气相色谱法测定饮水中1,2,3-三氯苯的方法研究

建立了液液萃取-气相色谱法测定饮用水1,2,3-三氯苯的方法。根据测定研究,得出其方法检出限为0.05ug/L,建立的曲线回归系数高于0.995,回收率在91.17%-106.25%之间,符合要求。     

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Determination of pesticides of different chemical classes in drinking water of the state of Santa Catarina (Brazil) using solid-phase microextraction coupled to chromatographic determinations

The evaluation of the concentration of pesticides in drinking water presents a real concern. In this study, a simple and rapid method based on solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry and electron capture detectors was developed aiming at multiclass determination of 23 pesticides regulated by the Brazilian legislation. The extraction was carried out by direct immersion mode (DI-SPME) using DVB/Car/PDMS fiber coating. In order to improve the extraction efficiency, parameters such as temperature, salting-out effect, and extraction time were optimized. The method was evaluated using drinking water samples spiked with the analytes at different concentrations, and it showed good linearity in the range studied. The values obtained for limits of quantification (LOQ) were below the limits established by Brazilian regulations. Accuracy and precision of the method exhibited satisfactory results, providing relative recoveries from 70 to 123.34% at three spiked levels, and the relative standard deviations ranged from 0.53 to 24.8%. The method was applied in 20 drinking water samples from 13 cities in the State of Santa Catarina, Brazil.

     

有机改性剂对水中有机氯农药提取效率的影响研究

通过有机改性剂在液液萃取和固相萃取条件下水中有机氯农药的提取效率比对分析,首次探讨了有机改性剂对水中有机氯农药提取效率的影响。结果表明,(1)液液萃取前处理水样中不加有机改性剂、固相萃取前处理水样中添加一定量有机改性剂时,水中有机氯农药的提取效率较高;(2)采用正交实验优化水中有机氯农药固相萃取的提取效率实验表明,有机改性剂添加量对其影响大于有机改性剂种类对其影响;最佳优化方案为水样中添加1%甲醇时,提取效率最高。     

N-亚硝基二甲胺及其前体物在污水处理厂中去除的研究进展

N-亚硝基二甲胺(NDMA)是近年来发现的水或废水氯消毒的副产物,被美国环境保护署认定为可疑致癌化合物.介绍了NDMA的形成机制及其与NDMA前体物的来源.综述了NDMA及其前体物在污水处理厂中的去除现状和去除技术.在此基础上,展望了NDMA及其前体物的未来研究方向,提出了开展国内NDMA研究工作的必要性.     

气相色谱/质谱测定苯酚丙酮生产废水中半挥发性有机物

建立了用二氯甲烷液液萃取对苯酚丙酮生产废水进行预处理,气相色谱/质谱法同时测定废水中半挥发性有毒有机物异丁酸、异丙苯、α-甲基苯乙烯、2-苯基丙醛、苯乙酮、2-苯基-2-丙醇、α-甲基苯甲醇、苯酚和苯甲酸等的定性定量分析方法。色谱条件为:DB-17MS型色谱柱,程序升温,进样量为1μL,质量选择检测器(MSD)。实验结果表明,该色谱条件对苯酚丙酮生产废水中各半挥发性组分具有较好的分离效果。而对9种组分的最低检出限均低于0.04mg/L,精密度实验相对标准偏差2.14%～5.15%,实际水样的加标回收率稳定。苯酚丙酮生产废水中的主要污染物为2-苯基-2-丙醇,其次为苯酚、异丁酸和异丙苯。     

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%.     

Gas chromatography/mass spectrometry applied for the analysis of triazine herbicides in environmental waters

The excess use of triazine herbicides in agriculture causes severe contamination to the environment especially for ground water. Gas chromatography coupled with mass spectrometry (GC/MS) was used to analyze simazine, atrazine (ATR), cyanazine, as well as the degradation products of ATR such as deethylatrazine and deisopropylatrazine in environmental water samples. These compounds were baseline separated by the established GC method. The water samples were pre-concentrated by solid-phase-extraction (SPE) and analyzed by ion trap MS at sub- to low-ppt levels. Recovery of ATR by the SPE pre-concentration using a C18 cartridge was determined as 90.5 +/- 3.5%. Detection limit of the method using selected ion monitoring technique for ATR was 1.7 ppt when one liter water was analyzed. The relative analytical error for ATR fortified water samples at 200 ppt was -12.5% (n=12) with triple analysis and the relative standard deviation was 3.2%. Trace levels of ATR at 3.9 and 9.7 ppt were determined in water samples collected from a reservoir and a river in Hong Kong.     

Multiresidue analysis of organophosphate and pyrethroid pesticides in duplicate-diet solid food by pressurized liquid extraction

An analytical method was developed for determining organophosphate pesticides (OPP) and pyrethroid pesticides (PYR) in duplicate-diet solid food. The method consisted of pressurized liquid extraction (PLE) with dichloromethane followed by cleanup with gel permeation and solid phase extraction columns and gas chromatography/mass spectrometry (GC/MS) analysis. Quantitative recoveries (73-117 %) of the target pesticides were obtained for spiked duplicate-diet food samples. The percent standard deviation (% RSD) of replicate food samples was within ± 20 %. Another method was developed for determining a common OPP metabolite, 3, 5, 6-trichloro-2-pyridinol (TCP) in duplicate-diet food. The method consisted of a PLE with methanol followed by liquid-liquid partitioning, derivatization, and GC/MS analysis. Recoveries of TCP ranged from 83 to 101 % for spiked duplicate-diet food samples. The % RSD of replicate food samples was within ± 15 %. The results confirmed that these methods are reliable and robust, and that they can be used in routine analysis. In addition, a storage stability study for a common OPP, chlorpyrifos (CPF), in solid food samples was performed. The fortified (15)N-(13)C-labeled CPF was stable over 16 mo storage at -20° C in the dark. The developed analytical methods were successfully applied to 278 duplicate-diet food samples from preschool children, demonstrating that these methods are robust and suitable for routine analysis in future exposure monitoring studies.     

饮用水中异嗅物质-土臭素及二甲基异冰片的测定方法

导致饮用水土霉味的常见物质为土臭素(GSM)和二甲基异冰片(2-MIB),此两种物质通常在原水及饮用水中痕量存在,浓度低于几百ng/L.总结了用感官分析法和仪器分析法测定痕量GSM和2-MIB.对液液萃取、固相萃取、固相微萃取及各种衍生水样预处理方法进行了对比,评价了各种方法的优劣,并对异嗅物质分析方法的发展提出了展望.     

Effects of wavelength and water quality on photodegradation of N-Nitrosodimethylamine (NDMA)

N-Nitrosodimethylamine (NDMA) is a potent carcinogen that yields a cancer risk of 10⁻⁶ at concentrations as low as 0.7 ng L⁻¹. Tentative guideline values are set at 3 ng L⁻¹ in California, USA; 9 ng L⁻¹ in Ontario, Canada; 40 ng L⁻¹ nationwide in Canada; and 100 ng L⁻¹ by the World Health Organization. NDMA is a great concern in treating reclaimed water as well as drinking water. UV degradation can be considered effective degradation method. A 1-log reduction of NDMA is achieved by 1000 mJ cm⁻² of a 254-nm low pressure (LP) mercury UV lamp. However, a higher degradation efficiency than that provided by LP lamps is desired in practical treatment. In this study, the effects of wavelength and water quality were investigated to achieve higher degradation efficiency. The effects of wavelength were examined by comparing three UV lamps: a 222-nm Kr Cl Excimer UV lamp, a 254-nm LP mercury UV lamp, and a 230- to 270-nm filtered medium pressure (FMP) mercury UV lamp. The 222-nm lamp and FMP lamp achieved 4 times and 2.8 times higher degradation efficiency, respectively, than the conventional 254-nm LP lamp. Effects on water quality were also simulated by using absorption spectrum data of nitrate solutions and process water from a drinking-water treatment plant. In the simulation, the 222-nm lamp was affected by UV-absorbing compounds in the water, whereas the FMP lamp showed more stable degradation efficiency. Appropriate use of these three types of lamps could enhance the efficiency of degradation of NDMA.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

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%.     

Pressurised liquid-liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils

Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.     

Multiresidue analysis of organophosphate and pyrethroid pesticides in duplicate-diet solid food by pressurized liquid extraction

An analytical method was developed for determining organophosphate pesticides (OPP) and pyrethroid pesticides (PYR) in duplicate-diet solid food. The method consisted of pressurized liquid extraction (PLE) with dichloromethane followed by cleanup with gel permeation and solid phase extraction columns and gas chromatography/mass spectrometry (GC/MS) analysis. Quantitative recoveries (73–117 %) of the target pesticides were obtained for spiked duplicate-diet food samples. The percent standard deviation (% RSD) of replicate food samples was within ± 20 %. Another method was developed for determining a common OPP metabolite, 3, 5, 6-trichloro-2-pyridinol (TCP) in duplicate-diet food. The method consisted of a PLE with methanol followed by liquid-liquid partitioning, derivatization, and GC/MS analysis. Recoveries of TCP ranged from 83 to 101 % for spiked duplicate-diet food samples. The % RSD of replicate food samples was within ± 15 %. The results confirmed that these methods are reliable and robust, and that they can be used in routine analysis. In addition, a storage stability study for a common OPP, chlorpyrifos (CPF), in solid food samples was performed. The fortified ¹⁵N-¹³C-labeled CPF was stable over 16 mo storage at ?20° C in the dark. The developed analytical methods were successfully applied to 278 duplicate-diet food samples from preschool children, demonstrating that these methods are robust and suitable for routine analysis in future exposure monitoring studies.     

再生水中消毒副产物——卤乙酸的测定方法研究

参照美国国家环保局(USEPA)推荐的饮用水卤乙酸类消毒副产物测定方法(Method 552.3),通过优化该方法的预处理条件和改变检测方法,提出了酸化萃取-衍生化-中和萃取-GC-MS测定再生水中卤乙酸含量的分析方法,并分析了北方某市再生水中4种卤乙酸类消毒副产物含量。结果表明,该方法适用于我国再生水水质,能够有效地消除再生水中共存污染物的干扰;其相对标准偏差(n=7)小于10%,方法的精密度较好;检出限与USEPA方法基本一致;样品加标回收率满足USEPA 6251B标准方法中(100±30)%要求;再生水中的卤乙酸比自来水高出几十倍,对环境和人类存在一定的潜在危害。     

Bio-reduction of N-nitrosodimethylamine (NDMA) using a hydrogen-based membrane biofilm reactor

N-Nitrosodimethylamine (NDMA) is a disinfection by-product shown to be carcinogenic, mutagenic, and teratogenic. A feasible detoxification pathway for NDMA is a three-step bio-reduction that leads to ammonia and dimethylamine. This study examines the bio-reduction of NDMA in a H2-based membrane biofilm reactor (MBfR) that also is active in nitrate and sulfate reductions. In particular, the study investigates the effects of H2 availability and the relative loadings of NDMA, nitrate, and sulfate, which potentially are competing electron acceptors. The results demonstrate that NDMA was bio-reduced to a major extent (i.e., at least 96%) in a H2-based MBfR in which the electron-equivalent fluxes from H2 oxidation were dominated by nitrate and sulfate reductions. NDMA reduction kinetics responded to NDMA concentration, H2 pressure, and the presence of competing acceptors. The most important factor controlling NDMA-reduction kinetics was the H2 availability, controlled primarily by the H2 pressure, and secondarily by competition from nitrate reduction.     

Hair analysis: another approach for the assessment of human exposure to selected persistent organochlorine pollutants

Hair analysis was used for the assessment of exposure to organochlorine pollutants in specimens from Greece, Romania and Belgium. A simple method (using 3 N HCI as incubation reagent, liquid-liquid extraction with hexane/ dichloromethane (DCM), alumina/acid silica clean-up and GC-ECD/GC-MS analysis) was used for screening of specimens. The highest organochlorine load (up to 148 ng/g hair for the sum of PCB, DDT and hexachlorocyclohexane (HCH) isomers) was found in samples from a group of Greek women with past occupational exposure to pesticides. DDTs were the main organochlorine pollutants in Greek samples (up to 70%), while in Belgian hair samples their contribution was reduced to 40%. PCB mean concentration was higher in Belgian specimens (up to 14 ng/g hair). Lindane (y-HCH) was the main HCH isomer found in the samples (up to 82% in the Greek samples). Contribution of p,p'-DDT to the sum of DDTs was higher in Greek samples and indicates recent exposure to technical DDT. Similar PCB 153/sum PCBs ratios were found for each of the three countries suggesting similar sources of pollution with PCBs (mainly dietary). Artificially coloured hair samples were found to have lower, but not statistically significant concentrations of organochlorine pollutants than the non-coloured hair.     

Leaching behaviour of wood treated with creosote

The results of a laboratory investigation on the leaching behaviour of wood treated with creosote and of untreated wood are reported. A special leaching test derived from the German standard method DEV S4 test (DIN 38414) has been developed. Samples were leached in deionized water, in a solution buffered at pH 4.7 and in a solution of humic substances. The organic fraction of the leachate was extracted using liquid-liquid extraction. The extracts were analysed qualitatively with GC/MSD and quantified with GC/FID. The results were compared with those of Soxhlet-extracts from creosote-treated wood.     

Comparisons of coarse and fine versions of two carbons for reducing the bioavailabilities of sediment-bound hydrophobic organic contaminants

Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p^′-DDE (DDE), 2,2^′,5,5^′-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 °C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments––agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity––the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.