Methodological refinements in the determination of 146 polychlorinated biphenyls,including non-ortho- and mono-ortho-substituted PCBs,and 26 organochlorine pesticides as demonstrated in heron eggs

A method for the determination of 146 polychlorinated biphenyls (PCBs), including four non-ortho- and eight mono-ortho-substituted congeners, and 26 chlorinated pesticides is described. The method consists of ultrasonic extraction, Florisil cleanup, HPLC fractionation over porous graphitic carbon (PGC), and final determination with GC/ECD, GC/MS, or both. Two PCB congeners (PCB 30 and PCB 161) and two polybromobiphenyls (2,4',5-tribromobiphenyl and 3,3',4,4'-tetrabromobiphenyl) were used as surrogate standards to evaluate the analytical efficiency. Four PCB congeners, PCB 14 and PCB 159 for the first fraction, PCB 61 for the second fraction, and PCB 204 for the third fraction, were used as internal standards to monitor the GC performance. The retention behavior of PCBs and pesticides on the PGC column are discussed. The method was found to be reproducible, effective, and reliable under the operational conditions proposed and was applied successfully to the analysis of individual PCBs and chlorinated pesticides in black-crowned night heron (Nycticorax nycticorax) egg samples.     

新型液-液微萃取--气相色谱法测定海水中的有机氯农药

本文采用了一种新型的液---液两相微萃取技术作为海水样品前处理方法,对海水中的八种有机氯农药(α-BHC,β-BHC,γ-BHC,δ-BHC,p,p,-DDE,o,p,-DDT,p,p,-DDD,p,p,-DDT)进行萃取、富集和分离,采用配微池电子捕获检测器气相色谱法分析测定。对影响萃取效率的因素进行了优化。结果表明,在优化条件下,六六六、滴滴涕在1.0-100.0μg/L范围内有良好的线性关系,R≥0.9963,检测限为0.004~0.016μg/L。     

Quantitative enzyme-linked immunosorbent assay for determination of polychlorinated biphenyls in environmental soil and sediment samples

An enzyme-linked immunosorbent assay (ELISA) for the quantitative determination of Aroclors 1242, 1248, 1254, and 1260 in soil and sediments was developed and its performance compared with that of gas chromatography (GC). The detection limits for Aroclors 1242 and 1248 in soil are 10.5 and 9 ng/g, respectively. The assay linear dynamic range is 50-1333 ng/g. Cross-reactivity of the assay with 37 structurally related potential cocontaminants in environmental soil samples was examined; none of the chlorinated anisoles, benzenes, or phenols exhibited >3% cross-reactivity, with <0.1% cross-reactivity being the norm. Soil spike recoveries of 107% and 104% were obtained for Aroclors 1242 and 1248, respectively, for a spike level of 5 mg/kg, with corresponding relative standard deviations of 14% and 17%. One hundred forty-eight environmental soil, sediment, and paper pulp samples, obtained from two EPA listed Superfund sites, were analyzed by ELISA and standard GC methods. Samples were extracted for ELISA analysis by shaking with methanol. Additional extractions of the same samples were performed either with supercritical carbon dioxide or by Soxhlet extraction with methanol. ELISA results for both the supercritical fluid and the Soxhlet extracts were in close agreement with the GC results, while the ELISA results for the methanol shake extracts were not. The data for the environmental samples demonstrated the capability of the ELISA to provide accurate results and reinforced the dependence of any detection method, including ELISA, on appropriate extraction procedures.     

Solid-phase microextraction and headspace solid-phase microextraction for the determination of polychlorinated biphenyls in water samples

A solid-phase microextraction (SPME) method has been developed for the quantification of polychlorinated biphenyls (PCBs) in water samples. Parameters such as sampling time, volume of water, volume of headspace, temperature, addition of salts, and agitation of the sample were studied. Because the time for reaching equilibrium between phases takes several hours or days, depending on the experimental conditions, it was necessary to work in nonequilibrium conditions to keep the sample analysis to a reasonable time. The possibility of sampling the headspace over the water sample (HSSPME), instead of immersing the fiber into the water (SPME), was also investigated, and despite the low partition of PCB into the headspace, HSSPME offered higher sensitivity than SPME at 100 °C. The adsorption kinetics for SPME at room temperature, SPME at 100 °C, and HSSPME at 100 °C were investigated and compared. The proposed HSSPME method exhibits excellent linearity and sensitivity. The detection limit was in the sub-ng/L level. This method has been applied to a real industrial harbor water and compared with liquid-liquid extraction. Both techniques offered similar results, but HSSPME was much more sensitive and considerably faster, by eliminating all the manual process intensive sample workup, and reduces solvent consumption entirely. The only drawback was that matrix effects were observed, but with the addition of deuterated surrogates to the sample or the use of a standard addition calibration, accurate quantification can be achieved.     

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 7.68-269.4 ng/L and 23.11-316.5 ng/g-dry weight (dw), respectively. The concentrations of OCPs in sediments were in the range of 8.22-152.1 ng/g-dw for HCHs (alpha-, beta-, gamma-, delta-HCH), 1.14-100.2 ng/g-dw for DDTs (p,p'-DDD, p,p'-DDE, p,p'-DDT o,p'-DDD), 9.41-69.66 ng/g-dw for other OCPs (aldrin, diedrin, endrin, heptachlor, heptachlor epoxide). The total OCPs concentrations in soils and wet deposition were 5.04-214.9 ng/g-dw and 16.18-242.4 ng/L, respectively. Among the OCPs, HCHs, DDTs and heptachlor were the most dominant compounds in the sediments. The dominant OCPs in water were gamma-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.     

Development of a dispersive liquid-liquid microextraction method for the determination of polychlorinated biphenyls in water

A very simple and powerful microextraction procedure, the dispersive liquid-liquid microextraction (DLLME), was used for the determination of the content of 10 polychlorinated biphenyls (PCBs) in water samples, using gas chromatography coupled with electron-capture detection (GC-ECD). The appropriate amount of acetone (disperser solvent) and chlorobenzene (extraction solvent) at the microlevel volume was used for this procedure. The conditions for the microextraction performance were investigated and optimized. The optimized method exhibited a good linearity (R(2)>0.996) over the studied range (0.005-2mugL(-1)), illustrating a satisfactory precision level with R.S.D. values between 4.1% and 11.0%. The values of the detection limit (S/N=3) were found to be lower than 0.002mugL(-1). Furthermore, a large enrichment factor for the analytes (up to a 540-fold) was achieved in a very short time for only a 5.00-mL water sample. The effectiveness of the method towards real samples was tested by analyzing well, river and seawater samples. The relative recoveries of the well, river and seawater samples, which had been spiked with different levels of PCBs were equal to 92.0-114.0%, 97.0-102.0% and 96.0-103.0%, respectively. The attained results demonstrated that DLLME combined with GC-ECD was a fast and inexpensive technique for the PCBs determination in water samples.     

100 kW steam plasma process for treatment of PCBs (polychlorinated biphenyls) waste

Non-transferred DC steam (H₂O) plasma working with 100 kW was applied to minimize production of the toxic byproducts such as dioxins and furans of which formation is not avoidable in the conventional incineration. In the steam plasma process of polychlorinated biphenyl (PCB) mixture waste, content of combustible gas that can be used as gaseous fuel was about 30% based on wet gas. For the mixture of 27% PCB and 73% CCl₄, total toxic equivalent concentration of PCDD/PCDF was about 0.056 ng TEQ/N m³. It is concluded that the steam plasma torch process was more effective for waste-to-energy and hazardous waste treatment than the air plasma torch process injected steam and the conventional incineration process.     

Measurement of selected polybrominated diphenyl ethers, polybrominated and polychlorinated biphenyls, and organochlorine pesticides in human serum and milk using comprehensive two-dimensional gas chromatography isotope dilution time-of-flight mass spectrometry

A new method using comprehensive two-dimensional gas chromatography and isotope dilution time-of-flight mass spectrometry (GCxGC-IDTOFMS) for the simultaneous measurement of selected polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and brominated flame retardants is presented. In contrast to the reference methods based on classical GC/MS, a single injection of the extract containing all compounds of interest results in accurate identification and quantification. Using GCxGC ensures the chromatographic separation of most compounds, and TOFMS allows mass spectral deconvolution of coeluting compounds as well as the use of (13)C-labeled internal standards for quantification. Isotope ratio measurements of the most intense ions for both native and labels ensure the required specificity. The use of this new method with an automated sample preparation procedure developed at the Centers for Disease Control and Prevention (CDC) for the analysis of human serum and milk compared favorably to conventional isotope-dilution one-dimensional gas chromatography-high-resolution mass spectrometry (GC-IDHRMS) for the different human serum and milk pools tested. The instrumental detection limits ranged between 0.5 pg/microL and 10 pg/microL and the method detection limits ranged between 1 and 15 pg/microL (N = 59 analytes). The reproducibility of the method was almost as good as with GC-IDHRMS, the relative standard deviations ranging between 1 and 11% for OCPs measured in human serum. OCP, PBDE, and PCB levels measured using the two methods were highly correlated, and the deviations between the two methods were below 20% for most analytes with concentrations above 1 ng/g milk lipids.     

Hybrid field-assisted solid-liquid-solid dispersive extraction for the determination of organochlorine pesticides in tobacco with gas chromatography

A novel one-step sample preparation technique termed hybrid field-assisted solid-liquid-solid dispersive extraction (HF-SLSDE) was developed in this study. A simple glass system equipped with a condenser was designed as an extraction vessel. The HF-SLSDE technique was a three-phase dispersive extraction approach. Target analytes were extracted from the sample into the extraction solvent enhanced by the hybrid field. Meanwhile, the interfering components were adsorbed by dispersing sorbent. No cleanup step preceded chromatographic analysis. The efficiency of the HF-SLSDE approach was demonstrated in the determination of organochlorine pesticide (OCP) residues in tobacco with a gas chromatography-electron capture detector (GC-ECD). Various operation conditions were studied systematically. Low detection limits (0.3-1.6 μg/kg) and low quantification limits (1.0-4.5 μg/kg) were achieved under the optimized conditions. The recoveries of OCPs ranged from 70.2% to 118.2%, with relative standard deviations of <9.6%, except for the lowest fortification level. Because of the effect of the hybrid field, HF-SLSDE showed significant predominance compared with other extraction techniques. The dispersing sorbent with good cleanup ability used in this study was also found to be a microwave absorption medium, which could heat the nonpolar extraction solvent under microwave irradiation. Different microstructures of tobacco samples before and after extractions demonstrated the mechanism of HF-SLSDE was based on an explosion at the cell level. According to the results, HF-SLSDE was proved to be a simple and effective sample preparation method for the analysis of pesticide residues in solid samples and could potentially be extended to other nonpolar target analytes in a complex matrix.     

Retention indexes for temperature-programmed gas chromatography of polychlorinated biphenyls

A noninteger retention index was defined based on a series of PCB internal standards, namely congeners 8 (2,4'-dichlorobiphenyl), 31 (2,4',5-trichlorobiphenyl), 44 (2,2',3,5'-tetrachlorobiphenyl), 101 (2,2',4,5,5'-pentachlorobiphenyl), 138 (2,2',3,4,4',5'-hexachlorobiphenyl), 180 (2,2',3,4,4',5,5'-heptachlorobiphenyl), and 194 (2,2',3,3',4,4',5,5'-octachlorobiphenyl). These retention index markers are common congeners present in technical mixtures and most environmental samples, and they show a linear dependence of retention time on the number of chlorine atoms, in the temperature-programmed analysis. The index values are calculated with a single regression equation instead of the Van den Dool and Kratz equation. The retention indexes of all 209 PCBs on two commonly used columns (DB-XLB and DB-5), as well as on a supplementary column of DB-17 in capillary gas chromatography, were determined using this system. The reliability of the retention index is quite good, with the average 95% confidence limits for three measurements on each PCB being +/-0.1 index unit under the same chromatographic conditions and +/-0.4 index unit under different column head pressures. The effect of heating rate of the programmed runs on the retention index was also investigated. The inversion of the elution order of some congener pairs on the DB-XLB column for different temperature heating rates was observed. Our index values were compared with those of Castello and Testini.     

Distribution of polychlorinated biphenyls in the Newark Bay Estuary

As part of the NJ Toxics Reduction Workplan for NY/NJ Harbor, ambient water samples were collected at 15 locations along the tidal portions of the Hackensack, Passaic, Raritan, Rahway and Elizabeth Rivers, and in Newark Bay, the Arthur Kill, and Kill van Kull. A Trace Organics Platform Sampler was used to collect a total of 73 dissolved phase and 73 suspended sediment phase samples between June 2000 and May 2002. These samples were analyzed for spatial and wet versus dry weather trends in the 114 polychlorinated biphenyls (PCBs; modified USEPA Method 1668A). Mean total PCB concentrations at the sampling locations ranged between 3.45 and 56 ng/L. PCB homolog groups distribution patterns at the sampling locations are presented.     

Dechlorination of polychlorinated biphenyls using magnesium and acidified alcohols

Polychlorinated biphenyls (PCBs) were widely used in industry until their regulation in the 1970s. However, due to their inherent stability, they are still a widespread environmental contaminant. A novel method of degradation of PCBs (via hydrodehalogenation) has been observed using magnesium powder, a carboxylic acid, and alcohol solvents and is described in this paper. The rates of degradation were determined while varying the type of acid (formic, acetic, propionic, butyric, valeric, benzoic, ascorbic, and phosphoric), the amount of magnesium from 0.05 to 0.25 g, the amount of acetic acid from 0.5 to 50 μL and the concentration of PCB-151 from 0.1 to 50 μg/mL, as well as the alcohol solvent (methanol, ethanol, propanol, butanol, octanol, and decanol). The results of these studies indicate that the most rapid PCB dechlorination is achieved using a matrix consisting of at least 0.02 g Mg/mL ethanol, and 10 μL acetic acid/mL ethanol in which case 50 ng/μL of PCB-151 is dechlorinated in approximately 40 min.     

An assessment of structure and toxicity correlation in organochlorine pesticides

Organochlorines are the most successful, profitably utilized and commercialized group of pesticides. They have gained huge popularity and prominence in a short span of time by virtue of their ability to control almost all kinds of pests including insect, fungi, rodent, etc. The toxicity of an individual pesticide to the pests is predominantly determined by its structure, the different moieties attached to parent compound, their spatial arrangements within molecule, nature of substituents, polarity, symmetry and asymmetry of molecules, the solubility and sorption values. The present paper discusses the toxicity in terms of LD(50) of organochlorine pesticides on the basis of their structures. Further, the mode of action of these pesticides has been discussed for a better understanding of toxicity. Finally an attempt has been made to understand the structure toxicity relationship in organochlorine pesticides.     

气相色谱-质谱法测定贝类样品中的有机氯农药

建立气相色谱质谱法测定贝类样品中10种有机氯农药(包括六氯苯、α-六六六、β-六六六、γ-六六六、δ-六六六、七氯、p,p′-DDE、o,p′-DDT、p,p′-DDD、p,p′-DDT)含量的分析方法。样品经高速组织匀浆机匀浆后采用正己烷振荡提取、自制酸性硅胶柱净化,内标法定量分析。10种有机氯农药在5.0~250.0μg/L范围内线性相关性良好,相关系数均在0.99以上;方法检出限为0.1~1.6μg/kg;方法准确度高、可靠性好,低、中、高不同浓度水平样品的加标回收率为62.3%~118%(n=7),相对标准偏差(RSD)为1.1%~21%。应用该方法对实际样品扇贝和花蛤进行分析,加标回收率在61.5%~120%之间,结果满意。     

Potential for biodegradation of polychlorinated biphenyls (PCBs) by Sinorhizobium meliloti

Resting cell assay and soil microcosms were set up to investigate the biodegradation capability and metabolic intermediate of polychlorinated biphenyls (PCBs) by a rhizobial strain Sinorhizobium meliloti. Biodegradation was observed immediately after 2,4,4'-TCB was supplied as a sole source of carbon and energy in liquid cultures. After 6 days, the percent biodegradation of 2,4,4'-TCB was 77.4% compared with the control. The main intermediate was identified as 2-hydroxy-6-oxo-6-phenylhex-2,4-dienoic acid (HOPDA) for 2,4,4'-TCB as determined by gas chromatography-mass spectrometry (GC-MS). Inoculation with S. meliloti greatly enhanced the degradation of target PCB mixtures in the soil. Moreover, soil culturable bacteria, fungi and biphenyl degrading bacteria counts showed significant increase after inoculation of S. meliloti. This study suggests that S. meliloti is promising in PCB bioremediation.     

Determination of polychlorinated biphenyls in milk samples by saponification-solid-phase microextraction.

A saponification-HSSPME procedure has been developed for the extraction of PCBs from milk samples. Saponification of the samples improves the PCB extraction efficiency and allows attaining lower background. A mixed-level fractional design has been used to optimize the sample preparation process. Five variables have been considered: extraction time, agitation, kind of microextraction fiber, concentration, and volume of NaOH aqueous solution. Also the kinetic of the process has been studied with the two fibers (100-microm PDMS and 65-microm PDMS-DVB) included in this study. Analyses were performed on a gas chromatograph equipped with an electron capture detector and a gas chromatograph coupled to a mass selective detector working in MS-MS mode. The proposed method is simple and rapid, and yields high sensitivity, with detection limits below 1 ng/mL, good linearity, and reproducibility. The method has been applied to liquid milk samples with different fat content covering the whole commercial range, and it has been validated with powdered milk certified reference material.