Occurrence and behaviour of organophosphorus insecticides in the River Wuchuan,southeast China

Organophosphorus (OP) insecticides are used worldwide, yet their persistence in the environment is not well understood. This paper summarises recent research on 17 OP insecticides in the River Wuchuan, an important catchment in China, by determining their concentrations in water, soil, sediment and plants by gas chromatography with flame photometric detection (GC-FPD). The concentrations of the total OP insecticides ranged from 92.77 to 229 ng l-1 in river water, 1.61 to 9.93 ng g-1 dry weight in soil, 1.24 to 7.56 ng g-1 dry weight in sediment and 75.28 to 326 ng g-1 dry weight in plants. There was a relatively high abundance of methamidophos, dichlorvos, malathion, omethoate and dimethoate in all water, soil, sediment and plant samples. On average, these five compounds collectively accounted for 64%, 71%, 71% and 54% of the total OP insecticide concentration in water, soil, sediment and plants, respectively, which was similar to the composition of OP insecticides in application formulations used in our study area and in China as a whole. The results therefore reflect the application pattern to some extent, and suggest that the sources of the OP insecticides are mainly from current usage. When compared with other areas, the levels of OP insecticides in the River Wuchuan were moderate. The animal and human risks from exposure to OP insecticides in water and plants were evaluated against relevant threshold values. The results therefore provide important information on the current contamination status of a key agricultural watershed in China, and point to the need for urgent action to control the use of some excessively applied and potentially persistent agrochemicals, such as methamidophos, omethoate and dimethoate.     

Distribution and sources of organochlorine pesticides in sediments of the Xiangjiang River, south-central China

The Xiangjiang River (XR), the second largest tributary of the Yangtze River, is mainly located in Hunan province in south-central China. Nineteen surface sediment samples (the top 3-cm layer) collected from XR were analyzed to determine the concentrations, distribution, sources, and ecological risk of organochlorine pesticides (OCPs). The concentrations of OCPs were 3.0–29.8 ng/g (dry weight) with a mean of 12.6?±?7.7 ng/g. The widely detected compounds included HCHs, DDTs, HCB, and dieldrin. Overall, the dominant OCPs in the sediments were mainly composed of residual and degradation products, e.g., β-HCH with a mean of 42.2 % in HCHs and p,p′-DDE with a mean of 43.5 % in DDTs, implying that OCPs in the sediments had suffered from long-term aging without fresh inputs in XR. However, there was a high proportion of p,p′-DDT to DDTs in three sites, suggesting that there was use of technical DDT from their surrounding areas at present. The ratios of α-HCH/γ-HCH and p,p′-DDD?+?p,p′-DDE/DDTs increase from the upper reaches to the lower reaches of XR, suggesting sediments enriched with α-HCH and metabolites DDD and DDE during sediment transport process and could be attributed to the transformation of γ-HCH to α-HCH and DDT to DDE or DDD. The assessment of the ecological risk indicates that the OCPs in the sediments of XR have a moderate adverse biological effect on organisms.     

Levels and source of organochlorine pesticides in surface waters of Qiantang River, China

Qiantang River is a typical river used for drinking water source, flowing through agricultural area in east China. Surface water samples at 45 sampling sites from the river were collected and analyzed for 13 organochlorine pesticides (OCPs) during six surveys in 2 years of 2005–2006. Sediments, soils, farmland runoff water and dry/wet deposition of this region were also measured for their OCPs residue in order to know possible source of OCPs contamination. The total OCPs concentrations in surface water were 7.68–615.2 ng/l. β-HCH, δ-HCH, Aldrin, Heptachlor, Heptachlor epoxide are the major OCPs in water. The maximum levels of OCPs in water were found in July, while significantly lower OCP concentrations were measured in January. Significant linear correlation was found between the concentration of HCH and that of total 13 OCPs in water. The measured OCP concentrations in sediments, soils, farmland runoff water and dry/wet deposition are discussed in relation to concentrations and patterns found in the surface water. Comparison of OCP levels in sediments and soils led to conclusion that erosion of soil contribute significantly to the contamination of water. The OCPs dry and wet deposition to water body was estimated to 0.49 and 0.86 ton/year, respectively. The ratio of α/γ-HCH and (DDE+DDD)/∑DDT in environmental matrix indicated there probably existed new OCPs input of lindane and dicofol into the river.     

Atmospheric depositional fluxes and sources apportionment of organochlorine pesticides in the Pearl River Delta region, South China

Organochlorine pesticides (OCPs) have variously been phased out in agricultural activities, but they are still widely detected in air, water, and soil systems due to their recalcitrant nature in the environment. The purposes of this study were to assess potential OCP pollution via dry and wet deposition over the fast developing Pearl River Delta area with 41,700 km², where the main effort has been focused on emerging pollutants such as petroleum hydrocarbons and PM2.5. We quantified both the dry and wet deposition fluxes of 19 OCPs including dichlorodiphenyltrichloroethanes (DDTs), endosulfans (Endos), and hexachlorocyclohexanes (HCHs). The results showed that each year about 67.4, 42.0, 15.0, and 8.07 kg of total OCPs, DDTs, Endos, and HCHs were returned to the ground, among which 11.7, 10.4, 0.84, and 0.16 kg were in the dry deposition forms. The large spatial variations in OCP deposition fluxes indicated that OCP pollution in the air is mainly influenced on local scales because evaporation from local soil is likely the major source of the phased out OCPs. Source analysis indicated that DDTs may be still in use as antifouling agent and/or dicofol, but Endos and HCHs were mainly derived from the residual of historical usage. The study suggests that the historical OCP pollutants are persistent at high levels in this area and should not be overlooked, while we tackle emerging pollutants.     

Incidence of organochlorine pesticides in soils of Shenzhen, China

To determine the incidence of organochlorine pesticides (OCPs) in soil in a rapid urbanization region, soil samples from various land use types in Shenzhen were collected in winter, 2007. The concentration of dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) ranged from non-detected to 149 ng g(-1) and 19 to 88 ng g(-1), respectively. The highest levels of OCPs were observed in soil from traffic and industry areas, reflecting that intensive human disturbance make the soil pollution accumulation more disperse. HCHs and DDTs profiles revealed that the sources were associated mainly with lindane and technical DDTs, respectively, while HCHs in the soil of Shenzhen might originate from both recent and historical sources. The loss of OCPs by soil erosion will enter surface runoff and impose impact on the water environment. Non-dietary exposure estimation indicates that children were the most sensitive group. The average daily exposure to OCPs for males was more serious than for females. Non-dietary exposure to DDTs and HCHs in residential blocks of Shenzhen were far below the acceptable daily intake recommended by the Food and Agriculture Organization/World Health Organization.     

Residues of organochlorine pesticides in water and suspended particulate matter from the Yangtze River catchment of Wuhan, China

The residues of 13 organochlorine pesticides (OCPs) in surface water and HCHs and DDTs in suspended particulate matter (SPM) from rivers and lakes in Yangtze River catchment of Wuhan, China, were investigated. The concentration of total OCPs in surface water varied from 1.01 to 46.49 ng l⁻¹ (mean 10.55 ng l⁻¹). The levels of total HCHs (ΣHCH) and total DDTs (ΣDDT) in surface water were in the range of 0.55–28.07 ng l⁻¹ and lower than detection limit to 16.71 ng l⁻¹, respectively, which was lower than Chinese standards on the whole. For OCPs residues in SPM, the mean levels varying from 0.20 to 34.72 ng l⁻¹ and 0.46 to 2.72 ng l⁻¹ for ΣHCH and ΣDDT, respectively, which ranked the relatively higher levels among Chinese studied rivers. Results from this investigation showed that previous excessive usage of technical OCPs was the main reason for the residues of HCHs and DDTs both in surface water and SPM, although some new sources were likely to occurred in the region. Apart from the OCPs in SPM originated from upstream in flood season, one of the important sources of OCP residues both in water and SPM in Yangtze River was supposed to be the inputs of its tributaries. Additionally, in situ water-SPM phase distributions of OCPs indicated that HCHs tended totransport with water as well as DDTs was prone to combine with SPM in Yangtze River catchment of Wuhan.     

Concentrations and inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in watershed soils in the Pearl River Delta,China

The concentration levels, source, and inventories of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in 55 surface vegetable soils in the watershed of the Pearl River Delta (PRD) were analyzed and compared with those of the surface sediments in the Pearl River Estuary (PRE) and northern South China Sea (SCS). The 16 priority PAHs on US EPA list range from 58 to 3,077 microg/kg (average: 315 microg/kg). The concentrations of DDTs and HCHs range from 3.58 to 831 microg/kg (average: 82.1 microg/kg) and from 0.19 to 42.3 microg/kg (average: 4.42 microg/kg). The ratios of DDT/ (DDD+DDE) are higher than 2 in majority of the soil samples, suggesting that DDT contamination still exists. The PAH ratios suggest that the source of PAHs is petroleum, and combustion of fossil fuel, biomass, and coal. The average concentrations of PAHs and the linear regression slope between PAHs and TOC for the soils and the sediments are quite similar. It was estimated that the soil mass inventories at 0-20 cm depth are 1,292 metric tons for PAHs and 356 metric tons for OCPs in the studied region. The average PAHs inventory per unit area for the soil samples investigated in PRD is about 0.86 time that of surface sediments in the Pearl River Estuary, and about 2.43 times that of surface sediments in the northern South China Sea. PAHs in the soils in PRD have similar source to those of the surface sediments in PRE. All of those may suggest that PAHs in PRE and SCS are probably mainly inputted from the soils in PRD via soil erosion and river transport.     

Tiered aquatic ecological risk assessment of organochlorine pesticides and their mixture in Jiangsu reach of Huaihe River, China

A tiered approach consisting of several probabilistic options was used to refine aquatic ecological risk assessment (ERA) of individuals and mixture of various Organochlorine Pesticides (OCPs) detected in Jiangsu reach of Huaihe River, China. The tiered approach ranged from determined Hazard Quotient (HQ) to Joint Probability Curve and Monte Carlo simulation based HQ-distribution. The results from all levels of ERA methods in the tiered framework are consistent with each other. The results show that Endrin, o,p'-Dichloro-Diphenyl-Trichloroethane (DDT), alpha-Endosulfan and beta-Endosulfan posed clear ecological risk; p,p'-DDT, p,p'-DDD, Aldrin, Heptachlorepoxide and Methoxychlor posed potential risk; while Hexachlorocyclohexanes, Heptachlor, Dieldrin and Hexachlorobenzene posed negligible risk. Further, based on the concept of total equivalent concentration, combined ecological risk caused by the mixture of all detected OCPs was calculated, and it proved to be significantly higher than the risk caused by any individual OCP. Despite inevitable uncertainties in current ERA, a comprehensive tiered approach can help to get a more credible result of risks of individuals and mixture of hazardous pollutants and screen the major risk pollutants contributing to the combined ecological risk.     

Size distribution and seasonal variations of particle-associated organochlorine pesticides in Jinan, China

The concentrations of organochlorine pesticides (OCPs) in atmospheric particulate matter in Jinan, China, over the period from July 2009 to June 2010, were determined to study their pollution levels, compositions, size distribution and seasonal variations. All target compounds except endosulfan sulfate were detected. The annual average concentration of ∑18 OCPs was 92 ± 82 pg m(-3). Total HCH, total endrin, aldrin, endosulfan compounds and total DDT compounds were the primary components, accounting for approximately 27%, 20%, 16%, 14% and 10% of total OCPs, respectively. The annual mean ng g(-1) concentrations of ∑18 OCPs in PM(2.5), PM(5), PM(10) and TSP were 481 ± 190, 433 ± 161, 414 ± 158 and 264 ± 193, respectively, indicating that most OCPs tend to be strongly absorbed by fine air particles which were strongly related to a potential health risk. Distinct seasonal trends were found in OCPs concentrations with high concentrations appearing in November and March whereas low concentrations appeared in the summer, which were significantly positively correlated with particulate mass concentrations and Air Pollution Index (API). The high OCPs levels could be attributed to the seasonal usage, long-range atmospheric transport as well as adverse meteorological conditions.     

Levels and distribution of PCDD/Fs, dl-PCBs, and organochlorine pesticides in sediments from the lower reaches of the Haihe River basin, China

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and organochlorine pesticides (OCPs) in surface sediments from the lower reaches of the Haihe River basin, northern China, were determined by high-resolution gas chromatograph–high-resolution mass spectrometer. The concentrations of 2,3,7,8-substituted PCDD/Fs, dl-PCBs, and total OCPs [sum of hexachlorobenzene, hexachlorocyclohexanes, and dichlorodiphenyltrichloroethane (DDTs)] in 17 sediment samples were in the ranges of 11.6–1,180,924 pg/g dry weight (dw), 18.7–50,017 pg/g dw, and 1.7–35,280 ng/g dw, respectively. The contamination levels in the samples varied significantly between the different sites. Abnormally high concentrations of PCDD/Fs, dl-PCBs, and some OCPs were found in sediments from the lower reaches of the main channel of the Haihe River and the Dagu Drainage River, which were attributed to the historical production of pentachlorophenol and other pesticides near these locations. High levels of DDTs were detected in the Yongding New River sediment, which were likely to have originated from the discharge of wastewater from a dicofol factory upstream. In samples taken from other sites, the concentrations of these pollutants were at levels comparable to those documented in other areas of China. This preliminary investigation suggests that historical pesticide production in the Haihe River basin has contributed significantly to the contamination of this aquatic ecosystem and that further attention to this issue is warranted.     

Residues and ecological risks of organochlorine pesticides in Lake Small Baiyangdian, North China

The levels of hexachlorocyclohexane (HCH) and dichloro-diphenyl-trichloroethane (DDT) in the water, suspended particulate matter (SPM), and sediments from Lake Small Baiyangdian were measured by gas chromatograph with a ⁶³Ni microelectron capture detector. The residual levels of the total HCHs in the water, SPM, and sediments were 1.59?±?2.24 ng L^?1, 25.42?±?1.72 ng g^?1 dw (dry weight), and 0.86?±?1.44 ng g^?1 dw, respectively. DDTs were not detected in the water samples. The concentrations of total DDTs were 158.79?±?1.67 ng g^?1 dw in SPM and 0.46?±?1.97 ng g^?1 dw in the sediments. Compared to other areas in China and abroad, the levels of residual HCH and DDT were relatively low in the water and sediments, but they were moderate to high in the SPM. Organic carbon partition coefficient values for HCH in this study were higher than previously published values and may reflect new input in this area. The residual HCHs in this area could be derived from a mixture of technical HCH and lindane because ongoing lindane use may be occurring. DDT in the majority of the study area was primarily attributed to historical discharge, but some regions may be receiving new input. The ecological risks of γ-HCH in the water were very low according to species sensitivity distribution models. The concentrations of HCH and DDT in the sediments from the study area did not exceed the sediment quality guidelines, which indicate little risk for benthic organisms.     

Assessment of organochlorine pesticides and plasticisers in the Selangor River basin and possible pollution sources

A study on the quality of water abstracted for potable use was conducted in the Selangor River basin from November 2008 to July 2009. Seven sampling sites representing the intake points of water treatment plants in the basin were selected to determine the occurrence and level of 15 organochlorine pesticides (OCPs), six phthalate esters (PAEs) and bisphenol A (BPA). Results indicated OCPs were still detected regularly in 66.1 % of the samples with the Σ₁₅OCPs ranging from 0.6–25.2 ng/L. The first data on PAEs contamination in the basin revealed Σ₆PAEs concentrations were between 39.0 and 1,096.6 ng/L with a median concentration of 186.0 ng/L while BPA concentration ranged from <1.2 to 120.0 ng/L. Although di-n-butyl phthalate was detected in all the samples, concentrations of di-ethyl(hexyl)phthalate were higher. Sampling sites located downstream recorded the highest concentrations, together with samples collected during the dry season. Comparison of the detected contaminants with the Department of Environment Water Quality Index (DOE-WQI) showed some agreement between the concentration and the current classification of stream water. While the results suggest that the sites were only slightly polluted and suitable to be used as drinking water source, its presence is cause for concern especially to the fragile firefly “Pteroptyx tener” ecosystem located further downstream.     

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p ^′-DDT, o,p ^′-DDT, p,p ^′-DDE, p,p ^′-DDD, α-, β-, γ-, and δ-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g^???1 (mean, 1.02 ng g^???1) for ∑DDT, 0.09–12.89 ng g^???1 (mean, 1.08 ng g^???1) for ∑HCH. The concentration distribution of ∑DDT and ∑HCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while β-HCH and γ-HCH significantly dominated in the sediments for HCHs.     

Pollution by organochlorine pesticides in Navachiste-Macapule,Sinaloa, Mexico

The lagoon system of Navachiste-Macapule is located in northern Mexico, in the state of Sinaloa, with an area of 24,000 ha. The main economic activity in the area is agriculture, and the lagoon lies next to the irrigation district ID-063 which covers 116,615 ha. The purpose of this study is to evaluate the levels of pollution generated by organochlorine pesticides (OC) in the surface sediments of the lagoon and in the agricultural drains of the ID-063 that are supposedly transported into the system as a result of agricultural activities and runoff from adjacent land. For this, between 2006 and 2007, 45 surface sediment samples were collected (warm dry, rainy and cold dry) from 15 sampling sites, during the three climatic seasons. Of these, eight were located inside the lagoon in marine conditions (salinity >31 PSU) and seven in the agricultural drains of the ID-063 in freshwater conditions (salinity <5 PSU). The average concentration of the OC in the sediments was 44.75 ng g^− 1, among which the group of the alicyclic compounds presented the greatest concentrations. The average value of the total organic carbon (TOC) in the sediments of the system was 0.90%. The sediments collected inside the lagoon had an average OC concentration of 18.97 ng g^− 1, and the predominant type of sediment was fine to very fine sand. The average OC concentration in the sediments collected in the agricultural drains was 75.69 ng g^− 1, where fine sediments (silt) were predominant. The presence of methoxychlor, endrin and heptachlor suggested that these compounds were continuously used in the system, even though their use is forbidden in Mexico.     

Distribution and bioaccumulation of organochlorine pesticides (OCPs) in food web of Nansi Lake,China

The concentration of 12 organochlorine pesticides (OCPs) were measured in water, sediment, aquatic plant, and animal (shrimp and fish) of Nansi Lake by gas chromatography equipped with an electron capture detector. The total OCPs concentrations were 65.31–100.31 ng L^?1 in water, 2.9–6.91 ng g^?1 dry weight (dw) in sediments, 1.29–6.42 ng g^?1 dw in aquatic plants and 7.57–17.22 ng g^?1 dw in animals. The OCPs composition profiles showed that heptachlor compounds was also the predominant OCPs contaminants in addition to hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in Nansi Lake. According to the source of HCHs and DDTs in sediment samples, there was no new input and the HCHs pollution mainly came from the use of Lindane in Nansi Lake. Bioaccumulation of OCPs in aquatic biota indicated that DDTs and heptachlor compounds had a strong accumulation, followed by HCHs and drins. The accumulation abilities of fish for OCPs were higher than those of plants and shrimps. The OCPs biota-sediment accumulation factor values of Channa argus was the highest in fish samples, followed by Carassius auratus, and Cyprinus caspio. Risk assessment of sediment showed that heptachlor epoxide had a higher occurrence possibility of adverse ecological effects to benthic species. Based on the calculation of acceptable daily intake and hazard ratio, HCHs in fish and shrimps from Nansi Lake had a lifetime cancer risk of greater than one per million. The risk assessment of water, sediment, and fish indicated the water environment of Nansi Lake is at a safe level at present.     

Occurrence of organochlorine pesticides in indoor dust

Organochlorine pesticides are present in the environment and suspected of causing serious health effects. Diet has been the main exposure source, but indoor source release is gaining focus. Within a monitoring study of polychlorinated biphenyls of Danish buildings built during the 1960s and 1970s, we coincidently determined extreme levels of dichlorodiphenyltrichloroethane (DDT) levels in two of ten random samples. This raises concern and further large scale investigations are warranted to confirm this.     

The distribution of organochlorine pesticides (OCPs) in surface sediments of Bohai Sea Bay,China

The residues of organochlorine pesticides (OCPs) in 19 surface sediments of Bohai Sea Bay were determined in this study. Total OCP concentration in surface sediment ranged from 9.01 to 18.04 ng/g dry weight, with a mean concentration of 12.50 ng/g. These findings are in the mid-range of pesticide concentrations compared to those reported in other regions worldwide. DDTs and HCHs were the predominant species. The α-HCH/β-HCH ratios and the predominant γ-HCH indicate that the technical HCH contamination was due mainly to historical usage, although there appeared to be a fresh input of lindane. The results from \(\left( {\mbox{DDD}\,\mbox{+}\,\mbox{DDE}} \right)\mbox{/}\sum {\mbox{DDTs}} \) and DDD/DDE calculations suggest that the usage of DDT in agricultural activities was not terminated, and the historical/fresh inputs of DDT in these areas could be more easily degraded into DDD under an anoxic condition. PCA implies that the recent usage of DDT could serve as important fresh input sources for OCPs.     

Trends of organochlorine pesticides in drinking water supplies

The effectiveness of the treatment process for the removal of pesticides in the final water supplies in Delhi has been evaluated. Samples were collected during 2000–2005 from five water treatment plants (WTPs). Analysis was carried out to identify pesticides, which are more commonly encountered in treated drinking water. In most of the treatment plants, the concentrations of lindane, total endosulphan and total DDT were significantly less in the finished water. Monitoring of these less soluble pesticide in the finished water from WTPs was done quarterly to arrive at the quality trends and to plan for the mitigation action, in case the concentration of the parameter exceeded at any site or time.     

Monitoring of organochlorine pesticides in and around Keoladeo National Park, Bharatpur, Rajasthan, India

Keoladeo National Park (KNP) is an important wintering ground for thousands of birds that undertake a perilous journey over the Himalaya to make a seasonal home in a wetland ecosystem. However, this wetland is now getting polluted by various types of contaminants such as pesticides because of the agricultural practices in the catchment area from where the park receives water. Keeping this in mind, the present study has been undertaken to assess the organochlorine pesticide (OCP) residues in the sediments inside and around KNP. Samples were collected from the different blocks of the park. The concentrations of α-HCH, β-HCH, γ-HCH, δ-HCH, S-HCH, aldrin, dieldrin, heptachlor, hept.epoxide, endosulfan-I, endosulfan-II, endo.sulfate, S-endosulfan, endrin, 4,4'-DDE, 4,4'-DDD, and DDT were quantified using gas chromatography with electron capture detection. Analysis showed that the samples were contaminated with the above mentioned pesticides and that the concentration of total OCPs in the sediments varied from 0.1173 (dieldrin) to 5.558 ppm (γ HCH) in the samples collected from inside the park, whereas a range of pesticides varying in concentration from 0.1245 (4,4'-DDD) to 7.54 ppm (γ HCH) was found in samples from outside the park. Residues of S-HCH and S-endosulfan were not detected in any of the sediment samples. The occurrence of pesticides inside the park is a major threat to the park's biodiversity. Eco-friendly agriculture practices with minimal use of inorganic chemicals are suggested to minimize the pesticide residue levels in the park.