Determination of 3,4-dichlorinated biphenyl in soil samples by real-time immuno-PCR assay

A real-time fluorescent quantitative immuno-polymerase chain reaction (RT-IPCR) assay was developed for the detection of non-dioxin-like polychlorinated biphenyl (PCB) congener in soil samples. Based on the construction of 3,4-dichlorinated biphenyl (IUPAC PCB12) hapten and its immunogen, the specific polyclonal antibodies (pAbs) to PCB12 was obtained and used to develop a direct competitive RT-IPCR assay. Using the optimized assay, a standard curve for PCB12 was prepared. The linear range for the determination of PCB12 was from 10.0 to 1.0 × 10⁶ fg/mL with a correlation coefficient of 0.98 and a detection limit of 1.53 fg/mL. The RT-IPCR assays were tested for their cross-reactivity profiles using four selected congeners and four Aroclor products. The results for the soil samples correlated with the concentrations of PCBs obtained by gas chromatography/mass spectrometry. This highly specific, sensitive, and robust assay can be applied to on-site tests of PCBs and serve as a model for other pollutant immunoassays.     

Sustainable oil-in-water analysis using a supercritical fluid carbon dioxide extraction system directly interfaced with infrared spectroscopy

A direct aqueous supercritical fluid extraction (SFE) system using carbon dioxide provides a sustainable means by which a vast range of industries may continue to depend on well established infrared (IR) techniques to determine oil-in-water. The SFE-IR method provides an environmentally friendly substitute for current national standard IR reference methods for measuring oil-in-water that rely on using increasingly restricted ozone depleting solvents whose manufacture is being phased out in accordance with international law. The SFE-IR analysis of a 500 mL water sample can be accomplished in 15 min. A rapid on-line SFE-IR calibration method has been implemented. With this calibration method, SFE-IR accuracy for determining diesel oil in 500 mL spiked water samples using single wave number measurement was 86.0%–98.8% with precision (RSD) ranging from 2.5%–7.0%. Using a general purpose calculation which involves measuring infrared absorbance values at three di erent wave numbers, SFE-IR method accuracy for determining diesel oil in 500 mL spiked water samples was 83.7%–92.2% with RSD 1.0%–9.3%. Data is presented that indicates current long established national standard IR reference methods involving three wave number calculations should be reviewed since, without careful consideration, the inclusion of calculated aromatic hydrocarbon species contributions to final oil-in-water concentration values may provide less accurate results.     

Ru(bipy)32+-Ce(IV)化学发光体系检测环境水体中盐酸林可霉素

在酸性条件下,盐酸林可霉素（Lincomycin hydrochloride,LCHC）对Ru（bipy）₃²⁺-Ce（IV）化学发光体系有增敏作用,且化学发光强度随着LCHC浓度增加而增加,由此建立一种Ru（bipy）₃²⁺-Ce（IV）化学发光体系快速测定LCHC的新方法。在优化的条件下,化学发光强度与LCHC的浓度在1.0×10^-6 ~1.0×10^-3 g/mL范围内呈良好的线性关系,R²=0.999 01,方法检测限为3.0×10^-7 g/mL（3S/N）。对5.0×10^-5 g/mL的LCHC 11次连续测定,其相对标准偏差（RSD）为5.0%。并将建立的流动注射-化学发光分析方法应用到3种环境水体（南明河水、雨水和自来水）中LCHC的检测。环境水体中LCHC检测结果的RSD在1.7%~5.2%之间,加标回收率在86.7%~106.7%之间,结果准确可靠,令人满意。     

Rapid determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration

A rapid, simple and sensitive method was demonstrated for the determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration. With the presence of sulfuric acid, phenol could be transferred into a nitroso-compound by reacting with NaNO2. The titration end-point was obtained by the formation of a sharp cut in the oscillopolarographic with infinitesimal NaNO2 on double platinum electrodes. The results showed that phenol concentration had an excellent linear relationship over the range of 4.82×10-6-9.65×10-3 mol/L, the RSD of the proposed method was lower than 1.5%, and the spiked recoveries of three real water samples were in the range of 95.6%-106.9%.     

SPE-GC-MS/SIM测定水节霉发生地河水中半挥发性有机物

为测定水节霉发生地河水中ρ(SVOCs)(SVOCs为半挥发性有机物),比较了LLE(液液萃取)和SPE(固相萃取)前处理法提取加标空白水样中ρ(SVOCs)的GC-MS/SIM测定结果,确定并采用重现性好的SPE-GC-MS/SIM法测定了水节霉发生地河水中的ρ(SVOCs). 结果表明,LLE和SPE法对SVOCs的加标回收率分别为41.8%~121.5%和31.5%~124.4%,相对标准偏差分别为6.0%~18.0%和0.9%~14.5%,二者回收率相差不大,但SPE法的相对标准偏差小于LLE法,SPE法重现性较好,因此采用SPE-GC-MS/SIM法测定2011年2月水节霉发生地河水中的ρ(SVOCs),共检出29种SVOCs,其中ρ(邻苯二甲酸二乙酯)、ρ(∑PAHs)、ρ(硝基苯)、ρ(1,2-二氯苯)和ρ(1,4-二氯苯)分别为1 020.59、532.14、43.39、38.52和19.57 ng/L,均未超出GB 5749—2006《生活饮用水卫生标准》相关限值,表明水节霉发生地未发生SVOCs污染.      

无锡市大气中类二噁英多氯联苯污染水平

为了了解无锡市大气中类二噁英多氯联苯(Dioxin-like PCBs,DL-PCBs)水平,利用大流量空气采样器在无锡市分别采集了6个气相和6个颗粒相大气样品,气相色谱-质谱(GC-NCI-MS)测定样品中12种类二噁英多氯联苯。结果显示,大气样品中∑_(12)DL-PCBs的总浓度(气相+颗粒相)为1157～2 747 fg/m³,平均浓度为1759 fg/m3,平均浓度为1759 fg/m³。其中,气相的浓度为11 124～2 721 fg/m3。其中,气相的浓度为11 124～2 721 fg/m³,平均值为1 701fg/m3,平均值为1 701fg/m³;颗粒相的浓度为26～143 fg/m3;颗粒相的浓度为26～143 fg/m³,平均值为58fg/m3,平均值为58fg/m³。气相中∑_(12)DL-PCB含量占总量的97%,而颗粒相仅占3%。DL-PCBs的总毒性当量(气相+颗粒相)为2.16～4.47fg TEQ/m3。气相中∑_(12)DL-PCB含量占总量的97%,而颗粒相仅占3%。DL-PCBs的总毒性当量(气相+颗粒相)为2.16～4.47fg TEQ/m³,平均值为3.53fg TEQ/m3,平均值为3.53fg TEQ/m³。DL-PCBs单体中PCB-118的浓度最高,平均占总浓度的54%,其次是PCB-105和PCB-77,PCB+81在所有样品中均未检出。在所有DL-PCBs中,毒性当量浓度的主要贡献者为PCB-126,其平均贡献率为95%,其次为PCB-169,平均贡献率为3%。     

固相萃取-超高效液相色谱串联质谱法测定城市污水中5种β-受体阻断剂

β-受体阻断剂是一类常用的心血管疾病治疗药物. 建立了城市污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔5种β-受体阻断剂的超高效液相色谱-串联质谱联用检测方法. 水样经MCX固相萃取小柱富集、净化,采用0.1%甲酸水溶液与乙腈为流动相进行梯度洗脱,经BEH C18色谱柱分离,通过多反应监测模式进行测定. 该方法对5种β-受体阻断剂的线性范围为0.1～100.0 μg/L,相关系数(R2)均大于0.99. 污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔的定量限为0.2～2.0 ng/L,加标回收率为54.1%～113.4%,相对标准偏差小于22%,可用于城市污水中相关物质的分析测定.      

液相色谱质谱法测定水体及土壤中的类固醇激素

建立了水体和土壤中类固醇激素的液相色谱质谱分析方法。水样采用固相萃取方法富集,土壤样经加速溶剂萃取后由固相萃取净化和富集。处理好的样品经丹磺酰衍生化后上仪器分析。结果表明,类固醇激素在水体和土壤中的检出限分别为0.01~0.6ng/L和0.01~0.19ng/g,回收率分别为77%~97%和62%~119%,RSD小于6.04%和15.5%。该方法具有较高的准确度和精密度,适用于环境水体及土壤中类固醇激素残留的分析。     

金属罐消解—ICP-OES法直接测定土壤及植物中的铜、铅、锌

环境介质中的重金属种类繁多,而且含量高低不一。快速、准确地测定土壤及植物中的重金属含量是环境监测的重要任务之一。本文建立了金属罐消解—电感耦合等离子体发射光谱法(ICP-OES)同时测定土壤及植物中Cu、Pb、Zn的测试方法。试验表明,土壤及植物分别经HNO3-HF(2∶1)和HNO3-HF(2∶0.2)在190℃和150℃加热消解后完全分解溶出。经国家一级土壤及植物标准物质样品测定验证,结果与标准值吻合。土壤中Cu、Pb、Zn的加标回收率分别为99.4%～101.4%、99.5%～101.9%、99.7%～100.5%,RSD分别为2.05%、2.01%、1.79%;植物中Cu、Pb、Zn的加标回收率分别为99.3%～101.2%、96.9%～106.2%、99.7%～100.4%,RSD分别为2.84%、1.05%、0.985%。     

A new method of simultaneous determination of atmospheric amines in gaseous and particulate phases by gas chromatography-mass spectrometry

As more attention is being paid to the characteristics of atmospheric amines, there is also an increasing demand for reliable detection technologies. Herein, a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry (GC-MS). The amine samples were collected with and without phosphoric acid filters, followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis. Furthermore, the method was optimized and validated for determining 14 standard amines. The detection limits ranged from 0.0408-0.421 µg/mL (for gaseous samples) and 0.163-1.69 µg/mL (for particulate samples), respectively. The obtained recoveries ranged from 68.8%-180% and the relative standard deviation was less than 30%, indicating high precision and good reliability of the method. Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully. Methylamine, dimethylamine and diethylamine together accounted for 76.7% and 75.6% of particulate and gaseous samples, respectively. By comparing the measured and predicted values of gas-particle partition fractions, it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption. Moreover, the reaction between unprotonated amines and acid (aq.) in water phase likely promoted water absorption. Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl. The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.     

微波消解-双道原子荧光分析仪联合测定土壤中砷和汞

应用AFS-9530型双道原子荧光光谱法研究土壤样品中砷和汞的联合测定技术,将土壤样品置于(1+1)王水的微波消解体系中进行消解,加入1m L 5%的重铬酸钾溶液保护汞,加入5m L(5%硫脲+5%抗坏血酸)混合液将五价砷还原为三价,以硼氢化钾为还原剂在5%盐酸介质中测定砷和汞,最低检出限为砷0.55μg/L,汞0.30μg/L,回收率砷在93.5%—105.8%之间,汞在85.5%—104.9%之间,满足准确度要求。     

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.     

TiO2 nanotubes as solid-phase extraction adsorbent for the determination of polycyclic aromatic hydrocarbons in environmental water samples

An analytical method based on TiO2 nanotubes solid-phase extraction (SPE) combined with gas chromatography (GC) was established for the analysis of seven polycyclic aromatic hydrocarbons (PAHs): acenaphtylene, acenaphthene, anthracene, fluorene, phenanthrene, fluoranthene and pyrene. Factors a ecting the extraction e ciency including the eluent type and its volume, adsorbent amount, sample volume, sample pH and sample flow rate were optimized. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method. Under the optimized extraction conditions, the method showed good linearity in the range of 0.01–0.8 g/mL, repeatability of the extraction (RSD were between 6.7% and 13.5%, n = 5) and satisfactory detection limits (0.017–0.059 ng/mL). The developed method was successfully applied to the analysis of surface water (tap, river and dam) samples. The recoveries of PAHs spiked in environmental water samples ranged from 90% to 100%. All the results indicated the potential application of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.     

痕量磺胺二甲基嘧啶ELISA与HPLC检测方法比较

比较了城市污水中磺胺二甲基嘧啶(SM2)的两种检测方法,即酶联免疫(ELISA)法和SPE-HPLC法.HPLC法以Agilent ZORBAX Exlipse XDB-C18色谱柱为分析柱,流动相乙腈与超纯水的比例为2:8(V:V),270nm处检测SM2含量.结果表明,ELISA法的平均回收率为90.4%,相对标准...     

饮用水中超痕量镉的蒸气发生：原子荧光光谱法测定

研究了在特制测Ｃｄ固体试剂存在的水溶液中，Ｃｄ与ＫＢＨ４反应生成挥发性物种，以无色散原子荧光光谱法测定饮用水中超痕量Ｃｄ的分析方法，ＣＤＳＲ－１能巧妙地调节反应体系的ＰＨ值，使其达到最佳测定ＰＨ范围，且能提高挥发性物种发生率，方法的灵敏度可提高１－２数量级，方法线性范围为０－５μｇ／Ｌ，最低检出浓度为０．０８μｇ／Ｌ；精密度实验的变异系数为１．３％；回收率为９３．０％－１０６．０％。     

喷涂废水中邻苯二甲酸酯测定的优化研究

选取固相萃取GC-MS法定量检测喷涂废水中四种邻苯二甲酸酯类(PAEs),运用正交设计法,研究了pH、洗脱剂、洗脱体积、洗脱速率和水样流速对废水中PAEs回收率的影响。结果表明,pH为2.5时回收率最佳(均100%);在该pH下,洗脱剂对4种PAEs的回收率影响最大,水样流速次之,洗脱速率与洗脱体积对4种PAEs的回收率影响相对较小。样品前处理最优参数为:水样流速8mL/min、洗脱剂为乙酸乙酯、洗脱体积4mL、洗脱速率2mL/min;该条件下4种PAEs的线性范围为0.2～8.0μg/mL,相关系数均0.99,喷漆废水中平均加标回收率为61.1%～103%,相对标准偏差为3.1%～14.6%,均可满足试验要求。     

Development of an analytical method based on solid-phase extraction and LC-MS/MS for the monitoring of current-use pesticides and their metabolites in human urine

Pyrethroids, organophosphorus pesticides and fipronil have been listed as priority chemicals in human biomonitoring studies because of their wide use and potential health effects in humans. The determination of 13 pesticides, including pyrethroids(deltamethrin, cypermethrin, permethrin, cyfluthrin, bifenthrin), organophosphorus(chlorpyrifos, chlorpyrifosmethyl, and malathion), fipronil, neonicotinoids(imidacloprid, acetamiprid and thiacloprid)and triazole(prothioconazole), together with 13 corre...     

免疫磁珠分离与实时定量PCR技术联合检测水中轮状病毒的研究

建立了一种免疫磁珠分离技术联合实时定量PCR快速定量检测水中轮状病毒的方法.通过制备能够分离水中轮状病毒的特异免疫磁珠,优化分离条件,建立了免疫磁珠分离前处理方法,并与逆转录、实时定量PCR结合,成功用于水中轮状病毒的检测.研究发现,在1 mL水样中加入10 μL轮状病毒免疫磁珠、0.25 μL Tween 20、孵育2 h可达到较好的分离效果;免疫磁珠可用于3%牛肉浸膏等常用病毒洗脱液中的轮状病毒的分离,表明该分离技术能与已有的病毒浓集方法良好地整合.免疫磁珠分离技术与实时定量PCR联合用于检测水中轮状病毒,全过程需时约5 h,检测限为1×10⁴　copies/mL(相当于3～4　PFU/mＬ),检测结果与细胞病变试验检测结果有良好的线性相关关系（R²=0.981 6）,表明其能较好地表征水样的病毒感染风险.对接种已知量的轮状病毒的污水处理厂二级出水、再生水、地表水、自来水等水样的实验表明,该法可用于各种水样中轮状病毒的检测.     

广州大气二恶英污染水平及其季节变化特征

为了解广州环境空气中二恶英的污染发展趋势与季节变化, 应用高分辨率气相色谱-高分辨质谱仪(HRGC/HRMS)对广州6个区域大气样品中的17种2,3,7,8-PCDD/Fs含量进行了分析. 结果表明:2010─2011年广州大气ρ(二恶英)(以毒性当量浓度计)在112～5 620 fg/m3之间. 背景区、住宅区、商业区和交通区的大气ρ(二恶英)年均值较接近, 分别为356、323、370、461 fg/m3,范围分别为38~1 568、80~1 528、90~650、171~1 157 fg/m3; 郊区与工业区的大气ρ(二恶英)年均值相对较高, 分别为571和2 000 fg/m3,范围分别为54~2 967、265~10 676 fg/m3. 与2004─2005年广州市区环境空气污染水平相比, 市区(居住区、商业区、交通区)大气ρ(二恶英)变化不大, 而郊区和工业区的值有明显增加. 除工业区监测点外,广州秋、冬、春、夏季大气ρ(二恶英)分别为331、402、629、191 fg/m3,春季值较高与大气污染及不利气象条件在春季出现频率较高有关.