The level and distribution of selected organochlorine pesticides in sediments from River Chenab,Pakistan

Organochlorine pesticides (OCPs), viz. β-hexachlorocyclohexane (β-HCH), γ-HCH, aldrin, dieldrin, endrin, heptachlor, endosulfan-I, endosulfan-II, heptachlor endoepoxide, heptachlor exoepoxide, mirex, dicofol, o,p′-dichlorodiphenyltrichloroethane (o,p′-DDT), p,p′-dichlorodiphenyltrichloroethane (p,p′-DDT), dichlorodiphenyldichloroethane (DDD), and dichlorodiphenyltrichloroethylene (DDE) and 12 other physicochemical parameters were measured in surface sediments from River Chenab during two sampling seasons (summer and winter, 2007) to evaluate spatial and temporal trends of sediment pollution. Hierarchical agglomerative cluster analysis identified three groups of sites based on spatial similarities in physicochemical parameters and OCP residual concentrations. Spatial discriminant function analysis (DFA) segregated 14 parameters, viz. dicofol, endosulfan-I, heptachlor endoepoxide, dieldrin, DDD, DDE, endosulfan-II, o,p′-DDT, p,p′-DDT, pH, electrical conductivity (EC), Cl⁻¹, total P (%), and silt, which explained 96% of total variance between spatial groups. γ-HCH was the most frequently detected (63%) pesticide, followed by DDD (56%). The ratio of DDTs to their metabolites indicated current input and anaerobic biodegradation. Temporal DFA highlighted aldrin, heptachlor endoepoxide, Cl⁻¹, total P, and EC as important variables which caused variations between summer and winter. DDTs were relatively more prevalent as compared to other OCPs in the sediments samples during both seasons. DDT metabolites were detected at greater frequencies and concentrations in winter, whereas DDT isomers were more prevalent in summer sediment samples. Factor analysis identified agricultural and industrial activities as major sources of sediment OCP contamination. Concentrations of γ-HCH, heptachlor endoepoxide, dieldrin, and DDTs (isomers and metabolites) in all sediment samples were well above interim sediment quality guidelines (ISQGs) and probable effect limits (PEL) given by Canadian Sediment Quality Guidelines (CSQGs).     

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.     

Analysis of the insecticide hexachlorocyclohexane isomers in biological media. A review

Hexachlorocyclohexane (HCH) and lindane were used as insecticides since 1949s. They were progressively banished in most of the nations in the world, because of the their persistence and their potential toxicity and carcinogenicity. They are still occurring in the environment. These insecticides and isomers (α-HCH, β-HCH…) were detected in all media, e.g. soils, sediments, potable water, vegetables, human and animal tissues and air. In this review, we present the synthesis of the analytical procedures and materials used to determine the HCHs isomers in media such as vegetables, human tissues, animals tissues and rations. The analytical techniques which are presented permit to select the best analytical conditions to detect HCHs isomers.     

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.     

Pesticide Residues in Water From River Kaveri,South India

The residue levels of presistent chlorinated pesticides such as HCH (hexachlorocyclo-hexane) isomers and DDT (dichlorodiphenyl trichloroethane) compounds were quantified in water samples collected from the River Kaveri and its distributor River Coleroon in Tamil Nadu, South India. HCH showed higher levels in River Kaveri during premonsoon (July to September) and monsoon (October to December) months, reflecting the HCH usage during that season for paddy crops. But in the case of DDT no clear trend in residue level was observed. the α-HCH was detected as the dominant isomer in all the three sampling sites. Among DDT compounds, p,p'-DDT and p,p'-DDE showed higher percentage of the total. International comparison of residue levels revealed that the present values are comparable to the waters from Asian and South East Asian nations, but lower than some samples from other parts of India. the value of DDT is well below the EEC's maximum acceptable concentration for surface waters and lower than the recommended limit of 2000ng 1^-1 in USA water for protection of aquatic life (Water Quality Criteria, 1972).     

Residues of organochlorine pesticides (OCPs) in aquatic environment and risk assessment along Shaying River,China

Organochlorine pesticides (OCPs) are pesticides with global scale ubiquity, persistence and bioaccumulation, which leave long-term residuals in the water body. OCPs’ high toxicity poses significant threats to human health and aquatic biodiversity, making assessment of OCPs’ impact on aquatic ecology and human health urgently necessary. In this research, the presence of 16 OCPs in surface water and groundwater along Shaying River, China, as well as OCPs concentration correlations, was investigated at 24 selected sampling sites. At the same time, the ecological risk and human carcinogenic risk were also analyzed by risk quotient method and USEPA’s Risk Assessment Guidance, respectively. Results showed that the total concentration of OCPs ranged from 21.0 to 61.4 ng L^?1 in groundwater, and 12.3–77.5 ng L^?1 in surface water. Hexachlorocyclohexane (HCHs) and heptachlor were the prominent contaminants in groundwater, which indicated their use in the recent past and confirmed their persistence. The α-HCH/γ-HCH ratios in groundwater confirmed that γ-HCH (lindane) was used as main substitute of technical HCH in the study area. The correlation analysis illustrated that δ-HCH and γ-HCH played a dominant role in HCHs residue. Heptachlor and α-HCH, as well as endosulfan and heptachlor epoxide, had a strongly significant positive correlation, suggesting an associated usage of the two pair OCPs. An extremely high ecological risk for aquatic organism was observed for γ-HCH, heptachlor and dieldrin, while the carcinogenic risks posed by the selected OCPs in surface water and groundwater were all acceptable.     

Dynamic fate modeling of γ-hexachlorocyclohexane in the lower reaches of the Liao River

A QWASI model dependent on temperature is parameterized to describe the long-term fate of persistent organic pollutants (POPs) in the Liao River. The model parameters, namely fugacity capacity, degradation rate, and transfer coefficient, are profoundly affected by temperature. This model is used to simulate the fate of γ-hexachlorocyclohexane (γ-HCH) in the lower reaches of the Liao River from 1998 to 2008. Modeling results show that γ-HCH fugacity capacities in air, water, and sediment increase as temperature decreases, and the transfer and transformation rate coefficients increase as temperature increases. The variations of transfer and transformation parameter D values depend on fugacity capacities, and transfer and transformation coefficients simultaneously. The performance of the model is evaluated by comparing the predicted and observed concentrations in the water and sediment of the Liao River. The predicted values agree well with the observed value in the order of magnitude, in most cases within the factor of 3. It is believed that the model is appropriate for simulating the long term fate of POPs in the Liao River.     

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.     

Organochlorine pesticides in soils around Guanting Reservoir,China

Fifty-six representative samples of topsoil were collected around Guanting Reservoir, which is an important water source for Beijing. Concentrations of the insecticides HCH, DDT, and their metabolites were quantified by use of gas chromatography (GC) with electron capture detection (ECD). Organochlorine pesticides (OCPs) are still present in surface soils in the Guanting area. DDT accounts for about 93% of the total OCP content. Concentrations of α/γ, β/γ, and DDT/DDE are the result not only of historical use, but also of more recent depositions. Statistical analyses, including principal component analysis (PCA) and cluster analysis (CA), revealed associations between concentrations of OCPs and major soil characteristics. Geographical information system (GIS) technology was used to develop maps of the distributions of OCP concentrations. The areas of greatest contamination were primarily in the central part of the study area and were correlated with greater population density, heavier traffic, and more industrial activity.     

青藏高原纳木错流域持久性有机污染物的多介质迁移与归趋模拟

南亚排放的持久性有机污染物(POPs)可随大气传输到青藏高原,然而POPs在高原多介质间的迁移与分配尚不清晰。本研究利用三级逸度模型对4种POPs(六六六α-HCH,滴滴涕p,p'-DDT,菲Phe和苯并芘Ba P)在纳木错流域的迁移与归趋进行了模拟。结果表明,大气沉降是该区域污染物的主要输入过程,而降解损失则是主要的输出途径。就最终归趋而言,土壤是POPs在纳木错流域的重要储库,其存储了大于50%的POPs。此外,湖水和沉积物分别对α-HCH和PAHs具有较强的存储能力。灵敏度分析的结果表明,环境温度、大气中POPs的浓度及其理化性质是影响POPs在环境中分布的关键参数。本研究明确了纳木错流域不同POPs的迁移方向和归趋特征,这将为青藏高原生态安全评估提供科学依据。     

Sediment geochemistry and arsenic mobilization in shallow aquifers of the Datong basin,northern China

Understanding the mechanism of arsenic (As) mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Datong basin in northern China. The bulk geochemistry analysis of sediment samples from three 50-m boreholes drilled specifically for this study at As-contaminated aquifers, the groundwaters of which have an As concentration up to 1060 μg/l, revealed that the average bulk concentrations of major and trace elements of the samples are similar to those of the average upper continental crust. The average As content of the sediment samples (18.7 mg/kg) is higher than that of modern unconsolidated sediments (5–10 mg/kg). Moreover, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments, such as silt and clay. The concentration of NH₂OH–HCl-extracted iron (Fe) strongly correlated with that of extracted As, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. The results of microcosm experiments showed that As mobilization from sediments to groundwater is probably mainly related to changes in the redox conditions, with moderately reducing conditions being favorable for As release from sediments into groundwater.     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Ausbreitungs- und Abbauverhalten von Pestiziden im unterirdischen Wasser unter Boden

Pesticide leaching from subsoil to underground water can be effected through bypass flows and particle-bound-transport. The seepage and ground water zone have a certain barrier effect too, but the sorption and transformation of pesticides is less than in the subsoil. Dissolved and bound organic carbon content is decisive for the migration behaviour of pesticides in seepage and groundwater zone as well. Pesticides are subject to a measurable degradation in these compartments. Metabolites are usually transported faster than pesticides.     

Recent advances in research on cyclic volatile methylsiloxanes in sediment,soil and biosolid: a review

Three cyclic volatile methylsiloxanes (cVMS) were widely used in various processes of production and industrials and frequently added to consumer products. cVMS are continuously released into the environment, causing increasing environmental and human exposing risks. cVMS were investigated in air, water, biogas, soil, sediment, biosolid and organism. Many scholars focused on the occurrence, behaviours, fate and effects of cVMS in environmental matrices all over the world. However, few studies paid attention to the environmental behaviour of cVMS in the solid phase. We assessed their environmental behaviour and fate in soil, biosolid and sediment. High concentrations of cVMS were detected in biosolids. Volatilisation, adsorption and degradation were the major environmental behaviours for cVMS in the solid phase. Although some aquatic organisms showed an appropriate level of bioaccumulation and bioconcentration, there were no obvious evidence of trophic biomagnification in aquatic food webs for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). In addition, cVMS in the environment have not impacted for natural organisms because the concentrations in soil and sediment have not exceeded the maximum no-observed-effect-concentration threshold. Finally, regarding the major environmental behaviour in soil and sediment, suggestions for further study are proposed.     

Spatial variability and temporal trends of HCH and DDT in soils around Beijing Guanting Reservoir,China

Spatial variability and temporal trends in concentrations of the organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT), in surface soils around Beijing Guanting Reservoir (GTR) were studied in 2003 and 2007. Concentrations of the two OCPs in soils around GTR were generally less than reference values set by the Chinese government for the protection of agricultural production and human health. Among the OCPs, β-HCH and p, p′-DDE were the two predominant compounds. This result indicates that the HCH and DDT residues in soils were primarily from historical use. Based on kriging, a spatial distribution of HCH and DDT around the GTR was observed. Spatial variability indicated how HCH and DDT had been applied and been distributed in the past. Between 2003 and 2007, concentrations of HCH and DDT decreased more rapidly in orchard soils than those in fallow soils.     

A mathematical model to estimate nitrate release from ocher pellets applied to anaerobic benthic sediment

A mathematical model was developed to estimate nitrate release from ocher pellets in benthic sediment. Ocher pellets, called “limnomedicine,” consisting of ocher and calcium nitrate were used to suppress phosphorus release from contaminated sediment under anaerobic conditions. The proposed model represents the fate and transport of nitrate released from the pellets, in both the water column and the sediment. Most of the nitrate (83.6%) released from the pellets was consumed in the degradation of organic matter and FeS in the sediment over a period of 12 days. While an increase in pellet dosage helps to accelerate the sediment treatment rate, it also has the effect of increasing the mass of nitrate that diffuses into the water column. Quantitative analysis of these effects using the proposed mathematical model makes it possible to determine the proper pellet dosage based on sediment conditions such as organic matter content.     

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 (-HCH, -HCH, -HCH, -HCH), heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, -endosulfan, -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 -HCH. The mean levels of DDE among the water bird species were in the order as follows: black-crowned night heron (5464.26ng/g, dry weight) > Chinese pond heron (2791.12ng/g, dry weight) > little egret (1979.97ng/g, dry weight) > cattle egret (660.11ng/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 g/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 g/g (wet weight) DDE. The burdens of HCHs in this study were higher and the cyclodienes were lower than those found elsewhere.     

Untersuchungen zur Nachhaltigkeit der Sanierung von Tributylzinnkontaminiertem Hafensediment durch Landablagerung

To allow ships to pass, most harbours have to be liberated from sedimented material. These sediments often contain high concentrations of tributyltin (TBT), which is used as a biocide in antifouling paints. Thus, the problem of a disposal which is acceptable with respect to a minimum risk for humans and the environment arises. The aim of our project was to assess land deposition as an alternative in dealing with TBT-contaminated harbour sediments. Therefore, we followed the biological degradation of TBT under aerobic and anaerobic conditions at different temperatures using defined laboratory experiments, and got important information about the land deposition, performing field measurements including biomonitoring. The biological degradation of TBT is faster under aerobic conditions and with increasing temperature. The half-lives found show the dependency of the degradation rates on the temperature between 5–55°C. The degradation rate determined for water under the same conditions (just biological degradation, without photolysis) is almost 4 times higher than in sediment. The field studies showed degradation rates of a maximum of 10–15% per year in untreated sediment and 30% per year in restacked sediments. We did not observe any interference of released TBT with ground water or surrounding areas. The TBT uptake in plants was low. Based on our results a multidimensional risk evaluation was performed, concerning the TBT and its degradation products dibutyltin (DBT) and monobutylin (MBT) released from the deposition areas. The land deposition appears to be a sustainable solution for dealing with TBT-contaminated harbour sediments.     

Mineralization of particulate organic matter derived from coral-reef organisms in reef sediments of the Gulf of Aqaba

In situ and laboratory incubation experiments in a fringing reef in the Gulf of Aqaba were performed to study degradation rates of particulate organic matter in reef sediments. Coral mucus, clam eggs, and zooxanthellae were used as model particulate organic compounds for these experiments. Aerobic and anaerobic mineralization rates were calculated by dissolved inorganic carbon (DIC) and O₂ fluxes from the sediments under different particulate organic matter additions. Fast enhancement (approximately twofold) of O₂ and DIC fluxes were found with the addition of coral mucus and clam eggs compared with control incubations without addition. Most of the degradation is believed to have occurred anaerobically rather than aerobically (DIC:O₂ ratios were 4.3–28.1). Higher degradation rates of coral mucus and clam eggs were estimated in carbonate sediment than in silicate sediment (1.2–1.6-fold), which was attributed to the different physical and chemical properties of both sediments. Our study shows the significance of the reef sediment as a suitable site for microbial degradation of particulate organic material excreted from different reef community organisms. This may increase the regeneration of nutrients in the reef environment necessary to sustain high biological productivity.     

Assessment of persistent organic pollutants in soil and sediments from an urbanized flood plain area

Polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and phenolic compounds (PCs) are persistent organic compounds. Contamination of these potentially toxic organic pollutants in soils and sediments is most studied environmental compartments. In recent past, studies were carried out on PAHs, OCPs and PCs in various soils and sediments in India. But, this is the first study on these pollutants in soils and sediments from an urbanized river flood plain area in Delhi, India. During 2018, a total of fifty-four samples including twenty-seven each of soil and sediment were collected and analyzed for thirteen priority PAHs, four OCPs and six PCs. The detected concentration of ∑PAHs, ∑OCPs and ∑PCs in soils ranged between 473 and 1132, 13 and 41, and 639 and 2112 µg/kg, respectively, while their concentrations in sediments ranged between 1685 and 4010, 4.2 and 47, and 553 and 20,983 µg/kg, respectively. PAHs with 4-aromatic rings were the dominant compounds, accounting for 51 and 76% of total PAHs in soils and sediments, respectively. The contribution of seven carcinogen PAHs (7CPAHs) in soils and sediments accounted for 43% and 61%, respectively, to ∑PAHs. Among OCPs, p, p’-DDT was the dominant compound in soils, while α-HCH was found to be dominated in sediments. The concentrations of ∑CPs (chlorophenols) were dominated over ∑NPs (nitrophenols) in both the matrices. Various diagnostic tools were applied for the identification of their possible sources in soil and sediments. The observed concentrations of PAHs, OCPs and PCs were more or less comparable with the recently reports from various locations around the world including India. Soil quality guidelines and consensus-based sediment quality guidelines were applied for the assessment of ecotoxicological health effect.