液—液萃取处理高氯难降解有机废水

农药化工厂生产苯肼、苯唑醇、乙基氯化物过程排放的废水是高氯鸡生物降解有机废水,采用三辛胺作萃取剂,用液－液萃取处理,三辛胺与水中Cl^-离子形成萃合物而使Cl^-1转移到有机相。再经高效絮凝处理后,CODCr总去除率达89．8％,Cl^-总去除率达83．2％,BOD／COD比从0．02上升到0．34,可生化性大幅度提高。     

固相微萃取-气相色谱法测定饮用水及其水源水中的氯酚

利用固相微萃取(SPME)-气相色谱法(GC)联用技术测定饮用水及其水源水中的氯酚．优化萃取温度、萃取平衡时间、酸度、离子强度等实验条件．所建方法简便、精确，自来水和太湖水中均检测到氯酚。     

碳纳米管顶空固相微萃取-气相色谱法测定土壤中有机氯农药

采用碳纳米管顶空固相微萃取-气相色谱法测定了土壤中有机氯农药,探讨了萃取时间、萃取温度、搅拌速度、离子强度、有机溶剂和土壤加水量对萃取效率的影响.该方法的线性范围为0.5～50.0 ng/g,r0.991 5,检出限为0.03～0.33 ng/g.样品的加标回收率为91.4%～120.0%,相对标准偏差不大于12.7%.     

固相萃取-气相色谱/质谱法测定水中多环芳烃

建立了固相萃取-气相色谱／质谱联用测定水中多环芳烃(PAHs)的分析方法．优化了固相萃取条件。结果表明，固相萃取效率高、萃取时间短，采用MS的选择离子检测方式对实际水样中PAHs进行定性定量分析，平均回收率在80．4％～115％之间，相对标准偏差为7．03％～18．5％，方法的检出限在0．010～0．020μg／L之间。通过实际样品中PAHs的分析表明，该法快速，溶剂用量少，能满足痕量分析的要求。     

顶空箭型固相微萃取—气相色谱—串联质谱法测定水中9种藻致异味物质

通过单因素设计实验考查萃取时间、萃取温度和氯化钠加入量对9种藻致异味物质(2-甲基异莰醇、土臭素、2-异丙基-3-甲氧基吡嗪、2-异丁基-3-甲氧基吡嗪、2,4,6-三氯苯甲醚、2,3,6-三氯苯甲醚、2,3,4-三氯苯甲醚、β-紫罗兰酮、β-环柠檬醛)萃取效果的影响，并通过响应面设计进一步优化得到顶空箭型固相微萃取的条件，建立了顶空箭型固相微萃取—气相色谱—串联质谱法高效测定水中9种典型藻致异味物质的方法，并进行方法学验证。结果表明，最佳萃取条件为每5.0 mL水样萃取时间10.0 min、萃取温度40℃、氯化钠加入量1.78 g。利用优化方法分析苏州河实际水样，检出4种藻致异味物质，加标回收率为63.8%～140.0%,精密度为0.67%～15.50%,该方法可有效应用于地表水中藻致异味物质的检测。     

固相微萃取-毛细管气相色谱法快速分析水中酞酸酯

用固相微萃取富集水中酞酸酯，毛细管气相色谱分离分析，整个分析过程只需50min，检出限可达0.01-40.0μg／L，实验表明，固相微萃取是一种快速、简便、集萃取浓缩进样于一体的样品前处理技术，具有分析时间短、灵敏度高、无需有机溶剂的优点，已用于地面水源、海水、饮用水中酞酸酯含量的测定。     

固相萃取毛细管气相色谱法分析水中有机磷农药残留

探索了采用固相萃取对样品进行提取富集，以及配备氮磷检测器的毛细管气相色谱(CGC)法分析水中有机磷农药痕量残留的方法。结果表明：敌敌畏、内吸磷、乐果、甲基对硫磷、马拉硫磷和对硫磷等6种农药在20min内有较好的分离；3个不同浓度的标准添加，其回收率范围为52．1％～93．7％，最低检出限范围为1．11～5．21ng／L；同时利用该方法分析太湖梅梁湾水源地和长江沿岸水厂取水口水质，6种有机磷农药均有一定程度检出，但仍未超出集中水源地供水标准。     

城市污水处理厂不同工艺段中有机氯农药残留

建立了基于HLB固相萃取柱和气相色谱 /电子捕获 (GC/ECD)分析城市污水中有机氯农药的分析方法 ,同时分析了北京市高碑店和北小河两个污水处理厂中 4个不同工艺段水体中有机氯农药的浓度。在两个污水处理厂的水体中共检出了 6种有机氯类农药 ,分别是α 六六六、β 六六六、γ 六六六、δ 六六六、艾氏剂和 4 ,4’ 滴滴滴 ,浓度在 1 89—6 9 6ng/L之间。结果表明 ,曝气活性污泥法对六六六类有机氯农药的去除效果较好。     

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.     

固相微萃取-毛细管气相色谱法测定水中的低分子醛、酮、醇

固相微萃取是一种快速、简便、集萃取浓缩于一体的样品前处理技术,具有分析快速、灵敏度高、无需有机溶剂的优点.用固相微萃取-毛细管气相色谱分析水中甲醇、丙酮、异丙醇、乙醇、乙腈、丙烯腈,检出限可达0.003～0.03 mg/L.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Evaluation of activated carbon fiber filter for sampling of organochlorine pesticides in environmental water samples

A simple method for quantitative analyses of organic chlorine pesticides (OCPs) in environmental water samples such as rainwater, river water and seawater using activated carbon fiber filters (ACFF) is described. ACFF was used as adsorbent to collect the chemicals in water samples. The collection of OCPs was completed almost for one day by stirring the mixture of the sample and the ACFF chips at room temperature. The adsorbed OCPs on the ACFF could be extracted easily with toluene-ethanol (4:1) mixed solvent. The purified extract by a florisil column chromatograph was followed by the analysis using high-resolution gas chromatograph/high-resolution mass spectrometer. Recoveries of OCPs spiked to actual samples such as rainwater, river water and seawater samples were approximately more than 80%, and the coefficients of variations were within 10%. This method was applied to the actual samples and was confirmed to be applicable for monitoring sub-ng/l level OCPs in environmental water samples.     

Identification of some plasticizers compounds in landfill leachate

In this work it was described a simple method for extraction of plasticizer compounds (mainly phthalate esters and bisphenol A (BPA)) from landfill leachate samples. The samples were submitted to an extraction procedures based on precipitation, solid phase extraction (SPE) and ionic exchange chromatography (IEC). Firstly the landfill leachate sample was acidified by addition of HCl concentrated, in order to precipitate the organic compounds that are less soluble in water. The precipitate was washed with several solvents. The aqueous phase was then submitted to SPE with XAD-4 resin and IEC with Amberlyst A-27 resin. The instrumental analysis was performed by gas chromatography with mass spectrometer detector (GC/MSD) and the compounds were identified by the GC/MSD library (Wiley) and by using some standard substances. These methodologies allow the isolation and identification of the following compounds: dioctylphthalate, diisobutilphthalate, BPA, benzoic acid, palmitic acid and diisopentylphthalate. The methods are very simple, rapid and selective, for plasticizers extraction from landfill leachate matrices.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.