Organochlorine Pesticides In Water Research Articles

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 (SigmaHCH) and total DDTs (SigmaDDT) 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 SigmaHCH and SigmaDDT, 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 to transport (correction of totransport) with water as well as DDTs was prone to combine with SPM in Yangtze River catchment of Wuhan.

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. Beta-HCH, delta-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 alpha/gamma-HCH and (DDE+DDD)/ sigmaDDT in environmental matrix indicated there probably existed new OCPs input of lindane and dicofol into the river.

Accurate quantification of freely dissolved organochlorine pesticides in water in the presence of dissolved organic matter using triolein-embedded cellulose acetate membrane

A novel method is described using triolein-embedded cellulose acetate membrane (TECAM) for accurate determination of the freely dissolved fraction of organochlorine pesticides (OCPs) in waters rich in dissolved organic matter (DOM). The performance of the method was tested with an air-bridge system for extracting OCPs from aqueous solutions with and without humic acid. In addition, the partition coefficients between humic acid and water (K (doc)s) for 20 OCPs were determined by TECAM with negligible depletion extraction. Results show that TECAM predominantly extracts the freely dissolved compounds and its extraction efficiency decreases significantly with an increase in concentration of humic acid in water. The proposed methodology is suitable for facile laboratory K (doc) measurement for moderate to high hydrophobic compounds (log K (ow) > 4). The linear relationship between log K (ow) and log K (doc) obtained in this study agrees well with the results reported earlier. The kinetic uptake rate constants (k (u)s) and TECAM-water partition coefficients (K (TECAM)s) for the 20 OCPs were obtained using the controlled laboratory continuous-flow and static exposure system, respectively. These calibration parameters were used in the field experiment to estimate the freely dissolved concentrations of OCPs in the water of Taihu Lake in China. Our results show that TECAM can be used successfully to determine the freely dissolved OCPs in aquatic environments containing DOM, and the method is particularly suited for long-term water sampling. Figure Schematic diagram of water sampling with a triolein-embedded cellulose acetate membrane (TECAM).

Simultaneous analysis of polychlorinated biphenyls and organochlorine pesticides in water by headspace solid-phase microextraction with gas chromatography–tandem mass spectrometry

Headspace solid-phase microextraction combined with gas chromatography–ion trap tandem mass spectrometry (HS-SPME–GC–ITMS-MS) method has been developed and studied for the simultaneous determination of 15 organochlorine pesticides (OCPs) and 20 polychlorinated biphenyls (PCBs) in aqueous samples. To perform the HS-SPME polydimethylsiloxane (PDMS) (7, 30 and 100 μm film thickness) and polydimethylsiloxane–divinylbenzene (PDMS–DVB) fibers were initially compared on the basis of their absorption capacities for the selected compounds, and PDMS 100 μm film thickness was selected to accomplish the rests of essays. The influence of various parameters on OCPs and PCBs extraction efficiency by HS-SPME was thoroughly studied using GC-electron capture detector (ECD). Parameters such as collision induced dissociation (CID) resonant excitation amplitude and RF storage level were optimized to increase specificity and sensibility for ITMS-MS analysis. The performance of proposed HS-SPME–GC–ITMS-MS methodology with respect to linearity, reproducibility and limit of detection (LOD) was evaluated by water spiked with target compounds. The linear range of most compounds was found to be between 0.01 and 1 ng mL −1 and the limits of detection were between 0.4 and 26 pg mL −1. The reproducibility of the method ( n = 6), expressed as relative standard deviation (RSD), was between 5 and 21%. Finally, developed procedure was applied to determine selected OCPs and PCBs in river water samples in concentration below 0.1 ng mL −1 can be easily carried out with ultra-selectivity and precision.

The Contamination Levels of Organochlorine Pesticides in Water and Sediment Samples in Uluabat Lake, Turkey

The Uluabat Lake is a reservoir of 125 km2 surface area, in the boundaries of Bursa province, Turkey. The results showed that Uluabat Lake was still contaminated by organochlorine pesticides and their residues despite the existence of bans over a long time. Considerable amounts of organochlorine pesticides (HCB, p.p'-DDT, p.p'-DDE, alpha-, beta- and gamma-BHC, Aldrin, Heptachlor epoxide, Endrin, Endosulfan I and II) were detected in water and sediment samples during one-year study in this lake. Samples of water and sediment were collected in different regions, (6 sampling point) of the lake between February 2002 and November 2002. The mean levels of organochlorine pesticides in water and sediments were determined. According to results, it was found that various environs in Uluabat Lake were contaminated by 11 different organochlorine pesticides. Residue analyses showed that higher organochlorine pesticides and their residues were generally more accumulated in the sediment samples.

Determination of pyrethroid, organophosphate and organochlorine pesticides in water by headspace solid-phase microextraction

Simultaneous determination of pyrethroid, organophosphate (OP) and organochlorine (OC) pesticides in water was achieved with headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-electron-capture detection (GC-ECD). The parameters affecting HS-SPME of pesticides from water were optimized, including extraction temperature, sample and headspace volumes, and sodium chloride amounts. The effects of desorption temperature, desorption time, and position of the fibre in the GC inlet were also investigated. Extraction temperature was the most important factor affecting the recoveries of analytes, and the optimized temperature was 96°C. The addition of salt did not increase extraction efficiencies of the pesticides from the water. The optimized desorption conditions in the GC were as follows: desorption time of 10 min; desorption temperature of 260°C; and a 2 cm position of the fibre in the inlet. The method detection limits were in the low-ng/L level with a linearity range of 50–1000 ng/L for the OCs, 50–5000 ng/L for the OP, and 50–20 000 ng/L for the pyrethroids. These data demonstrated that HS-SPME is a sensitive method for the determination of pyrethroid, OC, and OP pesticides in water.

Accumulation of organochlorine pesticides by semipermeable membrane devices using composite complex

Semipermeable membrane devices (SPMDs) were developed for passive in situ monitoring of organochlorine pesticides (OCPs) in aqueous solution in both laboratory and field (Pearl River Delta, China) studies. The device consisted of a thin film of neutral lipid triolein, enclosed in thin-walled tubing made of composite cellulose acetate membrane (CA) supported by linear low density polyethylene (LLDPE) (CAPE). Results from the laboratory and field application indicated that triolein-CAPE (TCAPE) could quickly and efficiently accumulate hydrophobic OCPs in water and uptake equilibrium could reached within 20 h in the laboratory. Some mathematical relationships of TCAPE-water partition coefficient (log K sw), triolein–water partition coefficient (log K tw) and octanol–water partition coefficient (log K ow) were developed under the laboratory conditions. A good correlation of accumulation in TCAPE with r 2 values ranging from 0.55 to 0.86 for individual OCPs ( n = 8) and an excellent correlation of log K sw and log K ow was also obtained under the field conditions. The average OCPs concentration in the surface water could be estimated by measuring OCPs concentration in the device under the field conditions.

Uncertainty associated to the analysis of organochlorine pesticides in water by solid-phase microextraction/gas chromatography–electron capture detection—Evaluation using two different approaches

As the performances of analytical instrumentation are being gradually enhanced, the limits of detection become increasingly lower, allowing more environmental contaminants to be determined in different matrices. Problems emerge when dealing with data from different origins, once the uncertainty of the results is difficult to be compared, especially if its calculation procedure is rather different, as very often happens. Samples of two organochlorine pesticides of somewhat opposite characteristics (lindane and heptachlor, classified as persistent organic pollutants—POPs) were analyzed in aqueous media using headspace solid-phase microextraction (SPME) prior to gas chromatography–electron capture detection (GC–ECD) and this methodology was in-house validated. Detection limits of 0.097 and 0.050 μg l −1, average intermediate precision of 11.6% and 27.5%, and average recovery of 95.6% and 103.0%, for lindane and heptachlor, respectively, were found. In the absence of available interlaboratory studies to assess the reliability of the results, the expanded uncertainty was calculated following two different approaches ( bottom-up/Eurachem and modified top-down) and the results were compared. Globally it was clearly shown that, for both pesticides, the lower the concentration range, the higher the uncertainty associated to the results. Expanded uncertainties estimated by bottom-up/Eurachem approach varied from 51% to 14% for a lindane concentration range of 0.1–1 μg l −1, and from 48% to 24% for a heptachlor range of 0.1–2 μg l −1. Modified top-down approach pointed to 44% (lindane and heptachlor) in the same ranges, meaning that a uniform procedure for uncertainty estimation should be adopted.

Distribution of organochlorine pesticides in surface water and sediments from Qiantang River, East China

The levels of 13 organochlorine pesticides (OCPs) in surface water and sediments from Qiantang River in East China were investigated to evaluate their potential pollution and risks. A total of 180 surface water samples at 45 sampling sites and 48 sediment samples at 19 sampling stations were collected along the river in four seasons of 2005. Soil samples and wet deposition samples were also collected to provide evidence on the source of OCPs pollution. The total OCPs concentrations in surface water and sediments were 7.68–269.4ng/L and 23.11–316.5ng/g-dry weight (dw), respectively. The concentrations of OCPs in sediments were in the range of 8.22–152.1ng/g-dw for HCHs (α-, β-, γ-, δ-HCH), 1.14–100.2ng/g-dw for DDTs (p,p′-DDD, p,p′-DDE, p,p′-DDT o,p′-DDD), 9.41–69.66ng/g-dw for other OCPs (aldrin, diedrin, endrin, heptachlor, heptachlor epoxide). The total OCPs concentrations in soils and wet deposition were 5.04–214.9ng/g-dw and 16.18–242.4ng/L, respectively. Among the OCPs, HCHs, DDTs and heptachlor were the most dominant compounds in the sediments. The dominant OCPs in water were γ-HCH among HCHs, heptachlor among other OCPs and p,p′-DDE among DDTs. Also, different contamination patterns among sampling seasons were found. The concentrations of OCPs in sediment collected in spring were higher than those in summer and autumn. In contrast, the concentrations of OCPs in surface water in summer and autumn were higher among four sampling seasons. Distribution of HCHs, DDTs and other OCPs were different indicating their different contamination sources. The notable contamination was found in Fuchun reservoir. Composition analyses in sediments indicated a recent usage or discharge of lindane into the river.

Determination of 17 Kinds of Banned Organochlorine Pesticides in Water by Activated Carbon Fiber-Solid Phase Microextraction Coupled with GC-MS

Activated carbon fiber (ACF) as extraction fiber for solid-phase microextraction (SPME) and its application for the analysis of banned organochlorine pesticides (OCPs) were investigated. Firstly, ACF was activated by different concentration of zinc chloride, which indicated that ACF activated by 60% zinc chloride had a reasonable specific surface area, pore volume and pore distribution. Secondly, the parameters for the ACF-SPME procedure, the adsorption and desorption conditions, were also optimized when coupled with gas chromatography-mass spectrometry (GC-MS). Thirdly, the ACF-SPME was used to analyze 17 kinds of OCPs in water. The linearity of most pesticides was found to be between 0.2 and 50 microg/l with GC-MS under the selected ion monitoring (SIM) acquisition mode. The limits of detection (LOD) at the sub microg/l were obtained. The work demonstrated here shows that ACF is a promising alternative for the SPME procedure.

Ultratraces analysis of organochlorine pesticides in drinking water by solid phase extraction coupled with large volume injection/gas chromatography/mass spectrometry

This study describes an SPE coupled with large volume injection (LVI) analytical method for the analysis of organochlorine pesticides, BHC (alpha, beta, delta), aldrin, endosulfan (alpha, beta), endrin, dieldrin, and DDT, from aqueous samples. Determination was carried out by GC with MS. The LODs of organochlorine pesticides were determined at 10 ng/L concentration levels, and the results show that SPE-LVI-GC/MS has the potential to accurately determine organochlorine pesticides in water, as it avoids analyte classes in the various steps of a typical extraction procedure.

Determination of organochlorine pesticides and their derivations in water after HS-SPME using polymethylphenylvinylsiloxane-coated fiber by GC-ECD

A porous sol–gel polymethylphenylvinylsiloxane-coated fiber was applied to optimize the headspace solid-phase microextraction (HS-SPME) conditions for the analysis of 11 organochlorine pesticides (OCPs) and their derivations in water. Their determination was carried out using gas chromatography (GC) with electron capture detector (ECD). The method developed was applied to the analysis of lake water samples. Detection limits varied from 0.835 to 13.0 ng/l and relative standard deviations (RSD⩽11.8%) were obtained showing that the precision of the method is reliable. The method also showed good linearity for the tested concentration range with regression coefficients ( R 2) ranging between 0.980 and 0.999. Recoveries for all the analytes ranged from 71.5% to 115.5%. The results demonstrate the suitability of the HS-SPME/GC-ECD approach for the analysis of multi-residue OCPs in water.

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, α-HCH, δ-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=α-HCH+β-HCH+γ-HCH+δ-HCH), the predominance of α-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.

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, α-HCH, δ-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=α-HCH+β-HCH+γ-HCH+δ-HCH), the predominance of α-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.

Development and application of polymer-coated hollow fiber membrane microextraction to the determination of organochlorine pesticides in water

A novel extraction procedure coupled with gas chromatography–mass spectrometric detection for quantification of organochlorine pesticides (OCPs) in water is described. Amphiphilic polyhydroxylated polyparaphenylene (PH-PPP) was synthesized and coated on the surfaces of a porous polypropylene hollow fiber membrane (HFM). Due to the high porosity of the HFM, maximum active surface area to achieve high extraction efficiency is expected. The polymer-coated HFM was used for the extraction of 15 OCPs from water. The extraction efficiency was compared with emerging and established methods such as liquid-phase microextraction (LPME), solid-phase microextraction (SPME) and stir bar sorptive extraction (SBSE) techniques. We term the current procedure as polymer-coated hollow fiber microextraction (PC-HFME). PC-HFME showed good selectivity and sensitivity. Detection limits for OCPs were in the range of 0.001–0.008 μg l −1. The sensitivity and selectivity of the coated HFM could be adjusted by changing the characteristics of the coated PH-PPP film.

Solid-phase microextraction and gas chromatography-electron capture detection analysis of trace organochlorine pesticides in water using novel benzo-15-crown-5 sol-gel coating.

A novel dihydroxy-terminated benzo-15-crown-5 is synthesized and applied to prepare the solid-phase microextraction (SPME) fiber coating with sol-gel technology. Headspace SPME, as a simple, solvent-free method, is applied to the analysis of 16 organochlorine pesticides (OCPs) present at trace levels in a water sample. A homemade crown ether fiber coated with 80- micro m thickness was used for extraction. Analyses are performed using gas chromatography-electroncapture detection. The optimization of the extraction process is studied. Compared with commercially available SPME fibers, polydimethylsiloxane, the new phases show better selectivity and sensitivity toward OCPs. The linear concentrations range from 1 to 1000 ng/L, the detection limits are in the range of 0.01-0.5 ng/L, the recoveries are over 85%, and relative standard deviations are below 7.2% for these OCPs.

Analysis of Organochlorine Pesticides in Water by Novel Activated Carbon Fiber–Solid Phase Microextraction Coupled with Gas Chromatography–Mass Spectrometry

This study describes a fast activated carbon fiber-solid phase microextraction (ACF-SPME) method for determining organochlorine pesticides (OCPs) in water. The pesticides in this study consist of Hexachlorobenzene (HCB) and α-, β-, γ-hexachlorocyclohexanes (HCHs). The optimal experimental procedures for the adsorption and desorption of four OCPs were evaluated. The linearity was obtained with a RSD of 20% for the OCPs studied over a range from 1.0 to 100 µg/L. The limits of detection at ng/L level were achieved with GC-MS under selected ion monitoring (SIM) acquisition mode. The proposed method was applied to the determination of OCPs concentration in tap water. The results have demonstrated the suitability of the ACF-SPME-GC-MS approach for the analysis of multi-residue OCPs in water. Compared to the commercial fiber, ACF has shown its advantages in solvent-resistance, thermal stability, and the cost. The results obtained in this study suggest that ACF is a promising choice in solid phase microextraction.

Determination of organochlorine pesticides in water using microwave assisted headspace solid-phase microextraction and gas chromatography

A coupled technique, microwave-assisted headspace solid-phase microextraction (MA–HS-SPME), was investigated for one-step in situ sample pretreatment for organochlorine pesticides (OCPs) prior to gas chromatographic determination. The OCPs, aldrin, o,p′-DDE, p,p′-DDE, o,p′-DDT, p,p′-DDT, dieldrin, α-endosulfan, β-endosulfan, endosulfan sulfate, endrin, δ-HCH, γ-HCH, heptachlor, heptachlor epoxide, methoxychlor and trifluralin were collected by the proposed method and analyzed by gas chromatography with electron-capture detection (GC–ECD). To perform the MA–HS-SPME, six types of SPME fibers were examined and compared. The parameters affecting the efficiency in MA–HS-SPME process such as sampling time and temperature, microwave irradiation power, desorption temperature and time were studied to obtain the optimal conditions. The method was developed using spiked water samples such as field water and with 0.05% humic acid in a concentration range of 0.05–2.5 μg/l except endosulfan sulfate in 0.25–2.5 μg/l. The detection was linear over the studied concentration range with r 2>0.9978. The detection limits varied from 0.002 to 0.070 μg/l based on S/N=3 and the relative standard deviations for repeatability were <15%. A certified reference sample of OCPs in aqueous solution was analyzed by the proposed method and compared with the conventional liquid–liquid extraction procedure. These results are in good agreement. The results indicate that the proposed method provides a very simple, fast, and solvent-free procedure to achieve sample pretreatment prior to the trace-level screening determination of organochloride pesticides by gas chromatography.

Organochlorine insecticide residues in drinking and ground water in and around Delhi.

A multiresidue method was developed for the estimation of 15 organochlorine pesticides in water. 50 samples of drinking water supplied by the Municipal Corporation to the residential areas of Delhi and 20 ground water samples from nearby villages used for irrigation were monitored for the presence of organochlorine insecticides by the method developed. Although, organochlorine pesticides were detected in the ground water and irrigation water samples, the levels of pesticides were below the Maximum Contaminant Level as prescribed by WHO. No organochlorine insecticides were detected in any of the drinking water samples.

Application of static liquid-phase microextraction to the analysis of organochlorine pesticides in water

Static liquid-phase microextraction, with subsequent analysis by gas chromatography–electron-capture detection, has been applied to extract eight organochlorine pesticides from water. A conventional microsyringe was used to extract analytes from water samples over a concentration range of 0.05–100 μg/l. Factors relevant to the extraction process were investigated. The sensitivity of the method was enhanced with agitation, and increasing the extraction temperature, of the sample solution. Concentration factors of >50-fold were easily achieved within 25 min of extraction. The analytical data exhibited a relative standard deviation (RSD) range of 3.2% (lindane) to 10.7% (methoxychlor) for the eight pesticides; most RSD values were under 7%. Water samples collected from a reservoir, and from tap water in a chemical laboratory were analyzed using the procedure.