用固相萃取-高效液相色谱-三重四极杆串联质谱法测定海洋沉积物中13种氟喹诺酮类抗生素

为进一步探索海洋沉积物中氟喹诺酮类抗生素的污染情况,基于固相萃取-高效液相色谱-三重四极杆串联质谱(SPE-LC-MS/MS)技术,建立了海洋沉积物中 13 种FQs的测定方法;采用高效液相色谱-三重四极杆串联质谱多反应监测离子模式(MRM)对FQs进行分离检测。结果表明：在优化实验条件下,13种FQs的质量浓度为0.50~100 μg·L⁻¹,目标化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(R²>0.99),方法检出限为0.003~0.03 μg·kg⁻¹;在加标量为1 μg·kg⁻¹和10 μg·kg⁻¹时,空白加标的平均回收率为73.5%~124.6%和67.5%~118.5%,相对标准偏差(RSD)为1.0%~9.7%(n=7);以海洋沉积物为基质,13种目标物的加标回收率为67.7%~142.4%,RSD小于10.2%(n=6);使用该方法对广州某湾区海洋沉积物中 13 种 FQs 的残留量进行了实地检测,培氟沙星质量分数最高,为1.6 μg·kg⁻¹,氧氟沙星、环丙沙星和恩诺沙星质量分数次之,为0.7 μg·kg⁻¹。该方法实现了对海洋沉积物中 13种 FQs 的同时检测,具有快速、准确等优点,适用于海洋沉积物中13种FQs的测定。本研究成果可为海洋生态环境保护提供数据基础及技术支撑。     

顶空固相微萃取-气相色谱三重四极杆串联质谱同时测定饮用水中9种嗅味物质

针对新国标背景下饮用水不同异味类型致嗅物的同时检测需求,建立了基于顶空固相微萃取与气相色谱三重四极杆串联质谱联用的内标法同时测定9种关键致嗅物的分析方法。分析了萃取纤维类型、盐浓度、萃取温度、萃取和解析时间等条件对萃取效果的影响,优化后的测试条件为：使用CAR/PDMS-85 μm萃取纤维,氯化钠投加量为3 g,内标浓度为100 ng·L⁻¹,将10 mL水样于65 ℃条件下萃取30 min,250 ℃条件下解析300 s。该方法9种嗅味物质的标准曲线具有良好的线性 (R² >0.995) ,检出限为0.2~1.5 ng·L⁻¹,在超纯水、自来水和水源水中的加标回收率分别为84.0%~115% (10 ng·L⁻¹) 、80.5%~112% (50 ng·L⁻¹) 、88.8%~111% (250 ng·L⁻¹) ,相对标准偏差小于16%,满足样品定量分析要求。采用优化后的方法测定南方某水库水样,二甲基二硫醚 (12.1~41.6 ng·L⁻¹) 、二甲基三硫醚 (9.9~11.6 ng·L⁻¹) 、β-环柠檬醛 (5.8~13.1 ng·L⁻¹) 、2-甲基异莰醇 (11.1~25.3 ng·L⁻¹) 和土臭素 (5.6~8.7 ng·L⁻¹) 均有检出。     

液液萃取 — 超高效液相色谱 — 三重四级杆质谱测定地表水中19种磺胺类药物残留

建立了液液萃取—超高效液相色谱—三重四级杆质谱技术,测定地表水中19种磺胺类药物。通过乙酸乙酯超声萃取水样中的磺胺类药物,并用0.1%(体积分数)甲酸水溶液-甲醇作为流动相,C18色谱柱分离,在多反应监测(MRM)模式下测定。优化了萃取剂种类和用量、超声时间、流动相的组成等条件。在优化条件下,19种磺胺类药物在0.1～40.0μg/L范围内线性良好且相关系数均大于0.999 0,方法检出限为0.02～0.80ng/L,平均回收率为73.5%～92.8%,相对标准偏差为1.2%～8.7%。该方法操作简单、灵敏度高、所需样品及有机溶剂少,适用于实际的分析检验工作。     

固相萃取与气相色谱-质谱联用测定水中痕量多环芳烃

采用固相萃取与气相色谱-质谱联用测定水中痕量多环芳烃(PAHs)。通过正交试验,得到最佳固相萃取条件为:上样流速为5mL/min、采用二氯甲烷洗脱、洗脱剂用量为3mL、洗脱流速为2mL/min。测定结果显示,固相萃取与气相色谱—质谱联用技术对萘、菲、荧蒽3种PAHs的检出限为0.03～0.07μg/L,加标回收率为70%～100%,相对标准偏差为3.90%～9.58%。该方法精密度高、准确度好,能满足实际水样中痕量PAHs的测定要求。     

固相萃取—气相色谱—质谱测定再生水中邻苯二甲酸酯类物质

探讨了一种再生水中邻苯二甲酸酯类物质的测定方法——固相萃取—气相色谱—质谱,检测了相关再生水标准中涉及的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类物质。在质量浓度为20～1 000μg/L时,两类物质的回归方程的相关系数均大于0.999,检出限分别是0.060、0.002μg/L,DBP、DEHP的相对标准偏差分别为4.1%～7.4%、5.1%～6.1%。利用固相萃取技术进行预处理,平均加标回收率为96.6%、89.6%。检测了北京市4座再生水厂出水中DBP和DEHP含量,其中,DBP在1.74～5.59μg/L,低于《城市污水再生利用景观环境用水水质》(GB/T 18921—2002)规定的限值(不超过0.1mg/L),但高于《城市污水再生利用地下水回灌水质》(GB/T 19772—2005)规定的限值(不超过3μg/L);DEHP在0.42～4.93μg/L,满足GB/T 19772—2005要求(不超过8μg/L)。     

固相微萃取-气相色谱-质谱法测定地毯中总挥发性有机化合物

建立了一种固相微萃取与气相色谱质谱联用测定地毯中总挥发性有机化合物的方法,该方法简便快速,重现性好,分析结果同小型环境平衡舱法测定的结果比较吻合。     

高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调pH值至7.0左右,过固相萃取小柱进行富集,用14 mL甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250 μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(>0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/mL)和58.0%~107.8%(加标水平50 ng/mL),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5 ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

固相微萃取-气相色谱-质谱法测定地毯中总挥发性有机化合物

建立了一种固相微萃取与气相色谱-质谱联用测定地毯中总挥发性有机化合物的方法，该方法简便快速，重现性好，分析结果同小型环境平衡舱法测定的结果比较吻合。     

多壁碳纳米管固相萃取—高效液相色谱法测定水中7种三唑类农药残留

应用多壁碳纳米管自制固相萃取柱富集、净化,以乙腈-水为流动相,用乙酸乙酯洗脱,高效液相色谱进行分析检测,建立了环境水样中7种三唑类农药残留分析的方法。结果表明,在0.05~10.00mg/L线性范围内,方法检出限为0.000 9~0.047 7mg/L;农药的加标水平在0.25~1.00mg/L时,加标回收率为72.28%~106.60%,相对标准偏差为1.12%~9.73%。该方法操作简单,定性、定量准确,是对水样中三唑类农药残留液相色谱分析较理想的一种方法。     

顶空箭型固相微萃取—气相色谱—串联质谱法测定水中9种藻致异味物质

通过单因素设计实验考查萃取时间、萃取温度和氯化钠加入量对9种藻致异味物质(2-甲基异莰醇、土臭素、2-异丙基-3-甲氧基吡嗪、2-异丁基-3-甲氧基吡嗪、2,4,6-三氯苯甲醚、2,3,6-三氯苯甲醚、2,3,4-三氯苯甲醚、β-紫罗兰酮、β-环柠檬醛)萃取效果的影响,并通过响应面设计进一步优化得到顶空箭型固相微萃取的条件,建立了顶空箭型固相微萃取—气相色谱—串联质谱法高效测定水中9种典型藻致异味物质的方法,并进行方法学验证。结果表明,最佳萃取条件为每5.0 mL水样萃取时间10.0 min、萃取温度40℃、氯化钠加入量1.78 g。利用优化方法分析苏州河实际水样,检出4种藻致异味物质,加标回收率为63.8%～140.0%,精密度为0.67%～15.50%,该方法可有效应用于地表水中藻致异味物质的检测。     

Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

气质联用分析加硫酸化污泥中的有机酸

分别采用两种前处理方法分离富集加硫酸化污泥中的有机酸.方法一,利用阴离子交换树脂分离富集有机酸,在不洗脱的情况下直接和乙醇进行酯化反应,然后进行气质联用分析;方法二,利用活性炭纤维吸附型固相微萃取(ACF-SPME)的方法,顶空萃取分离后进行气质联用分析.两种方法的分析结果都未检测到酸化污泥中存在短链的有机酸,只检测到个别长链的和带苯环结构的有机酸.     

水体中17种持久性和可迁移有机污染物的检测

持久性和移动性有机污染物 (persistent and mobile organic contaminants, PMOCs) 在环境中降解缓慢,并且可以通过水体循环进行迁移。由于缺乏水体中PMOCs的高效富集和准确测定方法,导致关于PMOCs在水体中存在水平的可靠监测数据较少。通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了同时检测水中17种PMOCs的分析方法。采用HLB固相萃取柱对水样中的PMOCs进行富集,乙腈和含10 mmol·L⁻¹乙酸铵的水溶液作为流动相进行梯度洗脱,PMOCs检出限为0.04~0.35 ng·L⁻¹,定量限为0.13~1.16 ng·L⁻¹,回收率为65.01%~98.65%。在北京潮白河、广东北江和河北滹沱河进行布点采样,并测定其PMOCs的质量浓度。实验结果表明：17种PMOCs在潮白河、北江和滹沱河中均有检出,其ƩPMOCs平均质量浓度分别为604.69、740.45和505.11 ng·L⁻¹。潮白河地表水中安赛蜜、金刚烷胺和己内酰胺的质量浓度相对较高,分别高达261.75、143.84和153.71 ng·L⁻¹。北江中安赛蜜、磷酸三 (2-氯丙基) 酯和己内酰胺的质量浓度相对较高,分别高达433.14、444.46和108.76 ng·L⁻¹。滹沱河中金刚烷胺、己内酰胺和磷酸三 (2-氯丙基) 酯的质量浓度较高,分别高达218.10、101.14和222.60 ng·L⁻¹。本研究结果可为地表水和地下水水体中PMOCs的检测评价提供参考。     

在线固相萃取液质联用法测定饮用水源中的痕量联苯胺

建立了在线固相萃取液相色谱串联质谱法测定水中痕量联苯胺的方法。样品经自动进样器注入在线固相萃取小柱后,用富集泵流动相实现对样品的富集洗脱,然后用分析泵流动相将样品从富集柱冲洗至色谱柱后用串联质谱仪进行检测。该方法可在11 min内自动完成对样品的富集、净化、进样和检测过程。当进样量为5 mL时,联苯胺在0.010~2.0 μg·L-1范围内具有良好的线性关系,相关系数R为0.999,检出限为0.8 ng·L-1,实际水样的回收率为85%~104%。该方法具有简单、快速、重现性好、灵敏高等特点,可用于环境水体中痕量联苯胺的检测。     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China

Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H₂O (ERY-H₂O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.