Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Polybrominated diphenyl ethers and organochlorine pesticides in sewage sludge of wastewater treatment plants in China

The concentrations of chemicals in sewage sludge from wastewater treatment plants (WWTPs) may relate to their levels of use and environmental pollution in the region. In this work, sludge samples were collected from 31 WWTPs in 26 cities in China and analyzed for polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs). The concentrations of SigmaPBDE (sum of congeners 17, 28, 47, 66, 71, 85, 99, 100, 138, 153, 154, and 183) ranged from 6.2 to 57ng/g (dw). The concentration of decabromodiphenyl ether (BDE-209) ranged from below limit of detection (LOD) to 1109ng/g (dw) (with a median of 27ng/g (dw)), and averaged 55% (median 69%) of the total PBDEs. These levels are about 10-100 times lower than those found in Europe and North America. PBDE levels in sludge were not found to depend on the location and capacity of the WWTPs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from below detection limit to 167ng/g (dw), 11 to 1065ng/g (dw), and 7.5 to 319ng/g (dw), respectively. The major DDT degradation products were p,p'-DDE and p,p'-DDD. The major hexachlorocyclohexane (HCH) isomer in sludge is beta-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers.     

Influence of the application of sewage sludge on the degradation of pesticides in the soil

A study was made of the influence of the application of sewage sludge on the degradation of pesticides in the soil. Two kinds of sludge were used, with different characteristics, one from an urban treatment plant and one from a food processing plant. Three organophosphorus insecticides, fenitrothion, diazinon and dimethoate, were studied. The relative importance was determined of the chemical and biological degradation processes, which involved experiments on soil and sterile soil samples. A comparative study was also made of the degradation of pesticide residues and the evolution of the microbial population. The application of sludge seems to have a complex effect on the degradation of pesticides, determined by the bioavailability and biodegradability of their active ingredient. The biodegradation of pesticide residues brings about alterations in the microorganism population of the soil.     

Accumulation of organochlorine pesticides and polychlorinated biphenyls in sediments, aquatic organisms, birds, bird eggs and bat collected from South India

Concentrations of polychlorinated biphenyls (PCBs), DDT and its metabolites (DDTs), HCH isomers (HCHs), chlordane compounds (CHLs) and hexachlorobenzene (HCB) were determined in sediment, soil, whole body homogenates of resident and migratory birds and their prey items (including fish, green mussel, snail, earthworm, crabs, prawn, lizard and frogs), bird eggs and bats collected from southern India during 1995 and 1998. Accumulation pattern of organochlorines (OCs) in biota was, in general, in the order, HCHs > DDTs > PCBs > CHLs = HCB. Magnitude of OC concentrations increased in the order of sediments < green mussel < earthworm < from < lizard < fish < bird egg < bats < birds tissues. Biomagnification features of OCs were examined in resident and migrant birds to evaluate the exposure levels of these chemicals in wintering grounds of migrant birds. Accumulation of DDTs in migratory birds during wintering in India may be of concern due to the great biomagnification potential of DDTs. Eggs of some resident species contained noticeable concentrations of OCs. Concentrations of OCs in three species of bats analyzed in this study were lower than that found in passerine birds. In addition to OCs, butyltin compounds were also detected at low concentrations in bats.     

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.     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Adsorption/desorption of copper by a sandy soil amended with various rates of manure, sewage sludge, and incinerated sewage sludge

Organic amendments are sometimes applied to agricultural soils to improve the physical, chemical, and microbiological properties of the soils. The organic fractions in these soil amendments also influence metal reaction, particularly the adsorption and desorption of metals, which, in turn, determine the bioavailability of the metals and hence their phytotoxicities. In this study, a Quincy fine sandy (mixed, mesic, Xeric Torripsamments) soil was treated with 0 to 160 g kg(-1) rates of either manure, sewage sludge (SS), or incinerated sewage sludge (ISS) and equilibrated in a greenhouse at near field capacity moisture content for 100 days. Following the incubation period, the soil was dried and adsorption of copper (Cu) was evaluated in a batch equilibration study at either 0, 100, 200, or 400 mg L(-1) Cu concentrations in a 0.01M CaCl2 solution. The desorption of adsorbed Cu was evaluated by three successive elutions in 0.01M CaCl2. Copper adsorption increased with an increase in manure rates. At the highest rate of manure addition (160 g kg(-1) soil), Cu adsorption was two-fold greater than that by the unamended soil at all rates of Cu additions. With increasing rates of Cu additions, the adsorption of Cu decreased from 99.4 to 77.6% of Cu applied to the 160 g kg(-1) manure amended soil. The desorption of Cu decreased with an increase in rate of manure amendment. Effects of sewage sludge amendments on Cu adsorption were somewhat similar to those as described for manure additions. Likewise, the desorption of Cu was the least at the high rate of SS addition (160 g kg(-1)), although at the lower rates there was not a clear indication of the rate effects. In contrast to the above two amendments, the ISS amendment had the least effect on Cu adsorption. At the highest rate of ISS amendment, the Cu adsorption was roughly 50% of that at the similar rate of either manure or SS amendments, across all Cu rates.     

Transport and fate of organic wastes in groundwater at the Stringfellow hazardous waste disposal site, southern California

In January 1999, wastewater influent and effluent from the pretreatment plant at the Stringfellow hazardous waste disposal site were sampled along with groundwater at six locations along the groundwater contaminant plume. The objectives of this sampling and study were to identify at the compound class level the unidentified 40-60% of wastewater organic contaminants, and to determine what organic compound classes were being removed by the wastewater pretreatment plant, and what organic compound classes persisted during subsurface waste migration. The unidentified organic wastes are primarily chlorinated aromatic sulfonic acids derived from wastes from DDT manufacture. Trace amounts of EDTA and NTA organic complexing agents were discovered along with carboxylate metabolites of the common alkylphenolpolyethoxylate plasticizers and nonionic surfactants. The wastewater pretreatment plant removed most of the aromatic chlorinated sulfonic acids that have hydrophobic neutral properties, but the p-chlorobenzene-sulfonic acid which is the primary waste constituent passed through the pretreatment plant and was discharged in the treated wastewaters transported to an industrial sewer. During migration in groundwater, p-chlorobenzenesulfonic acid is removed by natural remediation processes. Wastewater organic contaminants have decreased 3- to 45-fold in the groundwater from 1985 to 1999 as a result of site remediation and natural remediation processes. The chlorinated aromatic sulfonic acids with hydrophobic neutral properties persist and have migrated into groundwater that underlies the adjacent residential community.     

Residues of organochlorine pesticides in environmental samples from the Shatt al-Arab River, Iraq

Application of high resolution gas chromatography has confirmed relatively low residue levels of sumDDT, endrin and dieldrin in the Shatt al-Arab River. Thus, average concentration of these compounds in the edible portion of the cyprinid (Barbus xanthopetrus) were 21, 4 and 2 microg kg(-1) wet weight respectively. Mean values of sumDDT, endrin and dieldrin in surface sediments were 5, 40 and 20 microg kg(-1) dry weight respectively. Shrimps sampled from the Shatt al-Arab River were found to contain residues of o, p'-DDD only (average concentration was 2 microg kg(-1) wet weight). However, comparison of these samples with those from an area affected directly by a point source of organochlorine pesticides has shown that the cyprinid of the same age group contained significantly higher residue levels (average concentrations of sumDDT, endrin and dieldrin were 166, 20 and 7 microg kg(-1) wet weight respectively). Thus, it may be concluded that there was no direct input of organochlorine pesticides to the Shatt al-Arab River, and transportation via the natural processes, such as drainage, appeared to be the sole source. Based upon the observation that the original compound (p,p'-DDT) has not been detected in this river, it has also been concluded that there was no recent contribution of DDT here. Relatively higher residue levels of sumDDT, endrin and dieldrin were encountered in the muscles of the Indian shad captured from the Shatt al-Arab River (average concentrations were 163, 80 and 28 microg kg(-1) wet weight respectively). However, these elevated values were attributed to this fish being migratory and it being exposed to these pesticides elsewhere.     

Distribution of organochlorine pesticides in seawater of the Bering and Chukchi Sea.

Organochlorine pesticides (OCPs) in the seawater collected in the Bering and Chukchi Seas during the First Chinese Arctic Research Expedition were confirmed by gas chromatography-mass spectrometry (GC-MS) and analyzed by capillary gas chromatography with micro-electron capture detector (GC-microECD). The average of hexachlorocyclohexanes (HCHs; sum of isomers alpha-, beta-, gamma-, delta-) was nearly equal in the Bering Sea (mean concentration 412.7 pg/l) and in the Chukchi Sea (mean concentration 445.8 pg/l), which showed no obvious latitudinal difference of these two regions. Compared with previously reported studies, concentrations of OCPs in these regions were much lower than the levels in the last decades. The ratio of alpha:gamma HCH was 5.0 and 3.4 for the Bering and Chukchi sea, respectively, which indicated the different pesticide composition in these two regions. Many other OCPs with different residue patterns were also found for the first time in the investigation regions. Heptachlor epoxide (in the Bering Sea) and heptachlor (in the Chukchi Sea) were main OCPs contaminants besides HCHs.     

Distribution characteristics of organochlorine pesticides in surface and vertical sediments from the Zha Long Wetland, China

Introduction

The Zha Long Wetland, the first water bird conservation area in China, lies on the northern bank of the Song Nen Plain with an area of 2,100 km². In many areas of the Zha Long Wetland, water pollution has led to a decrease in the wetland??s ecological function, vegetation degradation, a decrease in the number of bird species, and the depletion of fish resources.

Materials and methods

The sediments used in this study were collected from the surface sediment of seven sites and from different depths in three types of marshes in the Zha Long Wetland in northeast China in late October 2006. The levels and distribution patterns of 17 organochlorine pesticides (OCPs; ??-HCH, ??-HCH, ??-HCH, ??-HCH, p,p??-DDE, p,p??-DDD, p,p??-DDT, endosulfan I, endosulfan II, endosulfan sulfate, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, and methoxychlor) in surface sediments as well as hexachlorocyclohexane (HCH) and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) in vertical sediments were investigated.

Results and discussion

The concentrations of HCHs, DDTs, endosulfans, heptachlors, aldrin, and methoxychlor in surface sediments ranged from 10.44 to 41.97 ng/g, nd (undetectable levels) to 211.88 ng/g, nd to 69.89 ng/g, nd to 28.10 ng/g, 9.81 to 623.83 ng/g, and from nd to 3.99 ng/g, respectively. The highest levels of OCPs were detected in Tangtugangzi at a total concentration of 727.72 ng/g, where the dominant compound was endrin at a concentration of 483.04 ng/g. In the vertical sediments, the HCHs and DDTs were in the ranges of nd?C136.00 and nd?C214.06 ng/g, respectively.

Conclusions

Different distributions of HCHs, DDTs, and other OCPs indicated that they originated from different contamination sources. Composition analyses in surface sediments indicated recent OCP usage or discharge at some sample sites in the Zha Long Wetland.     

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.     

Concentrations,distributions, sources,and risk assessment of organochlorine pesticides in surface water of the East Lake,China

East Lake resides in the urban area of Wuhan City and is the largest urban lake in China. The concentrations of 16 organochlorine pesticides (OCPs) were analyzed in 108 surface water samples collected from the East Lake. The total concentrations of OCPs ranged from not detected to 120 ng L^?1 with predominance of δ-HCH, heptachlor, and α-HCH. The mean values of HCHs and DDTs were 7.40 and 5.70 ng L^?1, respectively, accounting for 40 and 31 % of the total OCPs. For the five lakelets in East Lake, Houhu Lake exhibited the highest concentrations of HCHs, DDTs, and total OCPs, which has been used actively for fisheries and surrounded by suburban rural areas and farmlands. Historical lindane or technical HCH input was probably the source of HCH, while technical DDTs might be the source of DDT in the East Lake. The ratio between heptachlor and its metabolic products indicated recent input of heptachlor. Although the combining ecological risks for all aquatic species in the East Lake calculated by species sensitivity distribution reached approximately 10^?5, the OCPs in the East Lake had slight effects on aquatic organisms. The carcinogenic risks and non-carcinogenic hazard indices of DDTs and HCHs indicated that water in the East Lake was not suitable as water sources for human. However, the results indicated the water quality was safe for people to swim in the urban lake.     

Immunologic effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides in Japanese infants

Effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides on lymphocyte subsets were investigated in the peripheral blood from 101 Japanese infants with approximately 10 months of age. Perinatal exposure to these organochlorine compounds were estimated by their contamination levels in the breast milk of the mothers. Lymphocyte subsets such as CD16+, HLA-DR+, CD4+, CD4+8+, CD8+, CD3+ and CD20+ cells in peripheral venous blood were assessed in a subgroup of 92 infants. Greater exposures to HCE, chlordane and dioxins were significantly associated with the increase in the percentages of CD8+ and CD3+ T lymphocytes and CD4+/CD8+ T cell ratios, respectively. In addition, higher HCH exposure was also associated with a decrease in the percentage of HLA-DR+ T lymphocytes. Furthermore effects of dioxins, DDT and PCBs on the percentage of CD16+ T lymphocyte were more pronounced by the combined exposure of dioxins and PCBs or by the combined exposure of DDT and PCBs. Effects of HCE on the percentages of CD8+ T lymphocyte were also more pronounced by the combined exposure of HCE and chlordane. In conclusion, our study suggests that greater exposures to dioxins, PCBs and organochlorine pesticides determined in this study (except dieldrin) influence the immune system of Japanese infant, although the clinical significance of these changes is uncertain.     

Review on the use of enzymes for the detection of organochlorine, organophosphate and carbamate pesticides in the environment

Pesticides are released intentionally into the environment and, through various processes, contaminate the environment. Three of the main classes of pesticides that pose a serious problem are organochlorines, organophosphates and carbamates. While pesticides are associated with many health effects, there is a lack of monitoring data on these contaminants. Traditional chromatographic methods are effective for the analysis of pesticides in the environment, but have limitations and prevent adequate monitoring. Enzymatic methods have been promoted for many years as an alternative method of detection of these pesticides. The main enzymes that have been utilised in this regard have been acetylcholinesterase, butyrylcholinesterase, alkaline phosphatase, organophosphorus hydrolase and tyrosinase. The enzymatic methods are based on the activation or inhibition of the enzyme by a pesticide which is proportional to the concentration of the pesticide. Research on enzymatic methods of detection, as well as some of the problems and challenges associated with these methods, is extensively discussed in this review. These methods can serve as a tool for screening large samples which can be followed up with the more traditional chromatographic methods of analysis.     

Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003

In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.     

Occurrence,spatial distribution,source, and ecological risk assessment of organochlorine pesticides in Dongting Lake,China

Environmental Science and Pollution Research - The occurrence, distribution, sources, and ecological risks of organochlorine pesticides in Dongting Lake of China were investigated. The average...     

Recent levels of organochlorine pesticides and polychlorinated biphenyls in sediments of the sewer system in Hanoi, Vietnam

The occurrence, temporal trend, sources and toxicity of PCBs and organochlorine pesticides were investigated in sediment samples from the sewer system of Hanoi City, including the rivers Nhue, To Lich, Lu, Set, Kim Nguu and the Yen So Lake. In general, the concentrations of the pollutants followed the order DDTs > PCBs > HCHs (β-HCH) > HCB. However, the pollution pattern was different for the DDTs and PCBs when the sampling locations were individually evaluated. The concentrations of the DDTs, PCBs, HCHs, and HCB ranged from 4.4 to 1100, 1.3 to 384, <0.2 to 36 and <0.2 to 22 ng/g d.w., respectively. These levels are higher than at any other location in Vietnam. Compared to measurements from 1997, the DDTs, PCBs, β-HCH and HCB levels show an increasing trend with DDT/DDE ratios, indicating very recent inputs into the environment although these persistent compounds are banned in Vietnam since 1995.     

The levels and distribution of organochlorine pesticides (OCPs) in sediments from the Haihe River, China

The levels and distribution patterns of the selected organochlorine pesticides (OCPs=p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD, alpha-, beta-, gamma- and delta-HCH) in surficial sediments from the Haihe River and Dagu Drainage River of Tianjin were investigated by means of gas chromatography coupled with micro-electronic capture detector (GC-microECD). Concentrations of OCPs in the sediments from the Haihe River ranged from 1.88 to 18.76ng g(-1) (mean 7.33ng g(-1)) for sum HCH, 0.32-80.18ng g(-1) (mean 15.94ng g(-1)) for sum DDT. Compared with the Haihe River, the Dagu Drainage River was much more contaminated by HCHs and DDTs, wherein sum HCH ranged from 33.24 to 141.03ng g(-1) (mean 87.74ng g(-1)) and sum DDT ranged from 3.60 to 83.49ng g(-1) with a mean value of 35.52ng g(-1). The concentration distribution of sum DDT and sum HCH was different indicated their different contamination sources. Composition analyses indicated that a recent usage or discharge of HCH and DDT into the Dagu Drainage River.