisole, 1.3 ng g(-1) alpha-HCH, 12 ng g(-1) beta-HCH and 2 ng g(-1) gamma-HCH, on fresh weight basis. The compounds p,p'-DDT, p,p'-DDE, p,p'DDD and o,p'-DDD were found in 100% of the samples, while pentachloroanisole, o,p'-DDT and o,p'-DDE were detected in 78%, 56% and 67% of the samples, respectively. The low DDE/DDT ratios (0.01-0.20) in all samples indicate recent input of significantly non-degraded DDT from the point source. The low alpha-/gamma-HCH ratios (<0.3-0.7) in most samples indicate recent input of lindane (99% gamma-HCH). The slightly high alpha-/gamma-HCH ratios in some samples might be due to photochemical or bacterial transformation of gamma-HCH to alpha-HCH, or could reflect input of technical HCH. The very strong positive correlations in the concentrations of p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT, o,p'-DDE and o,p'-DDD (r=0.91-0.98, n=18, p<0.01) indicate that they have a common source. The results suggest that young mango leaves are suitable bioindicators of recent inputs of organochlorine contaminants from a point source.     

Distribution of organochlorine pesticides, polychlorinated biphenyls and alpha-HCH enantiomers in pork tissues

The distribution of HCH isomers, DDT analogues and selected PCB congeners in pork organs collected from the same individuals raised in Romanian farms was investigated. Organochlorine pesticides (HCHs and DDTs) were the principal contaminants in all samples, while PCB concentrations were low, in accordance with previously reported concentrations from Romanian animal farms. The most part of the pollutant load in the body is retained in the adipose tissue, with HCHs ranging between 16 and 27.7 ng/g lipid and with higher concentrations of DDTs ranging between 65.9 and 334.5 ng/g lipid. The highest PCB levels (up to 32 ng/g lipid) were measured in lung and liver. The lipid-normalized concentrations in the brain were lower than in all other tissues due to the presence of the blood-brain barrier or due to a lower proportion of the neutral lipids such as triglycerides. The highest concentrations of DDTs were measured in muscle and fat, with p,p'-DDE being the principal contributor and with a variable contribution of p,p'-DDD and p,p'-DDT. In liver, p,p'-DDD has a higher contribution to the sum DDTs, while in all analyzed livers, the concentration of p,p'-DDT was very low. beta-HCH was the most persistent HCH isomer in all tissues, accounting for 40-97% of sum HCHs. For all animals, the highest concentrations of beta-HCH and HCHs were found in liver, while the lowest HCH concentrations were measured in brain and spinal marrow. Additionally, the distribution of alpha-HCH enantiomers in the tissues was discussed. In all samples (except 2 brain samples), (+) alpha-HCH was depleted and (-) alpha-HCH was enantioenriched. Enantiomeric ratios in brain were the highest measured values between all organs. For all studied animals, ERs increased in the order fat < muscle < liver < brain.     

Occurrence and vapor particle partitioning of heavy organic compounds in ambient air in Brazzaville, Congo

High volume air samples for organochlorine (OC) pesticides, polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) were collected during August-September 1989 in Brazzaville, Congo (4.14 degrees S, 15.14 degrees E). Average concentrations (ng/m3) were SigmaDDT=2.8; Sigma HCH (hexachlorocyclohexane)=0.42; Sigmachlordane=0.027; SigmaPCB=0.55 Sigma3-6 ring PAH=42; total DDT concentrations in Brazzaville fell between those reported in Porto Novo and Delhi (India) and were 20-100 times higher than those found in US cities. The average gamma-HCH to alpha-HCH ratio (11) indicated use of lindane instead of technical HCH. The similarities between chlordane levels in Brazzaville and the open ocean indicated that little or no local use occurs. PAH levels were about equal to or lower than those reported in US cities, whereas PCB levels were three times lower. Vapor/particle distribution coefficients for several OC and PAH were in good correlation with their vapor pressures. The fraction of PAH on particles was greater than that of OC pesticides.     

Relative sensitivity of Daphnia magna and Brachionus calyciflorus to five pesticides.

Comparative toxicity of several pesticides, lindane, endosulfan, pentachlorophenol (PCP),3,4-dichloroaniline (DCA) and copper sulphate has been tested to determine their lethality in two species of freshwater invertebrates, Daphnia magna and Brachionus calyciflorus. D. magna was more sensitive than B. calyciflorus to all the toxicants tested except to copper sulphate. DCA was the most toxic compound to D. magna and was followed in order of decreasing toxicity by copper sulphate, PCP, endosulfan and lindane. Copper sulphate was the most toxic chemical tested to the rotifer B. calyciflorus and was followed by PCP, endosulfan, lindane and DCA. The 24 hr LC50 values (mg/L) for D. magna and B. calyciflorus, respectively, were: lindane, 1.64 and 22.5; endosulfan, 0.62 and 5.15; DCA, 0.20 and 61.5; PCP, 0.39 and 2.16; copper sulphate, 0.38 and 0.076.     

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems

Gamma-hexachlorocyclohexane (gamma-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of alpha-, beta-, gamma-, delta-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While alpha- and gamma-HCH disappeared after 20-40d, the most recalcitrant isomers: beta- and delta-HCH were only degraded after 102d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.     

Biocatalytic dechlorination of lindane by nano-scale particles of Pd(0) deposited on Shewanella oneidensis

A new approach for the removal of the pesticide lindane (gamma-hexachlorocyclohexane or gamma-HCH) makes use of catalytic reduction of HCH to benzene over a metal catalyst, namely Pd(0). Since specific surface area plays an important role in reactivity of catalysts, this study investigated the use of bioPd(0), i.e. nano-scale Pd(0) particles precipitated on the biomass of Shewanella oneidensis, for the removal of lindane. It was demonstrated that bioPd(0) has catalytic activity towards dechlorination of gamma-HCH, with the addition of formate as electron donor, and that dechlorination with bioPd(0) was more efficient than with commercial powdered Pd(0). The biodegradable compound benzene was formed as reaction product and other HCH isomers could also be dechlorinated. Subsequently bioPd(0) was implemented in a membrane reactor technology for the treatment of gamma-HCH polluted water. In a fed-batch process configuration with formate as electron donor, a removal percentage of 98% of gamma-HCH saturated water (10 mg l(-1)) was achieved within 24h. The measured chloride mass balance approached the theoretical value. The results of this work showed that a complete, efficient and fast removal of lindane was achieved by biocatalysis with bioPd(0).     

Mass budgets and contribution of individual sources and sinks to the abundance of gamma-HCH, alpha-HCH and PCB 153 in the North Sea

Mass budgets of hexachlorocyclohexanes (alpha-HCH and gamma-HCH) and a polychlorinated biphenyl (PCB 153) for 1995--2001 were calculated based on model simulations and observations for the North Sea as a whole and the German Bight, a coastal shallow subregion. For the North Sea the air-sea fluxes of the three pollutants were net depositional and dominated by local sources (gamma-HCH and PCB 153) or atmospheric deposition (alpha-HCH). The air-sea fluxes were net volatilizational in the German Bight. Unlike HCH, PCB 153 does not show a downward trend in the North Sea marine environment during the study period. Due to its physicochemical properties it is expected to readily enter the food chains. Model results suggest that during studied period, the North Sea was a sink for PCB 153 and a source of HCHs for the outer world.     

Assessing spatial distribution,sources, and human health risk of organochlorine pesticide residues in the soils of arid and semiarid areas of northwest China

Thirty-two topsoil samples were collected to analyze the residue levels of organochlorine pesticides (OCPs) in topsoil of arid and semiarid areas of northwest China in 2011. Results showed that DDTs were the dominant contaminants with a mean concentration of 12.52 ng/g. The spatial distribution characteristics indicated that α-hexachlorocyclohexanes (HCHs) were mainly used in rural sites, whereas hexachlorobenzene (HCB) and endosulfan were detected mostly in urban areas. DDTs, heptachlor, and chlordane were found almost equally in both urban and rural areas. Source identification revealed that the current levels of HCHs in soils were attributable to the residues from their historical use and fresh usage of lindane (γ-HCH). DDTs were mainly from historical use and fresh usage of dicofol, and HCB was emitted from the chemical industry. It was also found that the current soil levels of heptachlor were mainly from its historical usage, endosulfan from fresh input, and chlordane from long-range atmospheric transport, respectively. The noncarcinogenic health risk assessment with a model was also conducted using USEPA standards for adults and children. Results indicated that health risk under nondietary exposure to OCPs decreased in the sequence of ΣDDT?>?ΣHCH?>?HCB?>?Σheptachlor?>?Σendosulfan?>?Σchlordane. According to the reference dose from the USEPA, the health risk under nondietary exposure to OCPs in the soil samples was at a relatively safe level.     

An anaerobic bioreactor allows the efficient degradation of HCH isomers in soil slurry

The insecticide gamma-hexachlorocyclohexane (gamma-HCH or lindane), which has been extensively used for agricultural and medical purposes, presents high persistence and toxicity to the environment and low solubility. This study intends to assess the efficiency of an anaerobic reactor to degrade HCH isomers contained in soil slurry cultures. This study was developed in two phases: experiments in flasks to optimize the process parameters, and assessment of the slurry process in the anaerobic slurry reactor operated for an approximate period of a year. The influence of different environmental conditions was evaluated: the HCH concentration (25-100 mg HCH kg-1), the type of substrate (volatile fatty acids or starch), the sludge concentration (2-8 g VSS l-1) and the replacement of spiked soil to simulate a fed-batch operation (10-50%). The best results were obtained when the reactor was operated with a sludge concentration of 8 g VSS l-1, starch concentration of 2 g COD l-1 and soil replacements of 10-20%. Under these conditions, alpha- and gamma-HCH were completely degraded after 10d while nearly 90% beta- and delta-HCH were removed only after 50 d. According to the obtained results related to the total degradation of the HCH isomers and the degradation rates, especially high for alpha- and gamma-HCH, the anaerobic slurry reactor appears to be a good alternative for the degradation of the HCH isomers present in polluted soil.     

Organochlorine pesticides in soil profiles from Tianjin, China

Soil cores were collected from soils at five sites in Tianjin area for the determination of hexachlorocyclohexane isomers (HCHs, including alpha-HCH, beta-HCH, gamma-HCH and delta-HCH), dichlorodiphenyltrichloroethane and metabolites (DDXs, including p,p'-DDT, p,p'-DDE and p,p'-DDD) and total organic carbon (TOC). The levels and vertical distributions of HCHs and DDXs are studied. Results show that the application of pesticides in the past years was the major contributor of HCHs and DDXs accumulation in the sampling areas. Significant positive correlations were seen between the residual and application amounts of HCHs and DDXs. Wastewater irrigation did not bring a significant contribution of HCHs or DDXs into the soils. HCHs and DDXs concentrations peak at the surface and decline in soil profile with depth, while fluctuations were observed in the plow layers of some cultivated soils caused by frequent cultivation activities and batch irrigation. Positive correlations were observed between the contents of TOC and HCHs and DDTs. Although the amounts of HCHs application in all sampling sites are larger than DDXs, at surface and near surface layers of most sampling sites, the concentrations of summation operatorHCHs are lower than summation operatorDDXs. The composition of DDXs in the applied pesticides and sampled soils indicates that there is no recent DDT input at the sample areas.     

Distribution and ecological risk assessment of organochlorine pesticides in surface sediments from the East Lake,China

Organochlorine pesticides (OCPs) are ubiquitous pollutants, and their presence in urban lakes is a concern for human and ecological health. Surface sediments in the East Lake, China, were collected in winter 2012 and summer 2013 to investigate concentrations, distribution patterns, possible sources, and potential ecological risks of OCPs in this area. The total concentrations of 14 OCPs ranged from 6.3 to 400 ng g^?1 dry weight (dw) with an average concentration of 79 ng g^?1 dw. The mean values of hexachlorocyclohexanes (HCHs) (α-, β-, γ-, and δ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (p,p’-DDE, p,p’-DDD, and p,p’-DDT) were 36 and 7.6 ng g^?1 dw, accounting for 45 and 10 % of the total OCPs, respectively. The concentrations of OCPs in sediment samples collected in winter were significantly higher than those in summer, especially the HCHs, of which in winter were two times greater than summer. Composition analyses indicated that DDTs and endosulfan were mainly from historical contribution. Historical use of technical HCH and new input of lindane were probably the source of HCHs in the East Lake. Most sampling sites of HCHs and DDTs were found to have the potential ecological risk based on levels specified in the sediment quality standards.     

Pine needle and semi-permeable membrane device derived organochlorine compounds (OCPs) concentrations in air in Mersin Province to Taurus,Turkey

Abstract

Organochlorine pesticides (OCPs) were analyzed in three different ages (half-, 1.5-, 2.5-year-old) for needles and semi permeable membrane devices (SPMDs) at three deployment periods from sea level to 1881 meter above sea level. Individual HCHs concentrations ranged between 1.4 and 129?pg/g fw depending on the age and sampling season while 2.5-year-old needles showed higher HCHs levels compared to half and 1.5- year-old. Correlation between elevation and HCH concentration in SPMDs was found but not in needle samples. Concentrations of HCHs in SPMDs indicated clearly cold condensation effect on accumulation in winter period and increased with altitude. Concentrations of DDTs in half and 1.5-year-old needles were lower than 2.5-year-old needles. The highest total concentration of DDTs was detected in 1-year-period SPMD. Higher concentrations were found in 2.5-year-old needles for other OCPs. Seasonal and altitude-dependent changes were not observed for other OCPs in SMPDs. Total accumulation of OCPs in SPMDs were found higher than in needles. On the contrary, an increased accumulation rate was observed for HCHs in SPMD. In general, Total concentrations of DDTs and HCHs were similar to total of other OCPs in all altitudes when dominating endosulfan wasnot taken into account in the computation of total concentration of other OCPs.     

Pesticides in rainfall in Europe

Papers and published reports investigating the presence of pesticides in rainfall in Europe were reviewed. Approximately half of the compounds that were analysed for were detected. For those detected, most concentrations were below about 100 ng/l, but larger concentrations, up to a few thousand nanograms per litre, were detected occasionally at most monitoring sites. The most frequently detected compounds were lindane (gamma-HCH) and its isomer (alpha-HCH), which were detected on 90-100% of sampling occasions at most of the sites where they were monitored. For compounds developed more recently, detection was usually limited to the spraying season. A classification of pesticides according to their deposition pattern is proposed.     

Organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in Singapore's coastal marine sediments

Persistent organic pollutants (POPs) are ubiquitous pollutants in the marine environment, particular in coastal areas affected by industry and shipping traffic. POPs are known for their recalcitrance and toxicity in the environment, and there is increasing concern over their global distribution and impact upon wildlife. Marine surface sediment samples taken within 6 km of the coastline of Singapore were analyzed to determine prevailing concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyl (PCBs) and polybrominated diphenyl ethers (PBDEs). Total PCB concentrations varied widely from 1.4 to 329.6 ng/g (average 73.9 ng/g), where high concentrations were detected at sample locations closest to industrial areas with intensive shipping traffic. Total DDT concentrations ranged from 2.2 to 11.9 ng/g (average 6.7 ng/g) and were lower than the concentration range of 3.3-46.2 ng/g measured for total HCH (average 18.1 ng/g). Ratios of DDT/(DDE+DDD) in sediments do not indicate recent inputs of DDT into Singapore's marine environment, but high concentrations of alpha-HCH and gamma-HCH show evidence for the usage of HCHs in Southeast Asia. Peak concentrations of cis- and trans-Chlordane were 10 ng/g. Among the PBDE congeners BDE 47, 99, and 100 only BDE 47 could be detected at a range of 3.4-13.8 ng/g (average 6.2 ng/g). The levels of OCPs, PCBs and PBDEs were compared to available data for other countries in Asia, and indicated relatively moderate levels of contamination. Peak concentrations of PCBs, HCH isomers, Chlordane, Heptachlor, Heptachlor epoxide and Dieldrin have the potential to induce ecotoxicological impacts based on levels specified in the sediment quality standards of the USEPA and Canadian Council of Ministers of the Environment.     

Gridded inventories of historical usage for selected organochlorine pesticides in Gansu Province, China

HCHs and DDTs were banned in 1983 in China; however, they are still remaining in various environmental media. Since endosulfan was introduced in China in 1994, it is widely used in agriculture. In this study, temporal and spatial uses of endosulfan, HCHs, and DDTs in Gansu province of China have been presented. It is estimated that the total usage is 701 tons for endosulfan between 1994 and 2007, 1,712 tons for HCHs between 1952 and 1983, and 462 tons for DDTs between 1951 and 1983, respectively. Endosulfan usage increased dramatically in 1998 due to its application on other crops except on cotton. The HCH and DDT usage displayed a rapid increase after 1972, reaching the peak in 1976 and in 1975, respectively; since then, they declined until being banned in 1983. The gridded usage inventories of these three kinds of organochlorine pesticides in Gansu province, with a 1/4° longitude by 1/6° latitude resolution, have been created by using different crops for endosulfan and the area of dry farmland for HCHs and DDTs as surrogate data. The most intensive use was in northwestern regions for endosulfan and southeastern regions for HCHs and DDTs in Gansu province.     

Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China

Tonghui River, a typical river in Beijing, People's Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides in water and sediment samples. Total PAHs, PCBs and organochlorine pesticides concentrations in water varied from 192.5 to 2651 ng/l, 31.58-344.9 ng/l and 134.9-3788 ng/l, respectively. The total PAHs, PCBs and organochlorine pesticides concentrations in surficial sediments were 127-928 ng/g, 0.78-8.47 ng/g and 1.79-13.98 ng/g dry weight, respectively. The results showed that the concentration of these selected organic pollutants in sediment was higher than those in surface water. It may be due to the fact that organic hydrophobic pollutants tend to stay in the sediments. The PAHs were dominated by 2-, 3-ring components in water samples and by 3- and 4-ring compounds in sediment. For organochlorines, alpha-HCH, delta-HCH, Heptachlor, Endosulfan II, DDT are the major organochlorine pesticides in water while Heptachlor, Dieldrin and DDE composed of 95% of total organochlorine pesticides in sediment. For HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH), the predominance of alpha-HCH of total HCHs were clearly observed in water and sediment. PCB18, PCB31 and PCB52 were predominant in water, on average these compounds collectively accounted for 67% of total PCBs. But in sediment, the predominant compounds were PCB28, PCB31 and PCB153, which accounted for 71% of total PCBs in sediment. The levels of micro pollutants in our study areas were compared with other studies.