Characteristics and risk assessment of organochlorine pesticide residues in surface sediments collected at the Qingshitan Reservoir

ABSTRACT

An ultrasonic extraction – gas chromatography – electron capture detector analytical method was used to measure the concentration and types of organochlorine (OC) pesticides in sediment to obtain a better understanding of the characteristics and hidden ecological risks associated with OC pesticide exposure in surface sediment of the Qingshitan Reservoir. Fifteen types of OC pesticides were detected in the sediment, and the sum concentration of these chemicals was in the 149.32–490.19 ng/g range (mean value: 319.39 ng/g). The concentrations of detected OC pesticides occurred in the following order: hexachlorohexanes (HCHs) (mean value: 200.17 ng/g) > DDTs (mean value: 36.92 ng/g) > heptachlors (mean value: 32.74 ng/g) > methoxychlor (mean value: 24.13 ng/g). There was a 100% detection rate for HCH isomers, and their concentrations occurred in the following order: β-HCH > δ-HCH > γ-HCH > α-HCH. β-HCH was the main component of HCHs. Ratios between α-HCH/γ-HCH and β-/(α+γ)-HCH were used to investigate the sources of pollution. Most of the surveyed areas were polluted by lindane, which originated from past pesticide residue usage, and no new inputs of HCHs were found. DDT was the major component of the DDTs, and accounted for 52%–87% of the DDTs. The ratios of (DDE+DDD)/DDT at all sample collection points were less than 1, indicating that degradation rate of DDTs in sediment was low and there was a new input of DDTs in these surveyed areas. The ratio of DDD/DDE was less than 1 at most of the sample collection points, indicating that the degradation of DDT in the sediments primarily took place under aerobic conditions. Comparison of OC pesticide residual levels in the underwater sediment collected at the Qingshitan Reservoir to other states and countries showed the pollution level of these chemicals of the Qingshitan Reservoir was relatively high. The ecological risk was assessed based on guideline values of effects range-low (ERL) and effects range-medium (ERM). The results showed that DDD, DDE, DDTs and endrin residues in the sediment posed a moderate ecological risk, but DDT and γ-HCH showed high ecological risk. These OC pesticides might adversely affect biological systems, and need to be addressed.     

Occurrence and distribution of organochlorine residues and metals in sediment,water and fish in the catchment area of lake baiyangdian,china

The occurrence and distribution of metals (Al, Cd, Cr, Cu, Pb, Zn), organochlorine residues (HCH, DDT and metabolites, PCBs) and EOC1 (extractable organic bound chlorine) were monitored in 1993 and 1996 in sediment, water and fish in the catchment area of Lake Baiyangdian, China. The levels of the metals, especially Cd and Zn, were significantly higher in the sediment than those in non‐polluted areas. PCBs and chlorinated pesticides constituted only a minor part (< 8.4%) of the extractable organic bound chlorine, indicating the presence of additional, unknown, organochlorine residues. Among the pesticides, DDT was widely distributed and high levels occurred in fish despite a ban of its production and use in 1983. The low quotient of pp‐DDT/pp‐DDE in sediment and fish indicated that the input of DDT to the catchment area was not of recent origin.     

Dr Gwyneth Dorothy Howells (1925–2009), former Editor in Chief of Chemistry and Ecology

This paper presents the results of the examination of concentrations of chlorinated hydrocarbons in surface sediments from the middle of the Adriatic. the sampling area was chosen as part of the protection programme of the Adriatic Sea and is located at two transverse transects, each consisting of four stations. the sediments were collected during the summer cruise of 1990. Quantification of individual components was performed by Capillary Gas Chromatography (CGC) using reference standards. Areal distribution of the concentrations of HCB, lindane, DDT and its metabolites, dieldrin, endrin and PCBs are presented. the values obtained varied within a wide range of concentration from 20 pg/g dry weight for lindane to 700 pg/g dry weight for Σ DDT and the sum of PCBs as Aroclor 1254 from 0.3 to 6.6 ng/g.

The main source of these compounds is thought to be from suspended matter entering the Adriatic sea via the River Po and transported by currents to its middle part.     

Accumulation of organochlorine insecticides in the blood of the general population of Nigeria

Gas Chromatographic determination of blood levels of organochlorine pesticides in people of Southern Nigeria is described. Among the compounds detected and quantified were the HCH‐isomers, DDT and its metabolites and dieldrin, the major pollutants being DDT, DDE and the HCH‐isomers. Delta‐HCH, HCB and Endrin were also detected in a few samples. Total DDT (DDT + DDE + DDD) ranged from 0.04–7.24 ppm, total HCH (alpha + beta + gamma) 0.08–5.64 ppm, and dieldrin 0.03–0.28 ppm.     

An improved activated carbon method to quantify dichlorodiphenyltrichloroethane (DDT) in surface water

Currently, South Africa is designing a strategy for surface water protection involving organic contaminants such as dichlorodiphenyltrichloroethane (DDT), which is currently used for malaria control in mosquito-infested areas. Here, we demonstrate the successful use of an improved activated carbon technique using dichloromethane instead of chloroform, and slower leaching rate of 15 mL/min to quantify DDT and its metabolites in surface water. The recovery tests for 2,4′DDT, 2,4′DDD, 2,4′DDE, and 4,4′DDT, 4,4′DDD, 4,4′DDE ranged from 75 to 84% and 87 to 96%, respectively (DDE: dichlorodiphenyldichloroethylene, DDD: dichlorodiphenyldichloroethane). The main advantages of this technique over conventional liquid–liquid extractions are reduced amount of organic solvent, little sample preparation, and larger sample throughput. Because activated charcoal is fairly cheap, the technique can be routinely used to quantify and monitor DDT and its metabolites in surface water samples.     

Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

Chlorinated Hydrocarbons in Surface Sediments From the Open Adriatic

This paper presents the results of the examination of concentrations of chlorinated hydrocarbons in surface sediments from the middle of the Adriatic. the sampling area was chosen as part of the protection programme of the Adriatic Sea and is located at two transverse transects, each consisting of four stations. the sediments were collected during the summer cruise of 1990. Quantification of individual components was performed by Capillary Gas Chromatography (CGC) using reference standards. Areal distribution of the concentrations of HCB, lindane, DDT and its metabolites, dieldrin, endrin and PCBs are presented. the values obtained varied within a wide range of concentration from 20 pg/g dry weight for lindane to 700 pg/g dry weight for Σ DDT and the sum of PCBs as Aroclor 1254 from 0.3 to 6.6 ng/g.

The main source of these compounds is thought to be from suspended matter entering the Adriatic sea via the River Po and transported by currents to its middle part.     

Historical trends of organochlorine pesticides (OCPs) recorded in sediments across the Tibetan Plateau

Sediment cores from four lakes across the Tibetan Plateau were used as natural archives to study the time trends of organochlorine pesticides (OCPs). The total concentrations of dichlorodiphenyltrichloroethane (ΣDDT) and hexachlorocyclohexane isomers (ΣHCH) were in the range of 0.04–1.61 and 0.08–1.88 ng/g based on dry weight (dw), while the input fluxes were in the range of 0.3–236 and 0.7–295 pg/cm²/y in the core sediments, respectively. The input fluxes of ΣDDT and ΣHCH generally peaked in sediment layers corresponding to the 1970s–1990s and peaked in top sediment layers. The ratio of α/γ-HCH decreased in the top layer sediments, implying that the contribution of lindane (pure γ-HCH) has been increasing in recent years. In addition, the ratio of o,p′-DDT/p,p′-DDT increased significantly over the last 15–20 years, suggesting that dicofol (characterized by high ratio of o,p′-DDT/p,p′-DDT about 7.0) has recently become a relatively more important source of DDT compared to technical DDT itself. The time trends of OCPs recorded in lake sediments examined the impact on such remote alpine regions by human activities.     

Bioaccumulation of organochlorine contaminants in fish species from Lake Qarun,a protected area of Egypt

The purpose of this study was to determine concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Nile tilapia (Oreochromis niloticus) and Bouri fish (Mugil cephalus) from Lake Qarun, a protected area of Egypt, and evaluate the relative ecological risk of these compounds. Different tissues of the fish species were analyzed for 26 chlorinated pesticides and 29 PCB congeners. Total concentrations (µg/kg wet weight, ww) of OCPs ranged between 1487 and 6217 (mean: 3260) and of PCBs between 9.0 and 61 (mean: 34). The trend of detected organochlorine pollutants was: endrin aldehyde > dieldrin > hexachlorobenzene > PCBs > endrin > 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethanes (DDTs). Heptachlor epoxide; oxy-, cis-, and trans-chlordane; trans-nonachlor; β-hexachlorocyclohexane; δ-hexachlorocyclohexane; and endosulfan I and endosulfan sulfate levels were below the detection limit. The ratios of (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylenes [DDEs] + 1,1-dichloro-2,2-bis(p-chlorophenyl)ethanes [DDDs])/ΣDDTs in fish tissues indicated no recent DDT exposure. Concentrations of DDTs and PCBs were generally comparable or higher than those found in studies of similar species worldwide. The concentrations of hexachlorobenzene, dieldrin, and endrin aldehyde in fish muscles exceeded the maximum residue level recommended by various organizations.     

DDT in fish from the Bulgarian region of the Black Sea

In spite of a worldwide reduction in the utilization of organochlorine pesticides (OCPs), they are still a problem for the aquatic environment and human health. The Black Sea is still being polluted with persistent chemicals, including OCPs. Aquatic organisms (sprat, scad, bluefish, shad, belted bonito, goby, and black mussel) with different feeding behaviours were sampled on a seasonal basis from the Bulgarian region of the Black Sea, and the concentrations of 13 OCP residues were determined. Although many of the OCPs were not detected in the samples, in all samples 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) was present mainly in the form of its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE). Only about 12% of the total DDT was present as the parent compound pp-DDT, which suggests that it was not being used recently in the region. The total DDT concentrations were generally below 150 μg kg^-1 fresh weight, but higher levels—up to 354 μg kg^-1 fresh weight—were also measured for fish species with a high fat content. Between-species differences were observed, even when the concentrations were presented on a fat-level basis. DDT concentrations did not show any significant changes over the 2-yr sampling period. Fish sampled in the northern areas of the Bulgarian Black Sea coast seemed to contain higher DDT levels than those from the southern areas, suggesting a major (historical) influence of the Danube River. For permanent monitoring purposes, the utility of Black Sea gobies and scad should be considered.     

Residues of organochlorinated pesticides in eggs of water birds from Tai Lake in China

The levels of organochlorine compounds in eggs of water birds from the colony on Tai Lake in China were studied. The eggs were collected in 2000 and belonged to the following species: 65 samples of black-crowned night heron (Nycticorax nycticorax), 36 samples of little egret (Egretta garzetta), 26 samples of cattle egret (Bubulcus ibis) from 13 clutches and 43 samples of Chinese pond heron (Ardeola bacchus) from 17 clutches. Dichlorodiphenyltrichloroethane (DDT) and its derivates (DDE and DDD), hexachlorocyclohexane (HCH) and its isomers (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH), heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, alpha-endosulfan, beta-endosulfan, and endosulfan sulfate were determined in the laboratory by gas chromatography. The data showed that DDE had the highest levels in all the samples, followed by beta-HCH. The mean levels of DDE among the water bird species were in the order as follows: black-crowned night heron (5464.26 ng/g, dry weight) > Chinese pond heron (2791.12 ng/g, dry weight) > little egret (1979.97 ng/g, dry weight) > cattle egret (660.11 ng/g, dry weight). DDT and its metabolites accounted for 90% of the total organochlorines, except that it was only 73% for cattle egret. The differences of the residue among the bird species were statistically significant and could be attributed to their variations in prey and habitat. Although the DDE burdens in Tai Lake were much lower than 8 microg/g (wet weight) which are thought to have significant adverse effects on black-crowned night herons, they would be expected to increase the risk of adverse effects on survival of chicks of herons and egrets, particularly black-crowned night heron, based on the critical value of 1 microg/g (wet weight) DDE. The burdens of HCHs in this study were higher and the cyclodienes were lower than those found elsewhere.     

Determination of pesticide residues in muscle of Cyprinus carpio from River Ravi

The levels of dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene (DDE), endosulfan, endosulfan sulfate, carbofuran, and cartap were determined in muscles of Cyprinus Carpio sampled from 10 different sites of River Ravi between Shahdara to Balloki Headworks to assess level of contamination of these pesticides by GC-ECD (gas chromatograph equipped with electron capture detector) method. All fish samples were found contaminated with different concentrations of DDT, DDE, endosulfan, and carbofuran. DDT and DDE concentrations were higher than maximum residue limits (MRL) in food standards, while endosulfan sulfate and cartap were not detected. These findings indicate that pesticide concentrations in fish muscles decreased in the order: DDT > DDE > carbofuran > endosulfan. Furthermore, the sampling sites after Degh fall and beyond Hudiara Nulla Fall river sampling sites were more polluted. It is proposed that constant monitoring programs are needed to assess potential exposure risks.     

Evaluation of organochlorine insecticide residue levels in locally marketed vegetables of Jaipur City,Rajasthan, India

Considerable quantities of organochlorine insecticides are still used worldwide and their persistent residues are widely distributed throughout the environment. Various researchers from different parts of India and abroad have highlighted the extent of pollution caused by these insecticides. In view of the above facts the present study was conducted during 1993-1996 to investigate the magnitude of contamination of organochlorine insecticides in vegetables which were brought for sale to the consumers in the local markets of Jaipur city, Rajasthan, India. Samples of vegetables (potato, tomato, cabbage, cauliflower, spinach and okra) were collected at beginning, middle and end of the seasons with respect to different vegetables and organochlorine levels were assessed using Gas Liquid Chromatograph (GLC) equipped with Electron Capture Detector (ECD). Most of the collected samples were found to be contaminated with residues of DDT and its metabolites (DDD, DDE) isomers of HCH (alpha,beta and gamma-HCH), heptachlor, heptachlor epoxide and aldrin. Some of the detected insecticides exceeded the limit of tolerance prescribed by WHO/FAO.     

珠江八大入海口表层沉积物中DDTs和HCHs残留调查

于2010年8月-2011年5月4次采集珠江八大人海口表层沉积物,采用气相色谱-电子捕获（GC—ECD）法分析沉积物中DDTs（p,P’-DDE、P,P’-DDD、0,P’-DDT、P,P-DDT）和HCHs（α-HCH、β-HCH、γ-HCH、δ-HCH）的污染现状。结果显示,珠江8大人海口表层沉积物中DDTs总含量介于1．02—3．08μg·kg-1之间（以干质量计,下同）,平均值为1．91μg·kg-1;HCHs总含量介于0．21—0．41μg·kg-1之间,平均值为0．31μg·kg-1。DDTs平均含量大于HCHs,其中P,P。DDT对污染的贡献最大,含量范围为ND～7．66μg·kg-1,平均值为2．12μg·kg-1。大部分样点伽（α-HCH）／w（γ-HCH）比值小于3,说明研究区α-HCH大都被降解,或者林丹正取代工业HCHs成为珠江口水环境中HCHs输入的主要来源;甜（DDT）／w（DDD＋DDE）比值大于2,表明沉积物中除早期农药残留外,仍然有新的DDTs类农药输入。     

Polychlorinated biphenyls and organochlorine pesticides in amniotic fluids of pregnant women in south-central Turkey†

The concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were determined in amniotic fluid of 200 pregnant women from the Cukurova region of Turkey. The concentrations of OCPs [hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), dichlorodiphenyl trichloroethane (p,p′-DDT), and various metabolites], and different PCB congeners (28, 52, 101, 118, 138, 153, 180) were determined by gas chromatography with electron capture detection as follows: HCB 6.6 ± 4.7, ΣHCH 21.6 ± 14.2, ΣDDT 12.5 ± 7.5, and ΣPCBs 74.0 ± 54 ng mL^?1. Correlations of maternal or gestational age and levels of OCPs and PCBs were not significant. The levels of these organochlorine compounds (OCs) were below detection limit for 5% of the samples, 80% contained more than one OC. This study illustrates that prenatal exposure of a fetus to OCs is prevalent in the Cukurova region.     

Organochlorine residues in maternal milk from inhabitants of the Thohoyandou area,South Africa

The presence of organochlorine compounds (OC) such as DDT and their metabolites in the environment have created a significant environmental concern over the years due to adverse effects. Consequently, DDT has been banned in many countries. However, it is still used in some countries including South Africa, particularly for vector-borne disease eradication programmes. Since the presence of DDT and its metabolites may provide an indication of the general exposure and use of these compounds, there was a need for such a study. Human breast milk samples (n = 30) were collected from mothers within the age range of 19–40 years from the Thohoyandou area, South Africa. The liquid–liquid extraction method was used to extract DDT and its metabolites from the samples. The crude extracts were subjected to column chromatography for measurements of OC levels. The concentration ranges of the contaminants were as follows: not detected (ND) to1770 ng g^?1 (2,4′-DDE); ND to 3977 ng g^?1 (4,4′-DDE); ND to 3250 ng g^?1 (2,4′-DDD); ND to 2580 ng g^?1 (4,4′-DDD) and ND to 2847 ng g^?1 (4,4′-DDT). The mean ΣDDE, ΣDDD and ΣDDT obtained from the villages were 1180 ng g^?1, 830 ng g^?1 and 690 ng g^?1, respectively. The total DDT ranged from 820–7473 ng g^?1. The estimated daily intake varied from 260 to 4696 ng g^?1, ND-10551 ng g^?1 and ND-4237 ng g^?1 for DDE, DDD and DDT, respectively. These values are significantly higher than the FAO/WHO acceptable daily intake (ADI) of 20 ng g^?1. The ΣDDT was found to decrease with increasing age of the mothers. The observed high levels of DDE compared to DDT indicated chronic exposure of the mothers to DDT, which is metabolized to DDE and retained in the body.     

Organochlorine pesticides and PCBs in sediments from the Yangtse River,China

Organochlorine Pesticides and PCBs pollution levels were determined in sediment samples taken from three sites along the Yangtse River (Nanjing part). The concentrations of various pesticides were in the range of 1.42–8.06 ng/g (t‐HCH), and <0.01–4.12ng/g (t‐DDT), while the concentrations of PCBs were below detection limit at all three sites. The contamination by Organochlorine Pesticides and PCBs in sediments from the Yangtse River was not significant when compared with that reported in the literature from some other countries’ rivers, which may be due to the high flow velocity and water amount of the Yangtse River.     

北京市郊再生水灌区土壤有机氯农药垂向分布特征

在北京市郊再生水灌区采用正三角型布点法进行了3个钻孔的采样工作,钻孔间隔为1m,从表层开始每隔0.5m取一个样,3个钻孔共36组样品,同时采集钻孔附近的灌溉水及地下水,分别测试了土壤的理化参数及其土壤、灌溉水及地下水中9种有机氯农药的质量分数。测试结果表明：表层土壤是有机氯农药的主要残留层,表层土壤中检出的DDTs和BHCs质量分数较高,分别为2814.21ng·kg^-1和1130.41ng·kg^-1,但均符合土壤环境质量一级标准,残留污染程度较轻;其他层位以七氯和艾氏剂为主要检出物,最高质量分数分别为1286.19ng·kg^-1和781.23ng·kg^-1;其中艾氏剂未在表层土壤中检出;灌区内未检出的γ-BHC和（DDE＋DDD）/DDT的计算值为1.80,都说明近期内没有新污染源的输入;检出的有机氯农药在土壤剖面上的迁移能力有HEP〉ALD〉BHCs〉DDTs〉HCB,与地下水中检出的规律一致。     

DDT und Metaboliten in Sedimenten Berliner Gewässer

Sediment samples from rivers and lakes of Berlin (Germany) were analysed for their contamination with organic compounds by means of qualitative and quantitative GC/MS analysis. The principal compounds detected were PAH, organotin derivates, several classes of chlorinated, brominated and mixed halogenated compounds and some of their related metabolites. The DDT metabolites DDD, DDE, DDCN, DDMU and DDMS were the most abundant compounds of halogenated pesticides in a wide range of samples. The main metabolite determined was p,p′-DDD, with concentrations up to 1230 μg/kg dw. The parent DDT compound was detected in only a few samples. The acute cytotoxicity of selected DDT-metabolites was determined with the permanent cell line RTG-2 from the gonads of the rainbow trout (Oncorhynchus mykiss). The results indicate a high cytotoxic potential of these metabolites. The oestrogenic potential was determined by the Dot-Blot/RNase-Protection-Assay an the order from o,p′-DDT>p,p′-DDMS>p,p′-DDMU≥p,p′-DDCN. Risk assessments based on chemical analysis of DDT, DDD and DDE alone is not able to estimate the real toxic potential of DDT and its metabolites. The development of a method for bioassay directed assessment seems to be an effective strategy to solve this problem. Especially scarce or not available data of combinatory effects, differences between different trophic levels and their availability to biota and low knowledge about the metabolism in situ as well as the enantioselective characteristics of most chiral DDT metabolites warrant future analyses.     

Organochlorine Residues in Coastal Birds From the Vellar River Watershed Areas,Parangipettai, Southern India

Organochlorine contaminants (HCHs, DDTs and PCBs) in the muscle tissues of 12 bird species collected from Vellar River watershed areas (S. India) were determined. the accumulation pattern of organochlorine residues in birds of different feeding groups for HCHs and PCBs was: scavengers > inland piscivores > coastal piscivores > insectivores. the pattern for DDTs was: coastal piscivores > scavengers > insectivores > inland piscivores. Scavengers accumulated all the three organochlorines to a higher degree than the other groups of birds. Marked variations in the accumulation pattern by different species and individuals of birds to the same and different organochlorine residues were observed. the differences in the accumulation pattern of residues in different species of birds with similar feeding habits could be attributed to different feeding areas and because migrants are exposed to contaminants in different geographical locations. HCH residues were generally found in higher concentrations than DDTs, reflecting increasing use of HCH pesticides since banning of DDT for agriculture. Levels of PCBs were lower than in birds in developed countries. Results are discussed in relation to future pest control and industrialisation in India.