Microwave-assisted steam distillation for simple determination of polychlorinated biphenyls and organochlorine pesticides in sediments

A novel sample extraction technique for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) analysis using microwave-heating device is developed. In this study, microwave-assisted extraction (MAE) and steam distillation techniques were combined. Desorption of the anatytes from solid matrixes was accelerated with water vapor which was generated by microwave irradiation. A sample holder in a commercial microwave extraction cell kept the sample from direct contact with the organic solvent for analytes trapping during the treatment process. Therefore, relatively clean extracts were obtained with small amount of solvents. Without any cleanup steps, the obtained extract could be analyzed with gas chromatograph/mass spectrometers (GC/MS). Six PCB congeners (PCB15, 28, 70, 101, 180, 194, 209) and three OCPs (gamma-HCH, 4,4'-DDE, 4,4'-DDD) in two marine sediment samples (a sediment collected from a bay of Kyusyu Island, Japan, and a certified reference material NIST SRM1944) were analyzed by using this microwave-assisted steam distillation (MASD) technique and another extraction method (exhaustive steam distillation, MAE, and Soxhlet extraction); and comparisons of the results are shown in this report. Although recovery yields of highly chlorinated biphenyls (PCB180, 194, 209) and relatively polar OCPs (gamma-HCH, 4,4'-DDD) were low (30-60%) compared with other analytes (PCB15, 28, 70, 101, 4,4'-DDE; recovery, 80-100%), use of isotope labeled internal standards for the MASD technique gave comparable results with the values obtained by other extraction methods and the certified values in the samples.     

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.     

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.     

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.     

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。     

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in the soil in a typical area of eastern China

The distribution and concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs, also called co-PCBs) in a typical area of eastern China were evaluated by analysis of 21 soil and 6 sediment samples. The range of WHO-TEQ values for the PCDD/Fs and dioxin-like PCBs in 17 soil samples representing the background investigation in the study area was 0.017-5.04 pg g(-1) (dry weight, dw), with a mean value 0.967(+/-1.361)pg g(-1) and medium value 0.348 pg g(-1), which indicates that the levels of PCDD/Fs and dioxin-like PCBs over the major part of this district were low. However, the WHO-TEQ values (6.52-16.7 pg g(-1) dw) for PCDD/Fs and dioxin-like PCBs in soil samples to the leeward of a known contaminated disassembly industrial park were much higher than that of the background investigation, and the levels of sediment samples downstream of this area were in the range 2.25-34.6 pg g(-1) (dw). The levels of WHO-TEQ in soil and sediment samples decreased with an increase in distance from the researched pollution source. The principal component analysis demonstrated that the PCDD/Fs and dioxin-like PCBs in major part of contaminated sediment and soil samples derived from the correlative matrix. Yet the different distribution patterns of them in part of sediment samples strongly indicate that other potential sources may be exist, further researches should be done to get more information about the sources and the distributions of the PCDD/Fs and PCBs.     

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.     

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.     

Semiautomated high-throughput extraction and cleanup method for the measurement of polybrominated diphenyl ethers, polybrominated biphenyls, and polychlorinated biphenyls in human serum

A semiautomated extraction and cleanup method has been developed for the measurement of eight polybrominated diphenyl ethers (PBDEs), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) and 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The method employs automated addition of internal standards ((13)C-labeled), addition of formic acid (denaturation agent), and dilution with water prior to automated overnight extraction using a modular solid-phase extraction (SPE) system. Removal of coextracted biogenic materials was performed on a two-layered 3-mL disposable cartridge containing activated silica gel and a mixture of silica gel and sulfuric acid. Sample cleanup was automated using the same modular SPE system. Reproducibility and precision of the liquid handler used for internal standard additions were shown to be 2 and 4%, respectively. Overall reproducibility during processing of eight batches of samples (N = 30/batch, including methods blanks) was below 10% for most analytes. Mean recoveries of the (13)C-labeled internal standards ranged from 69 to 95% for the seven monitored PBDEs; 76 and 98% were recovered for BB-153 and CB-153, respectively.     

Levels and distribution of organochlorine pesticides in shellfish from Qiantang River, China

Various shellfish collected from different locations along the Qiantang River in 2006 were analyzed for the levels of 13 organochlorine pesticides (OCPs) in order to elucidate the status of OCPs pollution in shellfish for human consumption. Total concentrations of OCPs in shellfish ranged from 16.9 to 78.6 ng/g wet weight (ww), with HCHs (alpha-, beta-, gamma-, delta-HCH), DDTs (p,p'-DDD, p,p'-DDE, p,p'-DDT, o,p'-DDD) and other OCPs (aldrin, diedrin, endrin, heptachlor and heptachlor epoxide) in the range of 3.33-13.2, 8.38-40.1 and 2.32-14.3 ng/g ww, respectively. The dominant OCPs in shellfish were p,p'-DDE among DDTs, beta-HCH among HCHs and heptachlor epoxide among other OCPs. It is noticeable that higher OCPs biota-sediment accumulation factor (BSAF) occurred at site with high concentration of OCPs in sediments. The field bioconcentration factor (BCF) increased exponentially with the increase of Kow (octanol-water partition coefficients) of the OCPs. Concentrations of DDTs and HCHs in shellfish from Qiantang River kept at middle level compared with those from marine environment. The concentrations of DDTs in more than 50% of edible shellfish in this study were higher than the limit of 14.4 ng/g ww for human consumption recommended by US EPA (2000).     

Occurrence, distribution and possible sources of organochlorine pesticides in agricultural soil of Shanghai, China

Surface soil samples from agricultural soil of Shanghai were collected and analyzed for 24 organochlorine pesticides (OCPs). The concentrations were in the ranges of nd–10.38 ng g⁻¹ for HCHs (sum of α-, β-, γ- and δ-HCH), 0.77–247.45 ng g⁻¹ for DDTs (sum of p,p′-DDT, p,p′-DDD, p,p′-DDE, and o,p′-DDT), 0.84–10.08 ng g⁻¹ for CHLs (sum of heptachlor, heptachlor epoxide, cis-chlordane, trans-chlordane, and trans-nonachlor), nd–3.68 ng g⁻¹ for endosulfan (sum of α- and β-endosulfan), 0.10–3.62 ng g⁻¹ for HCB and nd–5.69 ng g⁻¹ for other OCPs (sum of aldrin, dieldrin and endrin). The total OCPs concentrations ranged from 3.16 to 265.24 ng g⁻¹ and the main contaminated areas were distributed in the south regions of Shanghai (including Fengxian, Nanhui and Jinshan districts). According to the measured concentrations and detection frequencies, HCHs, DDTs, HCB and heptachlor epoxide were the most dominant compounds among the 24 OCPs. The different compositions of DDT, HCH, chlordane and endosulfan indicated that the residues of these compounds in most soil samples originated from historical application, besides slight recent introduction at some sampling locations. The correlation analysis showed no significant relationship between TOC and OCPs. The quality of Shanghai agricultural soil was classified as low pollution by OCPs.     

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.     

Concentration and congener patterns of polychlorinated biphenyls in industrial and municipal waste incinerator flue gas, Korea

In the present study, individual PCB congeners were determined in the flue gases of 10 industrial and 5 municipal solid waste incinerators using HRGC/HRMS. The total PCBs concentration of all congeners (168 tetra to deca-chlorinated congeners) ranged from 26 to 343 ng/Nm(3), and from 36 to 1095 ng/Nm(3) in industrial waste incinerators (IWI) and municipal solid waste incinerators (MSWI), respectively. The total TEQ concentrations of PCBs, calculated using WHO-TEF values, varied from 0.001 to 0.55 ng-TEQ/Nm(3) and from 0.001 to 8.29 ng-TEQ/Nm(3) in the industrial waste incinerators and municipal solid waste incinerators, respectively. In all samples, the contribution of PCB 126 to total TEQ of PCBs was higher than 87%. The homologue pattern of PCBs in the incinerator flue gas samples was generally dominated by tetra- and penta-CBs. The distribution of other homologues was less than 15% in most of the incinerators. The fraction of co-PCBs against to total PCBs ranged from 1% to 19% and from 2% to 31% in IWI and MSWI flue gas samples. Results of the present study reveal that the presence of non-ortho PCB congeners in the flue gas originated form the combustion process.     

Two trace analytical methods for determination of hydroxylated PCBs and other halogenated phenolic compounds in eggs from Norwegian birds of prey

Two new trace analytical methods are presented for identification and quantification of phenolic compounds in complex biological matrixes such as bird of prey eggs. One method is based on derivatization with methyl chloroformate prior to GC/high-resolution MS (HRMS) analysis in electron impact ionization mode. Alternatively, the underivatized phenolic analytes were separated and detected by HPLC coupled to time-of-flight MS (TOF-MS) in the negative ion electrospray ionization mode. For both methods, the egg samples were homogenized and dried with acidified sodium sulfate, cold column-extracted, and cleaned up by gel permeation chromatography and subsequently a Florisil column. Recovery rates for pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), and selected hydroxylated PCBs (HO-PCBs) from spiked hen's eggs (spiking level 1 ng/g of wet weight (ww)) were in the range of 56-98% for the HPLC/MS method and 57-108% for GC/MS including derivatization. Typical detection limits of the HPLC/TOF-MS method were 5 pg/g ww (1-2 pg injected) for HO-PCBs and PCP and 20 pg/g ww (3 pg injected) for TBBPA. The GC/HRMS method achieved detection limits of approximately 1 pg/g ww in predatory bird eggs for all analytes (0.2 pg injected for derivatized TBBPA and 0.05 pg injected for derivatized HO-PCBs and PCP). Eight eggs from four different Norwegian predatory bird species were analyzed. The concentrations determined with the two different quantification methods corresponded well with each other. PCP and TBBPA were found in all samples at concentrations up to 1350 and 13 pg/g ww, respectively (GC/HRMS values). A total of 55 penta- to nonachloro-HO-PCB congeners were detected in the eight eggs, 10 of those could be structurally identified. The maximum HO-PCB congener concentration was found for 4-HO-CB 187 in a peregrine falcon egg with estimated 388 pg/g ww. Another peregrine falcon egg was highest contaminated with sum HO-PCBs (estimated 2.1 ng/g ww). This level was 1.2 per thousand of the sum PCBs value for the same egg. Furthermore, indications were found that the HO-PCB congener distribution pattern could be species specific for predatory birds.     

Dechlorination of PCBs, CAHs, herbicides and pesticides neat and in soils at 25 degrees C using Na/NH3

The decomposition of aniline in supercritical water (SCW) was studied. Experiments were performed at various temperatures, pressures, residence times, dosage of oxidant H2O2 and initial aniline concentrations to investigate their effect on the destruction efficiency. Manganous sulfate and ferrous sulfate were screened out during the experiment to study the effect of the homogenous catalysts on destruction efficiency. The effect of pH was also studied. The experiments showed that the dosage of oxidant H2O2, experimental temperature, pressure, reaction residence time and even initial concentration of the aniline in wastewater have a significant affect on the TOC removal; manganous sulfate and ferrous sulfate improve the oxidation; TOC removal improves slightly with a decrease in the initial pH value. At a system temperature 450 degrees C, pressure 28 MPa, initial pH 4.0, residence time 46 s and K value 1.1, TOC removal can reach 100%.     

Semiautomated high-throughput extraction and cleanup method for the measurement of polybrominated diphenyl ethers and polybrominated and polychlorinated biphenyls in breast milk

A semiautomated extraction and cleanup method has been developed to measure eight polybrominated diphenyl ethers (PBDEs), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), and 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The method employs solid-phase dispersion on diatomaceous earth in a solid-phase extraction cartridge followed by automated addition of internal standards ((13)C-labeled). Extraction is then performed using an automated modular solid-phase extraction system. The extraction procedure includes drying the sample on diatomaceous earth by pressurized nitrogen and eluting target analytes and lipids with dichloromethane. Lipid content is determined gravimetrically. Lipid determinations performed using this method are compared with other standard methods and with a certified reference material. A relative standard deviation of 7.9% was obtained for 130 determinations of the lipid content in a breast milk quality control sample. Final analytical determination of target analytes was performed by gas chromatography-isotope dilution high-resolution mass spectrometry. Relative standard deviations for the measurements of target analytes for which a labeled internal standard was available were below 10% for analytes at concentrations above 1 ng/g of lipid. Mean recoveries of the (13)C-labeled internal standards ranged from 60 to 89% for the eight PBDE congeners; 74 and 113% were recovered for BB-153 and CB-153, respectively.