A rapid method for screening of the Stockholm Convention POPs in small amounts of human plasma using SPE and HRGC/HRMS

A rapid analytical screening method allowing simultaneous analysis of 23 persistent organic pollutants (POPs) in human plasma was developed. Sample preparation based on solid-phase extraction (SPE) with additional clean-up using small multilayer silica gel columns. SPE was performed using a custom made polystyrene-divinylbenzene sorbent for the extraction of chlorinated and brominated POPs. Special efforts to reduce sample volume and improve speed and efficiency of the analytical procedure were made. Determination of 16 polychlorinated biphenyls (PCBs), 5 organochlorine (OC) pesticides, octachlorinated dibenzo-p-dioxin (OCDD) and polybrominated diphenyl ether (BDE #47) in 0.5 mL human plasma was performed by using high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC/HRMS). Recovery of POPs ranged between 46% and 110%, and reproducibility was below 25% relative standard deviation (RSD) for all target compounds, except for trans-nonachlor and OCDD, which were present only at low levels. Limits of detection (LOD) were for the PCBs between 0.8 and 117.7 pg mL⁻¹ plasma and for the OC pesticides between 5.9 and 89.1 pg mL⁻¹ plasma. The LOD for OCDD and BDE #47 were 1.4 pg mL⁻¹ plasma, and 9.2 pg mL⁻¹ plasma, respectively. The presented method was successfully applied to 1016 human plasma samples from an epidemiological study on cardiovascular disease.     

Screening organic micropollutants in surface waters by SPE extraction and ecotoxicological testing

Complex mixtures of toxic substances occurring in surface waters are difficult to characterise by chemical analyses because each compound occurs at a very low concentration and requires a specific analytical method to be identified. Ecotoxicological tests on water extracts can be used as a screening tool to evaluate quickly and simply the overall quality of a water body with regard to micropollutant contamination. In this work, a pre-concentration procedure based on solid-phase extraction (SPE), suitable for both biological testing and analytical determination, is proposed. The extraction procedure is an improved version of a methodology used to evaluate the toxicity of organic micropollutants occurring in surface waters. It offers the advantage of using disposable commercial cartridges, which are easier to manage than the columns prepared with macromolecular resins. Water extracts from two representative Italian rivers, characterised by a different gradient of potential contamination and prepared according to the new concentration techniques, are used. The acute toxicity of the water extracts is tested on Daphnia magna and the bioluminescence inhibition in Vibrio fischeri. Criteria based on the concentration factor (CF) are proposed for assessing the hazard to aquatic life due to the exposure to toxic substances in surface waters. The aim of hazard ranking is to focus analytical efforts towards those samples that show the highest toxic potential.     

SPE和LC-MS／MS联用同时检测水体中的15种抗生素

采用（SPE）固相萃取柱进行分离富集,使用LC—MS／MS联用仪进行检测,建立了一种高效、低成本的可同时检测水体中多种抗生素的方法,并在河北省子牙河流域汪洋沟水体抗生素污染现状调查中得到应用。实验结果表明,（1）最优实验条件的选择为：水样体积为1L,洗脱剂用量为10mL,pH为3．0;（2）回收率达到69．2％～86．3％,相对标准偏差在1．8％～8．4％之间,表明检测结果准确度和灵敏度均较高;（3）在所检测的15种抗生素中,头孢西丁、土霉素、氯唑西林和布洛芬4种抗生素是该河流的主要抗生素污染物,其含量比重（中位数）高达73．5％,检测浓度最高（中位数）的是磺胺类抗生素,浓度为100．4ng／L;（4）各抗生素的含量从上游到下游大体呈逐渐衰减的趋势,这主要归因于下游支流的稀释作用,但水体中抗生素浓度仍远高于已有报道的地区;（5）污染源解析表明,水体中抗生素主要来源于制药企业的废水,部分来源于附近居民的生活污水。     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

Overview of passive Chemcatcher sampling with SPE pretreatment suitable for the analysis of NPEOs and NPs

The European Union Water Framework Directive (WFD; 2000/60/EC) is an important piece of environmental legislation that protects rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires the establishment and use of novel and low-cost monitoring programmes, and several methods, e.g. passive sampling, have been developed to make the sampling process more representative compared to spot sampling. This review considers passive sampling methods focusing mainly on a passive sampler named Chemcatcher®, which has been used for monitoring several harmful compounds in aquatic environments. Also, the sample treatment and analysis of nonylphenol ethoxylates (NPEOs) and nonylphenol (NPs) from water using solid phase extraction (SPE) is briefly summarized. The procedure of Chemcatcher passive sampling is quite similar to that of the SPE extraction since it concentrates the studied compounds from water as well. After sampling, the accumulated substances are extracted from the receiving phase of the sampler. The concentrations of NPEOs and NPs are currently monitored by taking conventional spot samples; SPE can be successfully used as a pretreatment procedure. Chemcatcher® passive sampling technique is a simple and useful monitoring tool and can be applied to new chemicals, such as NPEOs and NPs in aquatic environments.     

Extraction properties of new polymeric sorbents in SPE/GC analysis of phenol and hydroquinone from water samples

The influence of the polymers' properties on the solid-phase extraction recovery was studied. Different porous copolymers were used: di(methacryloyloxymethyl)naphtalene-divinylbenzene with ester functional groups (DMN-DVB), 4,4'-bis(maleimido)diphenylmethane-divinylbenzene with imide functional groups (BM-DVB), p,p'-dihydroxydiphenylmethane diglycidyl methacrylic ester-divinylbenzene (MEMDE-DVB) and p,p'-dihydroxydiphenylpropane diglycidyl methacrylic ester-divinylbenzene (MEDDE-DVB) with ester end hydroxyl functional groups. The extraction properties of new synthesized polymeric sorbents were compared with these of two commercial polymeric sorbents: styrene-divinylbenzene (SDB-1) and styrene-divinylbenzene with modified surface (StrataX). These sorbents were used in the SPE of phenol and hydroquinone from water samples.     

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。     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.     

基于电阻率法的人工湿地堵塞区域探测方法

人工湿地污水处理技术已经得到广泛的应用,但目前对人工湿地堵塞问题,无法对堵塞区域进行精确定位.为了解决这个问题,根据潜流人工湿地结构和堵塞区域的特点,建立了长、宽、高分别为146、119和102 cm水槽物理实验模型,利用改进的高密度电阻率测井法开展了探测和定位人工湿地堵塞区域的实验研究,并结合人工湿地堵塞模型的Vis...     

PM_(2.5)手工标准方法与自动监测法比对分析

选取金华、衢州、温州、丽水、宁波、杭州6个城市开展PM2.5手工标准方法和自动监测法比对实验,并用相关性和相对偏差两个指标对比对结果进行分析和评价。结果表明:(1)2013年6个采样城市采集的PM2.5手工和自动监测值均具有较好的相关性(相关系数均在0.95以上),截距均在-0.010~0.010mg/m3,但斜率相差较大(衢州和丽水在0.90以上;金华、温州和杭州在0.85~0.90;宁波在0.80以下)。(2)2013年6个城市采集的PM2.5手工和自动监测值的相对偏差为-34.2%~36.5%;PM2.5手工和自动监测值相对偏差在±15%范围内的数据占总数据量的82.6%;负偏差数据占总数据量的80.0%。(3)PM2.5手工标准方法和自动监测法的比对差异与地域、季节和PM2.5浓度等条件有关。总体上,不同地区PM2.5手工与自动监测值相对偏差绝对值(︱RD︱)年平均值为衢州丽水金华宁波温州杭州;春季PM2.5手工与自动监测值︱RD︱平均值高于夏季,秋季高于冬季;各采样城市PM2.5手工和自动监测值︱RD︱平均值在高质量浓度(PM2.5手工监测值(ρ1)0.150mg/m3)下最小,中质量浓度(0.050≤ρ1≤0.150mg/m3)下最大,低质量浓度(ρ10.050mg/m3)下介于两者之间。     

高浓度硝酸盐氮HACH测定方法中试剂国产化的探讨

通过试验对高浓度硝酸盐氮 HACH测定方法中各试剂的国产化进行探讨 ,认为用 1 0∶ 1硫酸溶液与 0 .0 4 g变色酸替代原进口试剂较合理 ,并有较好精密度与回收率。     

生物修复的新方法——菌根根际生物修复

本文介绍了菌根根际生物修复方法 ,讨论了菌根根际生物修复方法的理论依据、机理和优缺点 ,探讨了从引入固氮菌、外源细菌两个方面对菌根根际调控以提高修复效果的可能性     

微电解与Fenton试剂预处理农药废水的试验研究

农药废水是一种典型的高浓度有机工业废水 ,有机污染物浓度高 (CODCr>10 0 0 0mg L) ,可生化性差 (氯苯农药废水BOD5 CODCr=0 .0 3 ,对邻硝基氯苯农药废水BOD5 CODCr=0 .0 5 )。采用微电解和Fenton试剂氧化两种物化手段对菊酯、氯苯和对邻硝氯苯 3种废水按比例配制而成的综合农药废水进行预处理 ,结果表明 :在废水pH为 2— 2 .5时 ,经微电解处理后 ,BOD5 CODCr比值在 0 .45以上 ,可生化性提高 ;Fenton试剂对综合农药废水CODCr去除率为 60 %左右 ,色度去除率接近 10 0 %     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL^?1 and from 3.1 to 31.0 μg mL^?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL^?1corresponding to 0.036 mg Kg^?1mushroom sample based on the 3S_b criterion. The RSD is 5.03–1.83 % and 2.81–0.71 % for the concentration interval of diflubenzuron 0.31–3.1 μg mL^?1and 3.1–31.0 μg mL^?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.     

A sensitive and reliable quantification method for Bisphenol A based on modified competitive ELISA method

Bisphenol A (BPA), generally known as bisphenols, has been identified as a potential estrogenic substance. BPA must be conjugated to carrier protein and BSA was commonly used. 4,4-Bis(4-hydroxyphenyl) valeric acid (BHPVA) has a bisphenolic structure and a long carbon chain with a reactive carboxyl group on the end. In this study, BHPVA-BSA was used to produce polyclonal antibody against bisphenolic structure, and a modified competitive ELISA method for quantification of BPA was developed. This system was based on BHPVA-BSA for polyclonal antibody production against bisphenolic structure, and BHPVA-HRP for determination of BPA substituting detection antibody in competitive reaction. Recovery was assessed at 10 different concentrations (2-1000 ng/ml) of BHPVA, and the recovery range was from 96.3% to 107.2%. The variation was from 6.2% to 9.8% for intra assay and from 10.1% to 12.6% for inter assay. The quadratic was used to establish the curve regression. The range was found to be between 2 and 1000 ng/ml. This modified competitive ELISA method has proven to be a very useful tool for quantification of BPA without the unexpected interaction of BSA and anti-BSA polyclonal antibody.     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.     

测定苯胺类化合物pH控制范围及调节方法的研究

介绍了NEDA法反应机理及其酸度、pH调节方法对实验结果的影响，叙述了合理调整pH控制范围及改进pH调节方法，可以得到最大灵敏度、最佳分析效果及理想的实验方法。该方法可在化工、纺织、染料、生态、环境保护等相关领域广泛应用。     

含油污水的综合处理法及其应用

概述了竖向隔板分油法、蜂窝斜管分油法及磁性颗粒吸附过滤法 ,将这 3种方法结合处理某机修厂的含油污水 ,取得了满意效果。