超声波辅助萃取测定土壤中的多溴联苯醚

对土壤中多溴联苯醚(PBDEs)的测定方法进行了研究.土壤样品经超声波辅助萃取后用硅胶氧化铝复合柱净化,再用带电子捕获检测器的气相色谱仪(GC-ECD)进行测定.该方法测定PBDEs各单体的相关系数(R2)为0.999 54～0.999 97,方法线性关系良好.基质加标空白回收率在74.9%～118.1%,相对标准偏差(RSD)为5.9%～8.9%,方法检测限为5.9～9.2 ng/kg.     

超声波萃取-GC/MS法测定橡胶轮胎中的多环芳烃

建立了超声波萃取-气相色谱/质谱(GC/MS)联用测定轮胎制品中多环芳(PAHs)的分析方法.优化了超声波萃取条件,采用MS的选择离子检测方式对PAHs进行定性定量分析.结果表明,16种PAHs的平均加标回收率为75.4%～88.0%,相对标准偏差(n=5)为0.66%～11.90%,方法检出限在1.0～4.0 ng/mL.     

吹扫捕集-GC-MS测定废水中的硝基氯苯

建立了吹扫捕集-GC-MS测定水样中硝基氯苯类化合物的方法.考察了吹扫温度、吹扫时间等对吹扫捕集效率和方法检出限的影响.在室温下,当吹扫时间为30 min时,该方法的最低检出限可达0.002 mg/L,工作曲线的线性范围为2×10 -3 ～2 mg/L,相对标准偏差在2%～6%,加标回收率在97.0%～110.0%.与国家标准方法相比,该法具有操作简便、灵敏度高、线性范围宽且无须使用有毒有机溶剂等优点,可满足工业废水和地表水中硝基氯苯的测定要求.     

邻菲啰啉活化催化褪色光度法测定环境水体中痕量铜(Ⅱ)

根据邻菲啰啉活化痕量铜(Ⅱ)催化溴酸钾氧化甲基紫褪色反应,建立了催化褪色光度法测定痕量铜(Ⅱ)的新方法.讨论了介质、试剂用量、反应温度、反应时间、活化剂和共存离子的影响,确定了最佳试验条件.结果表明,在25 mL溶液中,72 ℃恒温反应15 min,加铜(Ⅱ)和不加铜(Ⅱ)的吸光度差值与铜(Ⅱ)质量浓度间的关系在铜(Ⅱ)质量浓度为2.40×10-3～5.12×10-2 mg/L时呈线性关系,符合比尔定律;该新方法的测定波长为578 nm,铜(Ⅱ)检出限为2.40×10-3 mg/L,用于环境水体中痕量铜(Ⅱ)的测定,最大相对标准偏差为3.14%,加标回收率为96.0%～105.0%,对比<水质铜的测定二乙基二硫代氨基甲酸钠分光光度法> (GB/T 7474-1987) 相对误差低于6.00%.     

气相色谱法分离和测定合成革用胶粘剂中的挥发性有机物

对合成革用胶粘剂中的发挥有机成份进行了色谱分离，并测定了胶粘剂中的9种挥发性有机物，方法的加标回收率为89.4%～102.8%，变异系数为1.2%～5.0%。     

水中总铁两种测定方法的比较

环境监测实验室常使用不同方法进行重复检测作为检测结果质量保证的手段之一。据此对测定水中总铁的两种方法 -邻菲啰啉分光光度法和火焰原子吸收法在校准曲线和检出限、方法精密度和准确度等进行了全面比较,得出两者校准曲线相关性均较好,检出限均为0.03 mg/L,精密度RSD均小于5%,加标回收率均在90%～105%。两者的测定结果无显著性差异。     

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%.     

反相高效液相色谱法测定污水中壬基酚聚氧乙烯醚总量

建立了固相萃取一反相液相色谱一荧光检测法分析污水中壬基酚聚氧乙烯醚总量的方法.固相萃取采用Wa-ters Oasis HLB固相萃取柱(30 μg×60 mg×3 mL),6 mL二氯甲烷/甲醇(90/10,V/V)混合溶剂洗脱,洗脱液用氮吹仪浓缩至1 mL,回收率为99.68%.采用ZORBAX Eclipse XDBC-18(4.6 mm×150 mm,5 μm)反相色谱柱,甲醇/水为流动相,流速1.0 mL/min,以每分钟增加2.5%的梯度陡度进行洗脱,流动相中甲醇比例由70%增加到100%,柱温23℃,进样量15μL.荧光检测器的激发波长230 nm,发射波长313 nm.采用外标法定量.该方法的空白加标和污水样品加标回收率均在90%以上,标准偏差小于10%,定量下限为0.97～1.90 μg/L.利用该方法分别对污水处理厂进水水样、二级处理出水水样、再生水水样进行了测定,测定结果的准确度和精密度满足痕量分析的要求.     

火焰原子吸收光谱法同时测定金属酸洗废液中的铜、铁、锌、镍

研究了准确测定金属酸洗废液中铜、铁、锌、镍 4种元素的原子吸收光度分析法。结果表明 ,可对同一份金属酸洗废液中 4种金属离子进行连续测定 ,方法的检出限均小于0 .139μg/m L ,RSD≤ 8.4 0 % (n=6 ) ,加标回收率 82 .2 %～10 0 .4 % (n=6 )。为金属酸洗废液中金属的回收及利用提供了一种方便、快速、准确的分析方法。     

超声波辅助萃取—气质联用色谱法测定活性污泥中的多溴联苯醚

建立了活性污泥中多溴联苯醚(PBDEs)的分析方法。活性污泥经超声波辅助萃取,用酸性硅胶、铜粉及复合硅胶柱纯化后,采用气质联用色谱(GC/MS)对7种PBDEs单体进行测定,内标法定量。结果表明,该方法具有很好的精密性和准确性,方法检测限为17～121 pg/g,加标回收率为84.5%～109.0%,相对标准偏差(RSD)为0.5%～2.8%,回收率指示物3,3’,4,4’-四溴联苯醚(BDE-77)的回收率平均值为89.2%,RSD为0.8%,能够满足活性污泥中PBDEs的测定要求。采用所建立的方法对杭州和台州的活性污泥样品进行了测定,结果显示,台州样品中PBDEs含量高于杭州样品,但两者都低于相关文献所报道的北美及欧洲国家活性污泥中PBDEs的含量。     

对氯气校正法测定高氯废水化学需氧量的方法研究

氯气校正法(HJ/T70-2001)是测定高氯废水化学需氧量的国标方法,为了减少样品测定过程带来的环境污染,研究在不改变HJ/T70-2001氧化体系及测试条件的情况下,将取样体积由20 mL减半为10 mL,试剂的使用量相应减半,对方法的检出限、相对误差、相对标准偏差等指标进行验证。结果表明,该方法的检出限符合要求,准确度较高,精密度较好,可用于高氯废水化学需氧量的测定。     

自配消解液分光光度法测定污水中的COD

以自配消解液代替ThermoFisher公司AQ4001COD测定系统的专用消解液，比较了自配消解液分光光度法与国家标准重铬酸钾法(GB 11914-1989)测定化学需氧量(COD)的差异。对比试验表明，自配消解液分光光度法测定COD的结果精确度和准确度高，与国家标准方法无显著性差异。自配消解液分光光度法测定水样COD值的相对标准偏差;低量程(30～150 mg/L)为1.38%～2.53%，中量程(0～1 500 mg/L)为0.47%～3.63%，高量程（2 000～15 000 mg/L）为0.17%～3.53%，在国家标准方法测试水样COD值的允许误差范围内。除制革废水外，自配消解液可以代替AQ4001COD测定系统的专用消解液，适用不同量程范围内污水COD的测定。自配消解液分光光度法具有试剂使用量少、速度快、经济、二次污染小等优点，值得在环境科学领域及废水水质监测中推广应用。     

嗅觉实验配气方法的改进及影响因素研究

配制气体样品是异味测试及相关研究的基础工作，配气稳定性直接影响测试结果准确度。三点比较式臭袋法使用微量进样针量取并转移液体标准物质到3L无臭气袋的传统配气方法。对于异味阈值较小物质或样品浓度处于较低范围时，为了降低取样体积波动对配气精度和稳定性的影响。提出先将标准注入100mL玻璃注射器，充分挥发混匀后再转移部分气体到无臭气袋的两步式配气方法。结果表明，2种配气方法的准确度不存在显著差异，但两步式配气法的配气稳定性明显优于传统方法。此外，研究还发现，常见异味物质在被注人气袋后3min内便能完全挥发并混合均匀。除一些挥发性和吸附性极强的物质外，气袋内的异味物质气体浓度能在配好后20min内基本保持不变。     

生态环境监测中高锰酸盐指数测定影响因素分析研究

文中从水浴时间、计时开始方式和溶液酸度3个方面,对环保部标准样品研究所低、中、高3个已知浓度标准样品进行实验分析。结果表明,在加入5 mL 1+3硫酸,从每锅第一个样品放入水浴锅开始计时和最佳水浴时间为29 min条件下,所测定的高锰酸盐指数值具有较高的准确度和精密度。     

Development of the automated cleanup system for the analysis of PCDDs, PCDFs and DL-PCBs

A new automated cleanup system for the analysis of dioxins (PCDDs, PCDFs and DL-PCBs) has been developed. It was controlled by PLC through the touch-panel. This automated cleanup system can simultaneously treat six samples in 2h, using only about 30 mL of solvent. In this study, the recovery rates of the internal standard added as cleanup spiked were between 70% and 120% in the fly ash sample. The RSDs (relative standard deviations) were below 15%. The shortest analysis time from cleanup to calculation of concentration was approximately 6h. Moreover, this automated cleanup system eliminates personal error in sample preparation and training time for the analyst, and improves the accuracy of the experiment. Additionally, this automated cleanup system allowed rapid analysis and less consumption of organic solvent.     

Inter-laboratory comparison study on measuring semi-volatile organic chemicals in standards and air samples

Measurements of semi-volatile organic chemicals (SVOCs) were compared among 21 laboratories from 7 countries through the analysis of standards, a blind sample, an air extract, and an atmospheric dust sample. Measurement accuracy strongly depended on analytes, laboratories, and types of standards and samples. Intra-laboratory precision was generally good with relative standard deviations (RSDs) of triplicate injections <10% and with median differences of duplicate samples between 2.1 and 22%. Inter-laboratory variability, measured by RSDs of all measurements, was in the range of 2.8-58% in analyzing standards, and 6.9-190% in analyzing blind sample and air extract. Inter-laboratory precision was poorer when samples were subject to cleanup processes, or when SVOCs were quantified at low concentrations. In general, inter-laboratory differences up to a factor of 2 can be expected to analyze atmospheric SVOCs. When comparing air measurements from different laboratories, caution should be exercised if the data variability is less than the inter-laboratory differences.     

Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg^?1 (square regression) and 250.0 and 2000.0 μg kg^?1 (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg^?1, respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

甲基橙分光光度法测定环境空气及工业废气中游离溴

以０．００５‰甲基橙溶液富集吸收,用分光光度法测定环境空气和工业废气中的游离溴,并对样品的采集、保存和最佳测定条件进行了研究。结果表明,方法的采样效率〉９７％,线性良好,精密度和准确度均较高,方法灵敏,按２０Ｌ采样体积计,方法的最低检出浓度为０．０２５ｍｇ／ｍ＾３。     

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.