Gas Chromatography-electron Capture Detection Research Articles

Development of a Sample Preparation Method for the Analysis of Current-Use Pesticides in Sediment Using Gas Chromatography

Pyrethroid insecticides have been implicated as the cause of sediment toxicity to Hyalella azteca in both agricultural and urban areas of California; however, for a subset of these toxic sediments (approximately 30%), the cause of toxicity remains unidentified. This article describes the analytical method development for seven additional pesticides that are being examined to determine if they might play a role in the unexplained toxicity. A pressurized liquid extraction method was optimized to simultaneously extract diazinon, methyl parathion, oxyfluorfen, dicofol, fenpropathrin, pyraclostrobin, and indoxacarb from sediment, and the extracts were cleaned using a two-step solid-phase extraction procedure. The final extract was analyzed for the target pesticides by gas chromatography/nitrogen-phosphorus detector (GC/NPD), and gas chromatography/electron capture detector (GC/ECD), after sulfur was removed by shaking with copper and cold crystallization. Three sediments were used as reference matrices to assess method accuracy and precision. Method detection limits were 0.23-1.8 ng/g dry sediment using seven replicates of sediment spiked at 1.0 ng/g dry sediment. Recoveries ranged from 61.6 to 118% with relative standard deviations of 2.1-17% when spiked at 5.0 and 50 ng/g dry sediment. The three reference sediments, spiked with 50 ng/g dry weight of the pesticide mixture, were aged for 0.25, 1, 4, 7, and 14 days. Recoveries of the pesticides in the sediments generally decreased with increased aging time, but the magnitude of the decline was pesticide and sediment dependent. The developed method was applied to field-collected sediments from the Central Valley of California.

Zaleplon (Sonata(R)) Analysis in Postmortem Specimens by Gas Chromatography--Electron Capture Detection

Zaleplon (Sonata) is a sedative hypnotic prescription medication used for the short-term treatment of insomnia. Although Zaleplon was approved by the FDA in 1999, there has been limited postmortem information about the drug cited in the toxicology literature. Zaleplon was separated from postmortem biological specimens utilizing liquid-liquid extraction coupled with a solid-phase extraction technique, and detection was accomplished by a gas chromatography-electron capture detector. The method was linear from 5.0 to 150 ng/mL with the limit of quantitation and detection determined to be 3.0 and 0.50 ng/mL, respectively. The postmortem tissue distribution of zaleplon in seven cases was as follows: 6.1-1490 ng/mL central blood (seven cases), < 3.0-503 ng/mL femoral blood (five cases), 108 ng/mL harvest blood (one case), 343-679 ng/g liver (four cases), 950 ng/g spleen (one case), < 3.0-85 ng/mL bile (three cases), 3.8-106 ng/mL urine (four cases), < 3.0-486 ng/mL vitreous humor (five cases), and 0.005-3.4 mg total gastric contents (four cases). A validated method for the analysis of zaleplon and postmortem concentrations of autopsy specimens are reported to aid the forensic toxicologist with interpretation of future casework.

Dispersive liquid–liquid microextraction method based on solidification of floating organic drop for extraction of organochlorine pesticides in water samples

A new simple and rapid dispersive liquid–liquid microextraction method has been developed for the extraction and analysis of organochlorine pesticides (OCPs) in water samples. The method is based on the solidification of a floating organic drop (DLLME-SFO) and is combined with gas chromatography/electron capture detection (GC/ECD). Very little solvent is required in this method. The disperser solvent (200 μL acetonitrile) containing 10 μL hexadecane (HEX) is rapidly injected by a syringe into the 5.0 mL water sample. After centrifugation, the fine HEX droplets (6 ± 0.5 μL) float at the top of the screw-cap test tube. The test tube is then cooled in an ice bath. After 5 min, the HEX solvent solidifies and is then transferred into a conical vial, where it melts quickly at room temperature, and 1 μL of it is injected into a gas chromatograph for analysis. Under optimum conditions, the enrichment factors and extraction recoveries are high and range between 37–872 and 82.9–102.5%, respectively. The linear range is wide (0.025–20 μg L −1), and the limits of detection are between 0.011 and 0.11 μg L −1 for most of the analytes. The relative standard deviation (RSD) for 1 μg L −1 of OCPs in water was in the range of 5.8–8.8%. The performance of the method was gauged by analyzing samples of lake and tap water.

Lindane residues in cultivated cucumber and in the most consumed fish in Caspian Sea (Iran)

In this study, the concentrations of lindane residues (organochlorine pesticides) were analyzed in samples of cultivated cucumbers (Cucumis sativus L.) and four species of most consumed fish (Sefid, Koli, Kilca and Kafal fish). Samples of cucumber were collected from five sites in Sari city (north, south, east, west and central areas) and samples of fish were caught using electric fishing from four major fishing centers (Chalous and Babolsar cities, Khazar Abad and Miankaleh regions) in Mazandaran province of Iran. Quantitative determination of the lindane content was performed by gas chromatography electron-capture detection (GC-ECD). The results showed that the concentration of lindane in cucumber samples and in the dorsal muscle of the selected fish were less than the Food and Agriculture Organization/World Health Organization (FAO/WHO) recommended intake.

Determination of Pyrethroid Residues in Pork Muscle by Immunoaffinity Cleanup and GC-ECD

A method was developed to determine six pyrethroids (tau-fluvalinate, fenpropathrin, λ-cyhalothrin, cyfluthrin, α-cypermethrin and deltamethrin) in pork muscle by immunoaffinity column cleanup and gas chromatography-electron capture detection. Spiked pork muscle samples at 5, 20, 50 μg kg−1 were extracted with petroleum spirit-diethyl ether (1:1, v/v). Fat was eliminated by liquid–liquid partition between acetonitrile and petroleum spirit. An immunoaffinity column (IAC) was used for further cleanup. The IAC column was prepared by coupling the polyclonal antibodies to the protein A sepharose gel and the resulting affinity gel columns were sufficiently stable for multiple reuse. Target compounds were adsorbed at pH 7.4 and after extensive washing, eluted with 3 mL methanol. Recoveries of the six pyrethroids were typically >70%. The detection limit was 2 μg kg−1 for λ-cyhalothrin and α-cypermethrin and 5 μg kg−1 for cyfluthrin, deltamethrin, fenpropathrin and tau-fluvalinate. Repeat analyses of pork muscle samples showed good repeatability. The method was applied to detect residues in meat samples.

Determination of some organochlorine pesticide residues in honeys from Konya, Turkey

In this study, 24 organochlorine pesticide residues in 109 different honey samples collected from stores and open markets in Konya, Turkey were analyzed by gas chromatography-electron capture detection. Aldrin, cis-chlordane, trans-chlordane, oxy-chlordane, 2,4(')-DDE, and 4,4(')-DDE were found in all honey samples. The mean value was 0.0540 microg g(-1) for oxy-chlordane. In the 55 samples of 109, levels of organochlorine pesticide residues of oxy-chlordane were determined as higher than those of Turkish Alimentarius Codex maximum residual limits (MRLs). Other organochlorine pesticide residues also exceeded MRLs except for cis-heptachlor epoxide and alpha-hexachlorocyclohexane. Since all of the honey samples are found contaminated and most of these samples exceeded MRLs, a control of organochlorine pesticide residues in honey is necessary for consumer health.

Miniaturized matrix solid phase dispersion procedure and solid phase microextraction for the analysis of organochlorinated pesticides and polybrominated diphenylethers in biota samples by gas chromatography electron capture detection

This work has developed a miniaturized method based on matrix solid phase dispersion (MSPD) using C18 as dispersant and acetonitrile–water as eluting solvent for the analysis of legislated organochlorinated pesticides (OCPs) and polybrominated diphenylethers (PBDEs) in biota samples by GC with electron capture (GC-ECD). The method has compared Florisil ®-acidic Silica and C18 as dispersant for samples as well as different solvents. Recovery studies showed that the combination of C18–Florisil ® was better when using low amount of samples (0.1 g) and with low volumes of acetonitrile–water (2.6 mL). The use of SPME for extracting the analytes from the solvent mixture before the injection resulted in detection limits between 0.3 and 7.0 μg kg −1 (expressed as wet mass). The miniaturized procedure was easier, faster, less time consuming than the conventional procedure and reduces the amounts of sample, dispersant and solvent volume by approximately 10 times. The proposed procedure was applied to analyse several biota samples from different parts of the Comunidad Valenciana.

Semi Permeable Membrane Device Reveals Indoor and Outdoor Contamination of Polychlorinated Biphenyls (PCBs)

Semi Permeable Membrane Device (SPMD) was deployed on an experimental basis for five days inside an Environmental Chemistry Laboratory and two sites outside the building in Kiel, Germany to understand the time-averaged contaminant profiles and concentrations of PCBs. Multi Dimensional High Resolution Gas Chromatography-Electron Capture Detection technique and high resolution clean up techniques were employed to SPMD derived triolein samples. Air concentrations were derived from well established mass transfer coefficients or rate constants for PCBs in SPMD. PCBs profiles in indoor and outdoor samples were distinctly different, exemplified by a particle free clean-up laboratory facility where particle associated higher chlorinated congeners were absent. SPMDs revealed the ‘occupational hazard’ to workers inside the building from chemical contamination derived from both building materials and chemicals used in the laboratory. Finger printing technique using principle component analysis (PCA) revealed that PCB contamination was derived from German commercial PCB mixtures. SPMD derived air concentrations in outdoor samples resembled levels recorded by similar devices in Europe. Ultimately, a simple sampling technique in combination with high resolution analytical techniques demonstrated the uptake of more than 60 PCB congeners within a short period of time.

Dieldrin uptake by vegetable crops grown in contaminated soils

The aim of these trials was to study the distribution of dieldrin in soil and its translocation to roots and the aerial parts of vegetable crops grown in greenhouses and fields. The main objectives were to characterize dieldrin accumulation in plant tissues in relation to the levels of soil contamination; uptake capability among plants belonging to different species, varieties and cultivars. The presence of the contaminant was quantified by gas chromatography-electron capture detector (GC-ECD) and confirmed by gas chromatography-mass spectrometer (GC-MS). The results showed a translocation of residues in cucurbitaceous fruits and flowers confirming that zucchini, cucumber and melon are crops with high uptake capability. The maximum level of dieldrin residue at 0.01 mg/kg was found to be a threshold value to safeguard the quality production of cucurbits. Tomato, lettuce and celery were identified as substitute crops to grow in contaminated fields.

Dispersive liquid‐liquid microextraction followed by gas chromatography–electron capture detection for determination of polychlorinated biphenyls in fish

A new method of dispersive liquid-liquid microextraction (DLLME) combined with GC-electron capture detection (GC-ECD) was proposed for the extraction and determination of four polychlorinated biphenyls (PCBs) congeners in fish samples. Acetone was used as extraction solvent for the extraction of PCBs from fish samples. The target analytes in the acetone solvent were rapidly transferred to chlorobenzene, which was used as extraction solvent in DLLME procedures. Under the optimum conditions, linearity was obtained in the concentration range from 1.25 to 1250 microg/kg for PCB 52, and 0.25 to 250 microg/kg for PCB 101, 138 and 153. Coefficients of correlation (r2) ranged from 0.9993 to 0.9999. The repeatability was tested by spiking fish samples at 10 microg/kg PCBs, and RSD% (n = 8) varied between 2.2 and 8.4%. The LODs were between 0.12 and 0.35 microg/kg. The enrichment factors of PCBs were from 87 to 123. The relative recoveries of the four PCB congeners for the perch, pomfret and yellow-fin tuna at spiking levels of 10, 20 and 50 microg/kg were in the range of 81.20-100.6%, 85.00-102.7% and 87.80-108.4%, respectively. The results demonstrated that DLLME combined with GC-ECD was a simple, rapid, and efficient technique for the extraction and determination of PCBs in fish samples.

Extending the working calibration ranges of four hexachlorocyclohexane isomers in gas chromatography–electron capture detector by radial basis function neural network

A radial basis function neural network (RBFNN) method was developed for the first time to model the nonlinear calibration curves of four hexachlorocyclohexane (HCH) isomers, aiming to extend their working calibration ranges in gas chromatography–electron capture detector (GC–ECD). Other 14 methods, including seven parametric curve fitting methods, two nonparametric curve fitting methods, and five other artificial neural network (ANN) methods, were also developed and compared. Only the RBFNN method, with logarithm-transform and normalization operation on the calibration data, was able to model the nonlinear calibration curves of the four HCH isomers adequately. The RBFNN method accurately predicted the concentrations of HCH isomers within and out of the linear ranges in certified test samples. Furthermore, no significant difference (p>0.05) was found between the results of HCH isomers concentrations in water samples calculated with RBFNN method and ordinary least squares (OLS) method (R2>0.9990). Conclusively, the working calibration ranges of the four HCH isomers were extended from 0.08–60ng/ml to 0.08–1000ng/ml without sacrificing accuracy and precision by means of RBFNN. The outstanding nonlinear modeling capability of RBFNN, along with its universal applicability to various problems as a “soft” modeling method, should make the method an appealing alternative to traditional modeling methods in the calibration analyses of various systems besides the GC–ECD.

Organophosphorus Insecticide Residues in Honey Produced in Turkey

In this study, a number of 15 organophoshorus (OP) insecticides were investigated in 275 honey samples in 33 different cities of Turkey, using gas chromatography electron capture detector. The limit of determination values was detected between 0.25 and 9.55 ng g(-1). The correlation coefficients obtained from calibration curves of the OP standards were found to be between 0.992 and 0.999. No insecticide residue was detected in the samples analyzed. This result is highly significant because of its impacts on public health and food safety.

Simultaneous Determination of 26 Pesticide Residues in 5 Chinese Medicinal Materials Using Solid-phase Extraction and GC-ECD Method

Aim To develop an analytical method for the simultaneous determination of 26 pesticide residues including 21 organochlorines and 5 pyrethroids in 5 crude Chinese medicinal materials by gas chromatography-electron capture detector (GC-ECD) method. Methods Florisil solid-phase extraction (SPE) was used for the clean-up of samples and GC-ECD for the determination. The separation of the target pesticides was carried out on HP-5 quartz capillary column in an optimized oven program with nitrogen as a carrier at a constant flow of 1.0 mL·min −1and the injection inlet valve was set at 260 °C and ECD at 330 °C. Results The florisil solid-phase extraction was effective for the clean-up of the samples. For 26 pesticides, LODs and LOQs of the developed method were 0.386–2.500 ng·g −1 and 0.879–6.250 ng·g −1, respectively, and the average recoveries were found to be 69.61%–112.80% (RSD = 2.43%–15.18%, n = 9). Conclusion The developed method can be used to simultaneously determine the 26 pesticide residues in 5 Chinese medicinal materials, and it is potential for the determination of other similar Chinese medicinal materials.

Validation of a headspace solid-phase microextraction procedure with gas chromatography-electron capture detection of pesticide residues in fruits and vegetables

Abstract Headspace solid-phase microextraction (HS-SPME) was evaluated for the determination of pesticide residues in fruits and vegetables by gas chromatography with an electron capture detector (GC-ECD). The fibre used was coated with polydimethylsiloxane (100 μm thickness) and the analytical conditions employed have been developed and optimised in a previous work [Chai, M. K., Tan, G. H., & Asha, L. (2008). Optimisation of headspace solid-phase microextraction for the determination of pesticide residues in vegetables and fruits. Analytical Sciences, 24 (2), 273–276]. The results show that the HS-SPME procedure gave a better linear range, accuracy, precision, detection and quantification limits and is adequate for analysing pesticide residues in fruits and vegetables. The average recoveries obtained for each pesticide ranged between 71% and 98% at three fortification levels with the relative standard deviation of less than 5%. Repeatability (0.3–3.7%) and intermediate precision (0.8–2.5%) were shown to be satisfactory. The limits of detection (0.01–1 μg L −1 ) and the limits of quantification (0.05–5 μg L −1 ) of these pesticides were much lower than the maximum residue levels (MRL), allowed for fruits and vegetables in Malaysia.

Distribution pattern of PCBs, HCB and PeCB using passive air and soil sampling in Estonia

Passive air sampling survey of the Central and Eastern Europe was initiated in 2006. This paper presents data on toxic organic compounds such as polychlorinated biphenyls (PCB 28, 52, 101, 118, 153, 138, and 180), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), hexachlorocyclohexane compounds (alpha-HCH, beta-HCH,gamma-HCH, delta-HCH), and dichloro-diphenyl-trichloroethane (DDT) compounds (p,p'DDE, p,p'DDD, p,p'DDT, o,p'DDE, o,p'DDD, and o,p'DDT) determined in ambient air and soil samples collected at Estonian monitoring stations. Ambient air and soil samples were collected in five sites in northern Estonia. Passive air samplers were deployed four times over 4-week periods covering the period April-August 2006. Samples were analyzed using gas chromatography-electron capture detector (HP 5890) supplied with a Quadrex fused silica column 5% Ph for organochlorine pesticides (OCPs). Local ground-boundary wind field was modeled for each monitoring station and sampling period on the basis of observed wind data from the nearest meteorological station with a high quality of time series and compared with upper air (at 850- and 500-hPa level) data from Tallinn-Harku aerological station. Median levels of PCB at Estonian stations varied between 3 and 9 ng/filter, although the maximum in Kohtla-Järve reached as high as 28 ng/filter. Sampling rates about 3.5 m(3)/day were determined by empirical measurements, making approximately 100 m(3) for a 28-day sampling cycle. In general, OCP levels in soil were at the limit of detection, except Tallinn site and Muuga Port affected mainly by local sources. However, the atmospheric PCB concentrations are in agreement with the soil analyses where highest PCB levels were found in the soil sample for Tallinn (12.0 ng/g dry weight). For HCB, the atmospheric distribution was quite uniform, with the background levels sometimes higher than the urban ones. HCB and PeCB concentrations were very low in May and June when meridional airflow from the southern sector dominated, and concentrations were slightly higher in July and August, most probably due to revolatilization of adsorbed HCB (with PeCB impurities) from former industrial applications during the summer month and possibly enhanced by forest fires in Russia. Also, the highest summary HCH and DDT levels (63.5 and 2.5 ng/filter, respectively) in Estonian monitoring stations were determined at the end of July and beginning of August when the ground-boundary wind direction was from NE with relatively high speed (4-7 m/s). The highest DDT levels in ambient air (3.5 ng/filter) were determined in the spring samples. For DDT and HCH, long-range atmospheric transport clearly dominates persistent OCP, atmospheric input to Estonia as well as for the Scandinavian countries. The DDE/DDT ratio was >1, indicating no fresh input. The passive air sampling demonstrates uniform distribution of OCPs. In the regional context, there is no indication of increased levels of concentrations of OCPs in the industrial Northeast Estonia where the oil shale processing causes certain pollution impacts. Though the passive sampling does not apply for monitoring of short-term fluxes, the method is capable of reflecting background levels in long-term prospective for potential effect on human health due to long-term exposition of OCPs. PCB and its congeners, HCB, PeCB, HCH, and DDT were very low in Estonia. None of the persistent organochlorine pesticides have ever been produced in Estonia, and as of today, all old OCP stocks in the country have been destroyed. Highest concentrations could be expected in March and April when southwestern airflow is still strong and dominant, but air humidity is lower and deposition takes place far from the place of origin of OCPs. In summer, the share of locally formed organic compounds increases and deposition depends strongly on weather conditions. In some cases in Tallinn and Muuga where local anthropogenic impact occurs, HCB and PeCB stem from revolatilization of industrial application. The passive air sampling could be employed more widely to explore long-term human exposure to OCP deposition and assess potential health risks. The survey based on passive air sampling could be extended from Central and Eastern Europe to other European regions to get methodically adjusted cross-European data coverage. Based on the results of the survey, the Lahemaa reference station is a feasible option to represent background monitoring of persistent organic pollutants.

Dispersive liquid–liquid microextraction combined with gas chromatography–electron capture detection for the determination of polychlorinated biphenyls in soils

In this article, dispersive liquid–liquid microextraction (DLLME) and gas chromatography–electron capture detection (GC–ECD) were presented for the extraction and determination of five polychlorinated biphenyls (PCBs) in soil samples. Acetone was used as extraction solvent for the extraction of PCBs from soil samples. In DLLME, the target analytes in the extraction solvent were rapidly transferred from the acetone extract to chlorobenzene when the extraction process began. The main advantages of this method are quick speed, high enrichment factor, high recovery and good repeatability. Under the optimum conditions, the method yields a linear calibration curve in the concentration range from 2 to 2000 μg kg −1for PCB 52, and 0.4 to 400 μg kg −1 for other target analytes. Coefficients of correlation ( r 2) ranged from 0.9993 to 0.9999. The repeatability was tested by spiking soil samples at a concentration level of 10 μg kg −1 for PCBs. The relative standard deviations (RSDs, n = 11) varied between 2.2% and 6.4%. The limits of detection (LODs), based on signal-to-noise (S/N) of 3, were between 0.20 and 0.50 μg kg −1. The relative recoveries of the five PCBs from soil S1, S2 and S3 at spiking levels of 10, 20 and 50 μg kg −1 were in the range of 88.70–103.8%, 82.50–106.3% and 82.30–113.6%, respectively. Therefore, DLLME combined with GC–ECD can be successfully applied for the determination of trace PCB residues in real soil samples.

Method development for the analysis of organophosphate and pyrethroid insecticides at low parts per trillion levels in water

In the current study, organophosphate and pyrethroid insecticides including diazinon, chlorpyrifos, bifenthrin, fenpropathrin, permethrin, λ-cyhalothrin, cyfluthrin, cypermethrin, esfenvalerate and deltamethrin were analyzed in laboratory and field-collected water samples. Water samples were extracted and analyzed by gas chromatography/electron capture detector (GC/ECD) and gas chromatography/nitrogen–phosphorous detector (GC/NPD). Comparison of results from liquid–liquid extraction and subsequent normal phase solid-phase extraction cleanup (LLE–NPSPE), and reversed phase solid-phase extraction (RPSPE) showed that LLE–NPSPE was the better choice to extract trace amounts of pesticides from water. Pesticide recoveries from four spiked water samples using LLE–NPSPE ranged from 63.2 to 148.8% at four spiking concentrations. Method detection limits were 0.72–1.69 ng/L using four different water sources. The stability of the target pesticides in lake water was investigated at 4 °C for 1 h, 1 d, 4 d, and 7 d under three conditions: (1) water samples only; (2) with 20 mL hexane used as a keeper solvent; and (3) with acidification to pH 2 with HCl. Results showed that water storage without treatment resulted in slow degradation of some pesticides with storage time, storage using water acidification led to significant degradation and loss of diazinon and chlorpyrifos, while water storage with hexane as a keeper solvent showed good stability for all of the target pesticides over the 7 d storage period.

Analysis of Hexachlorobenzene in Food Red Nos. 104 (Phloxine) and 105 (Rose Bengal) by GC-ECD

A simple and rapid method using electron capture detector gas chromatography (GC-ECD) was developed for the determination of hexachlorobenzene (HCB) in Food Red Nos. 104 and 105. The sample was dissolved in water and HCB was extracted with hexane. The GC-ECD operating conditions were as follows: column, InertCap 5 MS/NP (30 m x 0.25 mm i. d. with 0.25 microm film thickness); oven temperature, 60 degrees C(1 min)-->20 degrees C/min-->150 degrees C(10 min)-->20 degrees C/min-->280 degrees C(5 min); inlet temperature, 260 degrees C; detector temperature, 300 degrees C; carrier gas, nitrogen (constant press 25 psi); inlet mode, splitless. For the evaluation of the method, HCB spiked into R104 and R105 at the levels of 2 microg/g and 5 microg/g was determined in replicate in five laboratories. Mean recoveries of HCB from R104 and R105 were 98.2-103.7%. Repeatability relative standard deviation values were 2.9-6.0% and reproducibility relative standard deviation values were 4.2-9.3%. HORRAT value was less than one. From these results, the validity of this method was confirmed.

Headspace solid phase microextraction in the determination of pesticides in water samples from the Okavango Delta with gas chromatography-electron capture detection and time-of-flight mass spectrometry

Headspace solid phase microextraction (HS-SPME) was optimized for the analysis of pesticides with gas chromatography electron capture detection (GC-ECD) and high-resolution mass spectrometry. Factors influencing the extraction efficiency such as fiber type, extraction mode and temperature, effect of ionic strength, stirring and extraction time were evaluated. The lowest pesticide concentrations that could be detected in spiked aliquots after HS-SPME–GC-ECD ranged from 0.0005 to 0.0032 μg L − 1 . Consequently hexachlorobenzene, trans-chlordane, 4,4′-DDD and 4,4′-DDE were detected in water samples after HS-SPME at concentrations ranging from 2.4 to 61.4 μg L − 1 that are much higher than the 0.1 μg L − 1 maximum limit of individual organochlorine pesticides in drinking water set by the European Community Directive. The same samples were cleaned with ISOLUTE C 18 SPE sorbent with an optimal acetone/n-hexane (1:1 v/v) mixture for the elution of analytes. No pesticides were detected after SPE clean-up and pre-concentration. Precision for both methods was satisfactory with relative standard deviations less than 20%. This work demonstrated the superiority of HS-SPME as a sample clean-up and pre-concentration technique for pesticides in water samples as well as the need to identify and control point sources of pesticides.

Validation of high-throughput measurement system with microwave-assisted extraction, fully automated sample preparation device, and gas chromatography-electron capture detector for determination of polychlorinated biphenyls in whale blubber

Validation of a high-throughput measurement system with microwave-assisted extraction (MAE), fully automated sample preparation device (SPD), and gas chromatography-electron capture detector (GC-ECD) for the determination of polychlorinated biphenyls (PCBs) in minke whale blubber was performed. PCB congeners accounting for >95% of the total PCBs burden in blubber were efficiently extracted with a small volume (20 mL) of n-hexane using MAE due to simultaneous saponification and extraction. Further, the crude extract obtained by MAE was rapidly purified and automatically substituted to a small volume (1 mL) of toluene using SPD without using concentrators. Furthermore, the concentration of PCBs in the purified and concentrated solution was accurately determined by GC-ECD. Moreover, the result of accuracy test using a certified material (SRM 1588b; Cod liver oil) showed good agreement with the NIST certified concentration values. In addition, the method quantification limit of total-PCB in whale blubbers was 41 ng g −1. This new measurement system for PCBs takes only four hours. Consequently, it indicated this method is the most suitable for the monitoring and screening of PCBs in the conservation of the marine ecosystem and safe distribution of foods.