固相萃取- GC/MS法测定水中有机氯农药

建立了固相萃取-气相色谱／质谱联用测定水中痕量六六六、滴滴涕和环氧七氯的方法。采用C18固相萃取柱富集水样，二氯甲烷／丙酮混合溶剂洗脱，加入菲-d10作为内标，利用气相色谱／质谱联用仪选择离子监测模式检测，内标法定量，定性、定量准确，线性响应良好，干扰小，按采样1 L计算，方法检出限为4．26ng／L～19、2ng／L，RSD在0、4％-6、3％之间，平均加标回收率在77．7％～118％之间，实际样品测定结果表明方法能满足环境水体中痕量有机氯农药的监测要求。     

使用保留时间锁定和GC/MS对ppt级的农药进行定性和定量分析

在质谱全扫描模式下典型的农药定量限在亚ppm级范围。使用保留时间锁定气相色谱 /质谱方法 ,选择离子检测 ,实验室可以将目标化合物定量限降低至ppb级 (pg/μl)以下。如在方法中使用大体积进样 ,目标化合物可在ppt级进行定量。专门建立的 5 6 7种化合物的保留时间锁定农药质谱库 ,能够在很短的时间内从采集样品数据文件中自动筛选出这5 6 7种化合物。谱库也可以用于选择离子检测方法采集样品的快速筛选。使用化合物谱库信息 ,可以在 2小时之内建立一个包括 80种目标化合物的选择离子检测方法 ,而不需运行任何分析过程     

快速溶剂萃取—凝胶渗透色谱净化-GC／MS分析土壤中酞酸酯（PAEs）

采用毛细管柱气相色谱-质谱选择离子检测技术，结合加速溶剂萃取和凝胶渗透色谱净化方法，分析土壤中的6种酞酸酯类（PAFs）化合物。结果表明，土壤中6种PAEs检出限在14—42μg/kg间，加标平均回收率为65．5％～104．4％，相对标准偏差为5．19％～9．61％。方法具有操作简便、纯化效果好和对环境友好的特点，且具有很强的实用性。     

全二维气相色谱/飞行时间质谱联用监测环境空气中VOCs

采用全采样系统-全二维气相色谱/飞行时间质谱联用技术监测环境空气中的VOCs,优化了调制周期、升温程序、进样体积等分析条件.39种目标化合物在0 μg/m3～10.0 μg/m3范围内线性良好,检出限范围为0.03 μg/m3～0.09 μg/m3,标准气体平行测定的RSD为1.1％ ～5.3％.应用于化工园区环境空气样品测定,与热脱附-气相色谱/质谱法相比,目标物的分离效果更佳.     

浊点萃取-分光光度法测定水中痕量六价铬

利用非离子表面活性剂Triton X-114的浊点现象萃取，以二苯碳酰二肼为显色剂，采用分光光度法测定水中痕量六价铬，优化了试验条件，考察了共存离子的干扰。方法在0mg／L-12.0mg／L范围内线性良好，检出限为0.0015mg／L，标准溶液测定的RSD为2.7％，水样加标回收率为98.1％-102％。     

气相色谱/质谱法测定环境毒饵中溴敌隆

采用气相色谱／质谱联用法测定环境毒饵中溴敌隆，优化了试验条件。方法在0mg／L～10．0mg／L范围内线性良好，检出限为0．01mg／kg，标准溶液测定的相对标准偏差为2．2％～4．6％，样品加标回收率为92．5％-96．3％。     

超声波提取-GC/MS法测定生物体内硝基苯类化合物

以洪泽湖中6种代表性生物为研究对象，采用超声波法提取样品中硝基苯类化合物，用凝胶色谱净化、浓缩，气相色谱／质谱联用法测定。该法与索氏提取法在同等试验条件下进行加标回收试验，前者回收率高且稳定，简便可行。方法检出限为0．008μg／g～0．030μg／g，平均加标回收率为76．5％～109％，重复测定3次的RSD为1．5％～13．0％。     

选择离子监测法测定空气中氯化苄

以１，２，４－三甲苯为内标，采用气相色谱／质谱联机的选择离子监测法（ＳＴＭ）对生产车间及周围环境空气中的氯上进行监测，检出下限为１．４ｎｇ，空气中氯化苄的检出浓度为０．０２５ｍｇ／ｍ＾３，回收率为９３％￣１０５％，具有较好的重现性和准确性。     

吹扫捕集／气相色谱-质谱联用测定水中26种挥发性有机物

建立了吹扫-捕集与气相色谱-质谱（GC-MS）联用测定水中卤代烃、氯苯类化合物和苯系物等挥发性有机物（VOCs）的方法．采用吹扫-捕集法对水中的VOCs进行富集，热解吸后导入GC-MS分离各组分并用选择离子检测（SIM）进行测定，一次进样可同时对水中26种VOCs进行准确定性和定量．VOCs的线性相关系数为0．9974（0．9999，平均加标回收率为92．3％（96．5％，相对标准偏差为1．35％（5．18％（n=6），方法检出限为0．001（0．05g／L）．     

GC-MS测定土壤中酞酸酯类化合物

采用毛细管柱气相色谱-质谱联用选择离子检测(GC-MS-SIM)技术,结合快速萃取和佛罗里硅土柱净化方法分析土壤中的六种酞酸酯类(PAEs)化合物。结果表明,六种PAEs峰形好,平均加标回收率为76.7%~110%,相对标准偏差为2.5%~4.5%。方法具有操作简便、回收率高、纯化效果好和对环境友好的特点,且具有很强的实用性。     

大气预浓缩仪-GC/FPD测定环境空气中的痕量硫化物

采用大气预浓缩仪-GC/FPD建立了环境空气中7种含硫化合物的测定方法。结果表明,经惰性化改造后的大气预浓缩仪-GC/FPD测定系统的基线低,对硫化物无残留。7种化合物的线性回归方程的相关系数均在0.995以上,高、中、低3种浓度的空白加标回收率分别为98.6%~105.3%、99.1%~103.7%、85.7%~99.7%,除硫化氢的相对标准偏差为10.9%外,其余6种含硫化合物的相对标准偏差可控制在6.9%以内。当进样体积为400 m L时,方法的检出限在0.10~1.1 ng/m3。CO2、H2O对实际样品的测定无干扰。因此,该方法能够满足目前监测工作的要求,更加适用于环境空气中痕量含硫化合物的测定。     

High throughput analysis of solid-bound endocrine disruptors by LDTD-APCI-MS/MS

The development of a high-throughput method for the analysis of 14 endocrine-disrupting substances in environmental solid matrices has been investigated. Selected compounds were: hormones (estrogens and progestogens), parabens and triclocarban. The ultrafast method (15 s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). This novel approach was tested and validated in three different solid matrices (municipal sludge cakes, aquatic sediments and agricultural soils) and its performance was evaluated by estimation of extraction recovery, linearity, precision, and detection limits. In contrast to other methods based on LC-MS/MS, a cleanup step is not necessary or minimal for the municipal sludge cake matrix. Extraction recoveries ranged from 80 to 109% for all compounds in all matrix types except for estriol which was 60-75%. The intra- and inter-day precisions, as indicated by % RSD, were ≤ 14% and ≤ 16%, respectively. The method detection limits ranged from 0.7 to 4.0 ng g?1 in sediments and soil matrices and 2.8 to 16.8 ng g?1 for municipal sludge cake samples. The results for real environmental samples collected in different areas of Quebec (Canada) are illustrated.     

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

固相微萃取-气相色谱-质谱法测定饮用水中土嗅素和2-甲基异茨醇

采用固相微萃取法富集,气相色谱-质谱联用法定性和定量测定饮用水中致嗅物质土嗅素和2-甲基异茨醇。研究并讨论优化了纤维头的类型、盐的种类和浓度、温度、萃取时间等因素对异味化合物萃取量的影响。土嗅素和2-甲基异茨醇的检出限分别为1.02、2.13 ng/L,相对标准偏差分别为4.96%、7.74%。2种异味化合物在5~1 000 ng/L的范围内线性关系良好,相关系数均大于0.985。因此,用该方法能够很好地分析水中痕量的异味化合物。     

SPE-GC-MS/MS法测定水源水中多种有机氯EDCs

采用C 18柱固相萃取(SPE)-三重四级杆气相色谱-质谱法同时测定水中18种含有机氯的环境内分泌干扰物,方法在0.500μg/L^100μg/L范围内线性良好,方法检出限为0.04 ng/L^0.8 ng/L,空白水样的加标回收率为61.3%~108%,6次测定结果的RSD为3.8%~18.0%。将该方法用于饮用水源水监测,18种目标化合物的测定值为未检出~1.5 ng/L,平均加标回收率为71.9%~109%,平行测定结果的RSD<15%。     

热脱附/气相色谱法测定空气中含硫化合物

以固体CO2为冷却试剂，使空气中含硫化合物有效富集在-70℃条件下TANEX复合吸附管内，样品管在热脱附装置中120℃下解吸后，采用气相色谱脉冲式火焰光度检测器测定硫化氢、甲硫醇、二甲二硫和甲硫醚，优化了试验条件。4种含硫化合物检出限为0.1ng—0.5ng，标准管测定的RSD为12.7％—16.3％，实际气样加标回收率为78.3％—87.7％。     

On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters

A simple on-line method was developed for the analysis of pharmaceuticals, pesticides and some metabolites in drinking, surface and wastewater samples. The technique is based on the use of on-line solid-phase extraction combined with liquid chromatography electrospray tandem mass spectrometry with positive electrospray ionization (LC-ESI(PI)-MS/MS). The injection of only 1 mL of filtered water sample is used with a total analysis time of 20 min, including the period required to flush the SPE cartridge with organic solvent and reconditioning the LC column. Method detection limits were in the range of 2 to 24 ng L(-1) for the compounds of interest, with recoveries from 87 to 110% in surface as well as wastewater samples. Matrix effects were observed for some compounds without exceeding more than 25%. All results displayed a good degree of reproducibility, with relative standard deviations (RSD) of less than 12% for all compounds. Moreover, at least 200 samples were analyzed without altering the performance of the pre-concentration column. This method was preferred over traditional off-line procedures because it minimizes tedious sample preparation, increases productivity and sample throughput. The analysis of various water and wastewater samples showed that caffeine, carbamazepine and atrazine could be detected in all the samples analysed and the selected compounds are always present in at least one of the sample types.     

Effect of process conditions on the analysis of free and conjugated estrogen hormones by solid-phase extraction–gas chromatography/mass spectrometry (SPE–GC/MS)

Simultaneous analysis of 11 free estrogen hormones and five conjugated estrogens in water and municipal wastewater was studied. The analytical method was developed and tested for different types of solid-phase extraction adsorbents, eluents, sample containers and storage conditions, derivatization, and matrix effects. Varian Bond Elut C-18 solid-phase extraction adsorbent cartridge was selected based on its high recoveries for both free and conjugated estrogens. Sample storage conditions, as well as selection and pretreatment of sample container materials, can affect the trace level analysis of estrogens. Silanization of glassware is observed to provide low relative standard deviation (RSD) in the analysis and less percentage loss due to contacting with sample container materials. Light exposure during the test can significantly impact the results. The derivatized samples stored at −20°C for at least 6 days showed less than 10.5% average RSD in the analysis. The recovery efficiency in clean water varies from 72% to 101% for free estrogens and 78% to 82% for conjugated estrogens. The method detection limits (MDL) for most of the compounds range from 30 to 870 ng/L using a sample volume of 200 mL. With a sample volume of 3 L, the most sensitive compound produces a MDL of 0.03 ng/L. Dilute methanol is used to wash the loaded cartridge as a cleanup step in order to remove interfering species during analysis of wastewater samples. Using the optimized analytical methods, the concentration level of free estrogens in the influent and effluent municipal wastewaters is tested.     

超声波-气相色谱法测定鱼肉样品中硝基苯类化合物

以鱼肉样品为研究对象,采用超声波法提取鱼肉中的硝基苯类化合物,并通过凝胶色谱进行净化、浓缩,最后用气相色谱定量分析,得到生物样品中硝基苯类化合物的检出限,同时与传统的索氏提取法进行加标回收试验比较。结果表明:用超声波提取鱼肉样品中的硝基苯类化合物方法可行,回收率稳定,并且得到检出限为0.13~2.72 ng/g,加标回收率在60%~78%,RSD在0.04%~3.2%。     

Screening and quantification of emerging contaminants in Periyar River,Kerala (India) by using high-resolution mass spectrometry (LC-Q-ToF-MS)

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.