气相色谱／质谱测定电子垃圾拆解区土壤中四溴双酚A的方法

本研究建立气相色谱/质谱来测定电子垃圾拆解区土壤中四溴双酚 A（TBBPA）的方法。该化合物通过超声波辅助萃取,溶剂选择V（丙酮）﹕V（正己烷）=1﹕1或乙酸乙酯;净化柱选择酸化的氟罗里硅土和无水硫酸钠混合物或CleanertC18-SPE进行净化;净化液浓缩后经衍生反应,衍生试剂选用N,O-双（三甲基硅烷基）三氟乙酰胺（BSTFA）和含1%的三甲基氯硅烷（TMCS）。该方法测定电子垃圾拆解区土壤中TBBPA的检出限为（S/N=3）0.1μg·kg^-1加标回收率平均值为92.7%（n=5）,重现性RSD为2.52%（n=5）;线性范围是20～400μg·kg^-1相关系数0.999。该方法用于调查电子垃圾拆解区土壤中四溴双酚A,范围值为5.17～218.00μg·kg^-1其周围农田土壤中四溴双酚A,范围值为0.312～4.170μg·kg^-1     

气相色谱-质谱联用测定长江三角洲农田土壤中的合成麝香

采用索氏提取、硅胶/氧化铝复合层析柱的样品前处理方法及气相色谱-质谱联用仪(GC-MS)测定长江三角洲农田土壤样品中7种合成麝香(莎利麝香、粉檀麝香、特拉斯、佳乐麝香、吐纳麝香、二甲苯麝香、酮麝香)的含量,对其污染水平和分布状况进行了研究.结果表明,实际检出的3种合成麝香(佳乐麝香、吐纳麝香、酮麝香)含量分别0.96—16.98 ng·g-1、LOD—14.13 ng·g-1和LOD—0.84 ng·g-1;土壤样品中合成麝香的加标回收率为88.8%—109.3%,精密度为5.8%—9.6%;仪器检出限(LOD)和定量限(LOQ)分别为0.03—0.33 ng·g-1、0.10—1.10 ng·g-1.长江三角洲农田土壤样品中普遍含有合成麝香,虽然其总浓度较低,但因其具有的生物富集性会在农产品中富集,故应做好相关的食品安全风险评价.     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L^-1 and gave detection limits of 0.5–1.5 ng·L^-1 for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

气相色谱-质谱联用内标法测定土壤中11种酞酸酯

建立了土壤中11种酞酸酯(PAEs)的气相色谱-质谱联用(GC-MS)内标分析方法,通过优化色谱柱升温程序和载气流量后,11种酞酸酯在18 min内得到良好的分离.同时以连续7次进样后计算PAEs峰面积响应值和峰面积变异系数为衡量指标,并逐个优化GC-MS的进样口温度、GC与MS的接口温度、进样方式和进样体积等GC-MS仪器操作参数,确定了GC-MS分析PAEs的最优条件为进样口温度250℃,接口温度280℃,载气流速1.2 mL.min-1,进样体积1.0μL,非脉冲进样方式.该分析条件下PAEs各组分的检出限(S/N=3)为0.37—1.97μg.L-1.该分析方法用于土壤样品中酞酸酯含量分析,并用苯甲酸苄酯(BenzylBenzoate)作为内标物,用内标法对11种肽酸酯进行定量,方法检出限0.01—0.07 mg.kg-1,土壤加标回收率基本在93.0%—115.0%范围内,结果可行.     

气相色谱-质谱联用法同时测定污水中对羟基苯甲酸酯和甾体雌激素

利用气相色谱-质谱联用仪(GC-MS),结合固相萃取技术,建立了同时测定污水中7种对羟基苯甲酸酯和5种甾体雌激素的定量分析方法.结果表明,目标物在40℃衍生化反应60 min可达最佳衍生化效果;最佳萃取剂净化条件为:使用HC-C18型SPE柱,p H=7条件下萃取,洗脱液为乙酸乙酯∶丙酮(1∶1,V∶V).该方法检出限(LOD)为1.8—5.7 ng·L-1,线性范围20—2000 ng·L-1(r0.990),除少量目标物回收率稍高外,大部分目标物的回收率为82.2%—128.5%,相对标准偏差介于4.4%—21.2%之间.     

海洋沉积物中甾醇类物质的气相色谱/质谱方法分析

应用超声提取技术,结合硅胶-中性氧化铝柱层析净化分离,BSTFA+1%TMCS衍生,及气相色谱-质谱定性定量技术,建立了海洋表层沉积物中8种甾醇类化合物的定量分析方法.实验采用正交实验优化了提取过程中提取剂种类、试剂体积和超声时间,同时对比并优化了柱层析淋洗液的配比、用量以及衍生剂的用量.结果表明,50 mL二氯甲烷/甲醇(V/V,2∶1),超声40 min,超声3次,总甾醇的萃取率可达99.6%;3 g硅胶+2 g中性氧化铝层析,35 mL二氯甲烷/甲醇(V/V,9∶1)淋洗净化回收最佳;8种甾醇在0—848μg.L-1范围内有良好的线性关系;方法检测限为1.2—2.4 ng.g-1.在3种浓度水平0.05、0.1和1.0μg.g-1下,其平均回收率为76.2%—100.9%,相对标准偏差为1.0%—10.3%.应用本方法检测大连湾的3个沉积物样品,8种甾醇的含量在0.079—6.833μg.g-1范围内.本方法的灵敏度高、准确度好,适合用于沉积物样品中甾醇物质的检测要求.     

土壤中十氯酮检测方法研究

十氯酮（kepone）是一种毒性较高持久性有机污染物（POPs）。目前对于土壤中十氯酮的检测较少。采用索氏提取-硅胶氧化铝层析柱净化法,GC-MS对土壤中的十氯酮进行测定,该方法线性良好（r〉0.9996）,检测限较低（〈0.14μg.kg-1）,回收率稳定（平均值为90.1%~95.8%）。是测定土壤中十氯酮的较好方法。     

Field evaluation and determination of four herbicides in a wheat ecosystem by a simple and versatile QuEChERS method with liquid chromatography-tandem mass spectrometry

Wheat products are consumed worldwide and every day; therefore, herbicides misuse in the wheat ecosystem has become a global food safety issue. Here, a simple and versatile method, QuEChERS (quick, easy, cheap, effective, rugged, and safe) with liquid chromatography-tandem mass spectrometry was developed to measure four herbicides in soil, wheat, and wheat straw – florasulam, carfentrazone-ethyl, fluroxypyr-meptyl, and fluroxypyr. By adjusting the amount of graphitized carbon black from 0 to 10 mg, the herbicides could be extracted with satisfactory recoveries of 80%–110%. Application of two water-dispersible granules showed first-order kinetics as well as half-lives between 1.2 and 5.1 d under open-field conditions. The dissipation kinetics of the four herbicides differed in the soil, wheat, and wheat straw, with residual concentrations in straw at 2 h after application being higher than in soil and faster degradation occurring in straw. The terminal residues in soil, wheat grain, and wheat straw were all below the maximum residue limits. The developed method was easy to handle and versatile; thus, it will facilitate regulation and inspection for possible misuse against Good Agriculture Practices. Moreover, the results of this study will contribute to global environmental protection as well as food safety issues.     

Determination of pesticides in apples,grapes and apple juice from a Kosovo market by gradient liquid chromatography with tandem mass spectrometry

Apple, grape, and apple juice were analyzed for pesticides using a multireaction mode (MRM) method in samples taken from a Kosovo market. With this method it was possible to analyze about 100 pesticides in the ESI mode. In these samples some types of pesticides were found, but most of them did not exceed the maximum tolerance levels. In apple samples, six pesticides were detected but only three of them were in sufficient quantitites. Dimethoat was below the limit, while acephate and imazalil exceeded the limit. In grape and apple juice samples, all of pesticides which were found did not exceed the maximum tolerable limits.     

Identification of the largest individual sample value using composite sample data and certain modifications of the sweep-out method

Cost-effective hotspot identification is an important issue in hazardous waste site characterization and evaluation. Composite sampling techniques are known to be cost effective when the cost of measurement is substantially higher than the cost of sampling. Although compositing incurs no loss of information on the means, information on individual sample values is lost due to compositing. In particular, if the interest is in identifying the largest individual sample value, the composite sampling techniques are not able to do so. Under certain assumptions, it may be possible to satisfactorily predict individual sample values using the composite sample data, but it is not generally possible to identify the largest individual sample value. In this paper, we propose two methods of identifying the largest individual sample value with some additional measurement effort. Both methods are modifications of the simple sweep-out method proposed earlier. Since analytical results do not seem to be feasible, performance of the proposed methods is assessed via simulation. The simulation results show that both the proposed methods, namely the locally sequential sweep-out and the globally sequential sweep-out, are better than the simple sweep-out method.Prepared with partial support from the Statistical Analysis and Computing Branch, Environmental Statistics and Information Division, Office of Policy, Planning, and Evaluation, United States Environmental Protection Agency, Washington, DC under a Cooperative Agreement Number CR-821531. The contents have not been subjected to Agency review and therefore do not necessarily reflect the views of the Agency and no official endorsement should be inferred.     

高分辨气相色谱/高分辨质谱法测定南极样品中有机氯农药

建立了同位素稀释-高分辨气相色谱/高分辨质谱法(HRGC/HRMS)测定南极土壤、苔藓和地衣样品中23种有机氯农药的分析方法.样品经冷冻干燥、研磨处理后用正己烷∶二氯甲烷(1∶1,V∶V)混合溶剂进行加速溶剂萃取(ASE),萃取液经硅胶-氧化铝层析柱和C18小柱净化后,进HRGC/HRMS检测分析.样品中目标物定量采用平均相对响应因子法,6点标准曲线响应因子的相对标准偏差(RSD)≤20%,方法的线性范围为0.4—800μg·L-1,回收率在62%—101%之间.实际样品分析结果表明,23种OCPs的加标回收率为40%—100%,在土壤、苔藓和地衣样品中的检出限(LODs)分别为0.024—5.01、0.2—12.2、0.020—13.7 pg·g-1,可以满足南极环境样品中有机氯农药的检测分析.     

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 ??g·L^?1, and the method detection limits were less than 0.1 ??g·L^?1. For the reagent water samples fortified at 1.0 ??g·L^?1 and 2.0 ??g·L^?1, the obtained mean absolute recoveries were 70%?C130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 ??g·L^?1, the obtained mean absolute recoveries were 50%?C130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

吹扫捕集/气相色谱-原子荧光光度法测定土壤和沉积物中烷基汞

本文将原子荧光光谱检测技术与吹扫捕集/气相色谱检测技术联用,结合优化的碱性法消解前处理技术,建立了碱性法消解-吹扫捕集/气相色谱-原子荧光光谱(PT-GC-AFS)联用技术测定土壤和沉积物中烷基汞含量的方法,能够在一次分析中同时获得样品中甲基汞和乙基汞的含量.本文分别用酸性法和碱性法处理了沉积物标准样品ERM-CC580、沉积物实际样品和土壤实际样品,重点比较了本方法提出的碱性法消解和使用率较高的酸性法消解两种前处理方式.采用本方法处理实际样品进行了色谱分离研究,对低浓度的实际土壤样品进行了检出限实验,用3种不同浓度的沉积物和3种不同浓度的土壤样品验证了精密度,对沉积物标准参考物质ERM-CC580进行了测定,并用两种实际土壤样品和两种实际沉积物样品进行了加标回收率试验.实验表明,碱性法消解精密度和准确度优于酸性法消解,且步骤少、耗时短,使用的试剂种类少、毒性小,方法稳定性高、可操作性强,适用于分析测试实验室大量土壤/沉积物样品的烷基汞测定.采用碱性法消解土壤/沉积物样品,目标物实现完全分离,甲基汞、乙基汞的线性相关系数分别为0.9999、1.0000,最低检出限分别为0.02μg·kg~(-1)、0.10μg·kg~(-1)(取样量为0.50 g),样品分析甲基汞、乙基汞的RSD范围分别为1.0%—4.7%、2.5%—6.0%,加标回收率范围分别为85.1%—109%、90.3%—96.3%.     

基于分形方法的合肥大兴地区土壤中污染元素Hg异常下限

土壤污染元素异常下限值的确定对环境地球化学评价具有重要意义,传统异常下限值计算方法仪适用于元素含量数据呈正态分布的情况且地球化学意义不明确,而事实上土壤元素含量的空间分布很可能具有分形分布特征,元素背景和异常有各自独立的幂指数关系.文章探讨利用分形方法确定合肥大兴地区土壤中Hg元素的异常下限值.基于分形的含量-面积方法确定的合肥大兴地区土壤中污染元素Hg的异常下限值为0.13 mg/kg.与传统方法(平均值加两倍标准离差)对比显示,分形方法圈定的异常区域是有效的、合理的.     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.