COMPARISON BETWEEN SOLID–PHASE EXTRACTION METHODS FOR THE CHROMATOGRAPHIC DETERMINATION OF ORGANOPHOSPHORUS PESTICIDES IN WATER

A solid-phase microextraction (SPME) procedure has been developed to ex tract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng.mL^?1 for SPE and 1 to 100 ng.mL^?1 for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng.mL^?1 for SPME depending upon the analyte, and 100 ng.mL^?1 for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6 % to 5.8 % for SPME and 2.4 % to 9.2 % for SPE.

Along with the feature of being a solvent – free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE – 500 mL, SPME – 5 mL).     

Analysis of organophosphorus pesticides in whole milk by solid phase microextraction gas chromatography method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-microm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30 degrees C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 microgL-1 to 1.75 microgL-1 for coumaphos and 0.69 microgL-1 to 6.90 microgL-1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 microgL-1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 microgL-1 for dichlorvos and 0.066 microgL-1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Method development for determination of fluroxypyr in water

Improved methods for extraction and clean up of fluroxypyr residue in water have been established. Two methods of fluroxypyr extraction were used, namely, Direct Measurement of fluroxypyr and Concentration of fluroxypyr onto A Solid Phase Extraction (SPE) Adsorbent, followed by elution with solvent before determination of fluroxypyr. The recovery for Direct Measurement of fluroxypyr in water containing 8-100 microg L(-1), ranged from 86 to 110% with relative standard deviation of 0.7 to 2.15%. For the second method, three types of SPE were used, viz. C18, C18 end-capped and polyvinyl dibenzene (ISOLUTE ENV+). The procedure involved concentrating the analyte from fluroxypyr-spiked water at pH 3, followed by elution of the analyte with 4 mL of acentonitrile. The recovery of fluroxypyr from the spiked sample at 1 to 50 microg L(-1) after eluting through either C18 or C18 end-capped ranged from 40-64% (with relative standard deviation of 0.7 to 2.15) and 41-65% (with standard deviation of 1.52 to 11.9). The use of ISOLUTE ENV+, gave better results than the C18, C18 end-capped or the Direct Measurement Methods. The recovery and standard deviation of fluroxypyr from spiked water using ISOLUTE ENV+ ranged from 91-102% and 2.5 to 5.3, respectively.     

Parts-per-trillion LC-MS(Q) analysis of herbicides and transformation products in surface water

The goal of this study was to develop a robust method of analyzing surface water samples for S-triazine herbicides, chloroacetanilide herbicides, and their transformation products (TPs) using solid-phase extraction (SPE) followed by liquid chromatograph-mass spectrometry (LC-MS) with electrospray ionization (ESI) by in-source collision-induced dissociation (ISCID) capability of an orthogonal electrospray ionization probe on a single quadrupole LC-MS system. The method developed here met the goals of the study and yielded estimated method detection limits (EMDLs) averaging 0.3 ± 0.1 ng L(-1) for S-triazines and their TPs and 0.7 ± 0.4 ng L(-1) for chloroacetanilides and TPs. Spiked filtered river water yielded SPE recoveries ranging from 94.2 % ± 4.8 % for S-triazines and TPs after eliminating three compounds with less that 65 % recovery from analysis and 95.9 % ± 19 % for chloroacetanilides and their TPs. The method was field-tested with filtered water samples collected from four sites over a four-month period. Detectible values of S-triazines and TPs ranged from 0.3 to 1540 ng L(-1) with a mean of 79.3 and a median of 19.4 ng L(-1). Detectible values for chloroacetanilides and TPs ranged from 0.31 to 3780 ng L(-1) with a mean of 252 and a median of 25.6 ng L(-1). An additional goal was to determine if the method was useful for microbial degradation studies using native bacterial communities. The bacteria transformed atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) solely into 2-hydroxy atrazine (2-hydroxy-4-ethylamino-6-isopropylamino-S-triazine) with concentrations of 78.4, 63.3 and 32.5 ng L(-1) after 12 days of incubation compared with 6.3 and 7.1 ng L(-1) for control dark and control sunlight respectively.     

Acetaldehyde residue in polyethylene terephthalate (PET) bottles

A simple sample preparation technique was developed for rapid analysis of acetaldehyde residue in Polyethylene Terephthalate (PET) bottles. A laboratory-built heating system was used and coupled with gas chromatography-flame ionization detector (GC-FID) at optimized conditions. The results were a tremendous reduction of the sample preparation time from 24 hours, for the conventional method, to only one hour. The analysis took only 1.5 min with other good analytical performances i.e. a low detection limit, 0.3 ng mL(- 1) and a wide linear dynamic range, 0.3 ng mL(- 1) to 6.6 microg mL(- 1) with R(2) > 0.99.Acetaldehyde residue in freshly blown bottles were analyzed and found in the range of 0.4 to 1.1 ng mL(- 1). The results were good agreement with the conventional 24-hour airspace method (P < 0.01). The PET-bottle sampling technique was also developed to minimize the complication of sample transportation and pre-concentration. A purge and trap technique was found to be the most suitable. Then, it was implemented and compared, the results showed no significant difference (P < 0.01) with and without purge and trap.     

Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis

Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as for TCP, which suggest that those PFRs would not be suitable alternatives for BFRs. TPhP, diphenylcresylphosphate (DCP) and TCP would not be suitable alternatives either, because they are considered to be toxic to (aquatic) organisms. Diethylphosphinic acid is, just like TCEP, considered to be very persistent. From an environmental perspective, resorcinol-bis(diphenylphosphate) (RDP), bisphenol-A diphenyl phosphate (BADP) and melamine polyphosphate, may be suitable good substitutes for BFRs. Information on PFR analysis in air, water and sediment is limited to TCEP, TCPP, TPhP, TCP and some other organophosphate esters. For air sampling passive samplers have been used as well as solid phase extraction (SPE) membranes, SPE cartridges, and solid phase micro-extraction (SPME). For extraction of PFRs from water SPE is recommended, because this method gives good recoveries (67-105%) and acceptable relative standard deviations (RSDs) (<20%), and offers the option of on-line coupling with a detection system. For the extraction of PFRs from sediment microwave-assisted extraction (MAE) is recommended. The recoveries (78-105%) and RSDs (3-8%) are good and the method is faster and requires less solvent compared to other methods. For the final instrumental analysis of PFRs, gas chromatography-flame photometric detection (GC-FPD), GC-nitrogen-phosphorus detection (NPD), GC-atomic emission detection (AED), GC-mass spectrometry (MS) as well as liquid chromatography (LC)-MS/MS and GC-Inductively-coupled plasma-MS (ICP-MS) are used. GC-ICP-MS is a promising method, because it provides much less complex chromatograms while offering the same recoveries and limits of detection (LOD) (instrumental LOD is 5-10 ng mL(-1)) compared to GC-NPD and GC-MS, which are frequently used methods for PFR analysis. GC-MS offers a higher selectivity than GC-NPD and the possibility of using isotopically labeled compounds for quantification.     

Measurement of trihalomethanes in potable and recreational waters using solid phase micro extraction with gas chromatography-mass spectrometry

Solid phase micro extraction (SPME) was applied to the determination of selected trihalomethanes (THMs), chloroform, bromodichloromethane, dibromochloromethane, bromoform, in potable and recreational waters. The selected samples were environmentally significant due to mandatory limits imposed by regulatory agencies. Extraction of the analytes was performed using headspace SPME (fused silica fibre with a 100 microm poly(dimethylsiloxane coating) followed by thermal desorption at 220 degrees C and GC-MS analysis. A linear working range of 10-160 microg/l was established with relative standard deviations (%RSD) within the range, 0.9-19%. Limits of detection (LOD) were 1.0-2.8 microg/l. The highest THM concentration was 61.8 microg/l which was well within the proposed European Union directive of 100 microg/l. The total THMs determined in swimming pool waters ranged from 105-134 microg/l, with chloroform accounting for 84-86% of total THM.     

Oxidation of organophosphorus pesticides for the sensitive detection by a cholinesterase-based biosensor

A potentiometric flow injection-type biosensor developed in our laboratory was used for the determination of organophosphorus pesticides (OPs). The principle of the biosensor is that the degree of inhibition of a sensor enzyme by an OP is dependent on the concentration of the pesticide. The sensor system consisted of a reactor with acetylcholinesterase (AChE) immobilized on a controlled pore glass and a detector with a tubular H(+)-selective membrane electrode. In order to examine the possibility of enhancing the sensitivity of the sensor by converting OPs to oxidized forms (stronger inhibitors), a comparison of the degree of enzyme inhibition by OPs at 10(-6) M before and after their oxidation was made. All of the ten pesticides tested exhibited greater inhibitory power toward the sensor enzyme following oxidation. All of the oxidized pesticides at 10(-6) M inhibited the sensor enzyme to a considerable degree, demonstrating the utility of the developed method for the class-specific determination of OPs. A calibration curve for diazinon, over the concentration range of 10(-11)-10(-4) M, was obtained. The lower detection limit was 2 x 10(-10) M. Treatment of the inhibited enzyme with pyridine-2-aldoxime restored the enzyme to near full activity, allowing repeated use of the sensor.     

Solid-phase extraction and capillary electrophoresis determination of phenols from soil after alkaline CuO oxidation

Alkaline CuO oxidation has been used on molecular-level analyses of phenols from organic matter in the last decades. This method, originally developed by Hedges and Ertel [Hedges, J.I., Ertel, J.R., 1982. Characterization of lignin by gas capillary chromatography of cupric oxide oxidation products. Anal. Chem. 54, 174-178] has several drawbacks that have limited is wider utilization. In this paper, we propose a modification of the method using a solid-phase extraction (SPE) instead of a liquid-liquid extraction. The SPE procedure using C18 cartridges was optimized to obtain high recoveries. The sequential elution with acetonitrile and methanol was found to be the most appropriate procedure. Recoveries of the 12 phenols in individual standard solutions ranged from 84% to 113% with relative standard deviation (RSD) lower than 12%. Experiments with a mixed standard solution highlighted the competition between the different phenols for the adsorbing sites. Recoveries decreased with polarity, reaching 30% for p-hydroxybenzoic acid when present at a concentration of 2.5 x 10(-3)M. A sample soil subjected to a CuO oxidation was used to test the reproducibility of the SPE method and good results were achieved, RSD ranged between 0.4% and 28.3%. The performance of the CE method was also evaluated by correlation coefficients (higher than 0.9920), linearity (higher than 99.902%) and limit of detection (ranging from 2.64 x 10(-6) to 1.25 x 10(-5)M). SPE procedure presents several advantages such as fast sample preparation, good recoveries, good accuracy, low sample handling and safety improvement due to reduced solvent/sample exposure and glassware management.     

Validation of a pressurized solvent extraction and GC-NCI-MS method for the low level determination of 40 polybrominated diphenyl ethers in mothers' milk

This study reports an efficient method for the determination of 40 PBDEs from mono- to hepta-brominated in human milk. Pressurized liquid extraction (PLE) was optimized to recover PBDEs in a quantitative way using 1g of freeze dried milk. Due to the great amount of coextracted compounds, the clean-up step was optimized using alumina SPE disposable cartridges of 2 and 5g. Whereas 2g alumina SPE failed in providing good extraction yields, all PBDEs were satisfactorily recovered using 5g alumina SPE cartridges. Detection was performed with gas chromatography coupled to mass spectrometry with negative chemical ionization and method detection limits ranged from 0.01 to 0.05mugkg(-1) wet weight (ww) with a good intra and inter-day variation (coefficient of variation lower than 13.4%). This method was validated by participating in an interlaboratory exercise from Quasimeme (United Kingdom), where a standard solution containing seven congeners and a certified unspiked mothers' milk were analyzed. In the standard mixture, levels between 96.915 and 570.172mugl(-1) were quantified, whereas in certified mothers' milk, BDEs 47, 99, 100 and 154 were detected at levels from 0.010 and 0.061mugkg(-1) ww, with an error <30%. The applicability of the method was tested experimentally in five mothers' milk samples, where only BDE 47 was detected at a maximum concentration of 10.45mugkg(-1) lipid weight (lw). PLE succeeded in extracting all PBDEs from the sample with good reproducibility although the clean-up step had to be severely performed to eliminate sample interferences such as milk lipids and proteins.     

Separation of dissolved iron from the aqueous system with excess ligand

A new technique for the separation and pre-concentration of dissolved Fe(III) from the ligand-rich aqueous system is proposed. A solid phase extraction (SPE) system with an immobilized macrocyclic material, commonly known as molecular recognition technology (MRT) gel and available commercially, was used. Synthetic Fe(III) solution in aqueous matrices spiked with a 100-fold concentration of EDTA was used. Dissolved iron that was ‘captured’ by the MRT gel was eluted using hydrochloric acid and subsequently determined by graphite furnace atomic absorption spectrometry. The effect of different variables, such as pH, reagent concentration, flow rate and interfering ions, on the recovery of analyte was investigated. Quantitative maximum separation (∼100%) of the dissolved Fe(III) from synthetic aqueous solutions at a natural pH range was observed at a flow rate of 0.2 mL min^-1. The extraction efficiency of the MRT gel is largely unaltered by the coexisting ions commonly found in natural water. When compared with different SPE materials, the separation performance of MRT gel is also much higher.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.     

Development of a solid phase microextraction-gas chromatography-mass spectrometry method for the determination of pentachlorophenol in human plasma using experimental design

A new method, headspace solid-phase microextraction (HS-SPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS), which was used for the determination of trace amount of pentachlorophenol (PCP) in human plasma was presented. The acetylation derivatization reaction was firstly optimized using a Doehlert design. Then a series of parameters relevant to the headspace SPME procedure, including fiber coating, extraction temperature, extraction time and salt addition, were optimized using a two-level full factorial design expanded further to a central composite design. The validation of method showed that the optimized method had good linearity (R(2)=0.999) within the concentration ranges 0.1-50.0ngml(-1), and was sensitive with the limit of detection of 0.02ngml(-1). Intra- and inter-day precision for pentachlorophenol in human plasma samples were not greater than 11.9% and 12.6%, respectively. The proposed method, to our knowledge, describes the first application of HS-SPME with GC-MS for analysis of PCP in blood plasma sample. Application of the method to real human plasma samples, PCP was successfully detected in some cases at concentration levels 1.2-6.3ngml(-1).     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

A laboratory technique for investigation of diffusion and transformation of volatile organic compounds in low permeability media

A laboratory diffusion cell technique that permits spatial and temporal estimates of porewater concentrations over short intervals suitable for estimation of effective diffusion coefficients (De) and degradation rate constants (k) of volatile organic compounds (VOCs) in saturated low permeability media is presented. The diffusion cell is a sealed cylinder containing vapour reservoirs for sampling, including a vapour reservoir source and an array of vapour-filled "mini-boreholes", which are maintained water- and sediment-free by slightly negative porewater pressures. The vapour reservoirs were sampled by Solid Phase Micro-Extraction (SPME), resulting in minimal disturbance to the experimental system. Porewater concentrations are estimated from the measured vapour concentrations. Experiments were conducted using a non-reactive medium and five VOCs with a range in partitioning properties. Calibration experiments showed that equilibrium partition coefficients could be used for calculating concentrations in the vapour reservoir source from concentrations in the SPME coating after a 1-min microextraction and that the reservoir concentration was insignificantly affected by sampling. However, equilibrium was not reached during the one-min extraction of the boreholes; the microextraction reduced the borehole vapour concentrations, leading to diffusion of VOCs from porewater into the vapour-filled borehole. Thus, empirical partitioning coefficients were required for the determination of porewater VOC concentrations. The experimental data and numerical modelling indicate masses extracted by SPME extraction are relatively small, with minimal perturbation on processes studied in diffusion experiments. This technique shows promise for laboratory investigation of diffusion and transformation processes in low permeability media.     

Preparation of needle trap samplers to extract air compounds from indoor electric-vaporizing sources

In this study, gaseous benzene, toluene, ethylbenzene, and o-xylene (BTEX) were extracted by passive needle trap samplers (NTS) using divinylbenzene (DVB) particles (mesh sizes 60–80, 80–100, and 100–120, respectively) as packed sorbents. An aspirating pump measured sampling flow rates of NTS, and the relations between BTEX mass and sampling flow rates were sufficient to maintain the extraction performance of these self-designed DVB-NTS. Furthermore, this investigation compared the extraction efficiency of NTS with that of the 100-µm polydimethylsiloxane solid-phase microextration (PDMS SPME) fiber when applied to sample heating products from electric-vaporization anti-mosquito mats, and the experimental results indicated that NTS effectiveness increased with decreasing adsorbent particle diameter. Substantially less mass of gaseous BTEX was extracted using 100-µm PDMS SPME fiber than with NTS of 100–120 mesh DVB for 60-min TWA sampling of anti-mosquito mats. The 100–120 mesh DVB-NTS primarily adsorbed 4.2 ng acetone, 13.3 ng dichloromethane, and 4.5–25.3 ng C10–C12 alkanes.

Implications: The needle trap sampler (NTS) has been evaluated to be a device for sampling heating products from electric-vaporization anti-mosquito mats. Based on the experimental results, this investigation assessed NTS as suitable for occupational and environmental health applications.