水环境中磺胺类抗生素固相萃取-液质联用检测方法的建立及效果评估

为快速、同步检测分析磺胺类抗生素,有效削减并控制水体中磺胺类上抗生素含量,基于已有检测仪器和分析测试方法,建立了一种用于同时测定水体中8种磺胺类抗生素(磺胺氯哒嗪、磺胺间二甲氧嘧啶、磺胺二甲基嘧啶、磺胺甲恶唑、磺胺喹恶啉、磺胺甲氧哒嗪、磺胺甲噻二唑、磺胺吡啶)残留的固相萃取-液相色谱-三重四极杆串联质谱检测方法;在检测过程中,调节水样的pH为3,用HLB固相萃取柱进行净化、富集,在40 ℃条件下用氮吹浓缩吹干,用超纯水复溶至1 mL;以0.1%甲酸水溶液和0.1%甲酸乙腈溶液作为流动相,使用Phenomenex Kinetex F5 色谱柱(50 mm×3.0 mm, 2.6 μm)进行分离,在多反应监测模式(MRM)下对样品进行定量、定性分析。结果表明：8种磺胺类抗生素线性关系良好,且拟合度均大于0.999 0;检出限为0.1~0.5 μg·L⁻¹,定量限为0.5~2.0 μg·L⁻¹;质量浓度为1、5、50 μg·L⁻¹的混标溶液的加标回收率分别为78.85%~127.96%、76.69%~114.38%和73.55%~125.92%, 相对标准偏差均在15%以内。该方法快捷、高效、灵敏,能够满足水中磺胺类抗生素的定性、定量检测,可为我国检测方法标准体系的建设提供参考。     

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。     

百菌清农药残留的SPE-GC检测

对环境水样中百菌清农药残留进行了SPE-GC分析方法研究。环境水样通过Florisil柱富集、净化,3 mL乙酸乙酯洗脱,GC-ECD进行分析检测。实验表明,百菌清农药残留在0.01~10 mg/L范围内线性关系良好,相关系数为0.9993。外标法定量,检出限为0.0035 mg/L,对实际水样进行加标回收,回收率范围在93.47%~100.14%之间,6次重复测定相对标准偏差在3.97%~4.96%之间,并将方法应用于周边环境地表水的检测。该方法具有简便,快速,准确,灵敏度高等特点,能满足环境水样中农药残留分析要求。     

固相萃取-毛细管气相色谱法测定蔬菜、土壤和水中的毒死蜱残留量

采用固相萃取技术提取蔬菜、土壤和水体中毒死蜱,建立了蔬菜、土壤和水体中毒死蜱的固相萃取-气相色谱测定方法,并与传统方法进行了比较。添加浓度为0.1、1、10 mg·L-1,两种方法的水样平均回收率分别在93.7%~102.7%和96.2%~100.2%,变异系数分别在2.2%~7.7%和3.3%~5.1%;土壤平均回收率分别在91.3%~100.7%和92.0%~104.8%,变异系数分别在1.4%~7.0%和0.3%~5.2%;蔬菜平均回收率分别在89.4%~101.4%和92.5%~101.8%,变异系数分别在5.2%~7.1%和3.1%~6.0%。试验结果表明,固相萃取法与传统方法的回收率和变异系数相当,但前者更加省时、省力和省溶剂。     

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。     

水体中27种有机磷阻燃剂(OPFRs)的检测及风险评价

有机磷阻燃剂(organophosphorus flame retardants,OPFRs)具有致畸、致癌、致突变风险以及神经毒性作用。为了更好地研究其存在水平和健康风险,建立了固相萃取与高效液相色谱-串联质谱仪和气相色谱-质谱联用仪检测水体中27种OPFRs的分析方法,并对OPFRs进行了健康风险评价。20种OPFRs采用MCX固相萃取柱预处理和LC-MS/MS进行检测,以甲醇和含10 mmol·L⁻¹的甲酸水溶液作为流动相进行梯度洗脱,7种OPFRs采用HLB串联Envi-18固相萃取柱进行预处理并利用GC-MS进行检测。检测结果表明,27种OPFRs的检出限为0.02~2.53 ng·L⁻¹;定量限为0.06~8.43 ng·L⁻¹;回收率为65.82%~108.48%。2021年4月份,采集北京市潮白河地表水和地下水8个水样并检测其OPFRs。实测结果表明：除磷酸三(2-异丙基苯)酯、磷酸异癸基二苯酯、磷酸叔丁基苯二苯酯、磷酸二苄酯外,其余23种OPFRs均有不同程度检出,质量浓度为0~973.17 ng·L⁻¹;磷酸三(2-乙基己基)酯、磷酸三乙酯、磷酸三丙酯、磷酸三异丙酯含量相对较高,分别高达973.17、459.90、315.47、298.41 ng·L⁻¹。采用USEPA模型对水样中的OPFRs进行了健康风险评价, 13种OPFRs的非致癌风险值为0~6.17×10⁻⁴,4种OPFRs致癌风险值为1.37×10⁻⁹~1.07×10⁻⁷;在高暴露条件下,OPFRs的非致癌风险值为1.61×10⁻⁵~6.17×10⁻⁴,致癌风险值为1.00×10⁻⁸~1.07×10⁻⁷,均低于风险阈值。上述结果说明,水体中OPFRs产生的健康风险处于较低水平。此次采集的潮白河地表水和地下水水中OPFRs的致癌风险和非致癌风险均处于较低水平。本研究结果可为地表水和地下水水体中OPFRs的检测及风险评价提供参考。     

活性炭纤维固相微萃取-气质联用色谱测定废煤气脱硫剂中的萘

采用活性炭纤维固相微萃取-气质联用色谱法测定废煤气脱硫剂中的萘含量,探讨了萃取方式、萃取时间、萃取温度、解吸条件对萃取效率的影响.结果表明,最优萃取条件为40℃下顶空萃取10 min,260℃下解吸2 min.最优萃取条件下,检测方法的线性范围为200～870 mg/L,相关系数为0.998,检测限为10 ng/L.利...     

SPE-HPLC法检测环境水样中的痕量三氯卡班

建立了环境水样中三氯卡班(TCC)的预处理和测定方法。考察了3种固相萃取(SPE)小柱、5种洗脱液对TCC回收率的影响。结果表明,采用ENVI-18 SPE小柱、以乙酸乙酯/乙腈(1:1)为洗脱液、高效液相色谱仪-紫外检测器(HPLC-UV)检测,以蒸馏水为背景溶液TCC的加标回收率高达95%,仪器检出限与定量限分别为2.37与7.89μg/L。该方法用于实际环境水样,TCC加标浓度1~10μg/L,污水厂进水、出水与地表水中TCC的加标回收率分别在89.38%~96.90%、87.74%~94.34%与83.64%~94.61%之间,表明所建立的SPE-HPLC法适合城市生活污水和地表水中痕量TCC的检测。运用该方法测定实际环境水样中的TCC含量,集美污水处理厂进水与出水中TCC浓度分别为1.35与0.22μg/L;华大污水厂进水与出水中TCC浓度分别为1.05与0.53μg/L;白鹭湖水样中的TCC浓度为1.11μg/L。     

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。     

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。     

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。     

固相萃取-液相色谱-三重四极杆串联质谱测定养殖废水中17种氟喹诺酮类抗生素

采用固相萃取-液相色谱-三重四极杆串联质谱(SPE-LC-MS/MS)技术,建立了养殖废水中17种氟喹诺酮类抗生素(FQs)的测定方法。水样在采用固相萃取法富集前,先用 0.45 μm 的聚四氟乙烯滤膜过滤,而后加入5%甲醇(体积比),用盐酸溶液将水样pH调节至2.0±0.5,经固相萃取柱富集,最后用9 mL 0.1%甲酸甲醇洗脱。以C18柱为分离柱,0.1%甲酸−5 mmol·L⁻¹ 甲酸铵水溶液和甲醇为流动相,采用液相色谱－三重四极杆串联质谱多反应监测离子模式(MRM)对目标化合物进行了检测和分析。在优化实验条件下,17种FQs的线性范围为0.50 -100 μg·L⁻¹时,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0.08-0.3 ng·L⁻¹。在加标量为0.01 μg·L⁻¹和0.09 μg·L⁻¹时,空白加标的平均回收率为58.6%-104.2% 和65.3%-91.0%,相对标准偏差(RSD)在2.1%-19.3%(n=6)。以养殖废水为基质,17种FQs的加标回收率在47.8%-118.7%,RSD小于20%(n=6)。应用该方法测定了广州某水产养殖场的养殖废水。结果表明,氧氟沙星检出浓度最高(9.36 ng·L⁻¹),达氟沙星次之(5.96 ng·L⁻¹)。该方法快速、准确,可适用于养殖废水中17种FQs的测定。     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

GC-ECD和LC-MS/MS测定垃圾焚烧飞灰中氯苯和氯酚的方法

氯苯和氯酚是生活垃圾焚烧过程产生的重要污染物,目前对垃圾焚烧炉飞灰中氯苯和氯酚的研究较少。本文采用超声萃取法结合GC-ECD、LC-MS/MS,建立了飞灰等固体介质中的氯苯氯酚的定量检测方法,通过实验确定出较优的前处理条件,飞灰样品中滴加少量浓硫酸,以正己烷/丙酮（1：1）为萃取溶剂,40℃超声萃取20 min,萃取3次,然后液相萃取分离氯酚氯苯,分别净化,浓缩,最后进机检测,对三、四、五、六氯代苯和所有的氯酚均获得较好的回收率。应用建立的检测方法测试了3座正常运行过程中的生活垃圾焚烧炉飞灰的氯苯和氯酚含量,样品中一到四氯代氯酚的含量都在定量限以下,五氯酚含量范围为5~11 ng·g-1,三氯苯、四氯苯、五氯苯和六氯苯的含量在3~70 ng·g-1的范围。     

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)。     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Simultaneous and direct determination of glyphosate and AMPA in water samples from the hydroponic cultivation of eucalyptus seedlings using HPLC-ICP-MS/MS

Abstract

Glyphosate is the main herbicide currently used in the world due to wide applicability and efficiency in controlling weeds in many crops. However, its overuse may lead to undesirable impacts on the environment and to human health in the long run. This present study aimed to optimize and validate solid phase extraction (SPE) using an anionic resin for the simultaneous and direct determination of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using high-performance liquid chromatography combined with inductively coupled plasma with triple quadrupole mass spectrometer (HPLC-ICP-MS/MS). The results showed that recovery percentage and relative standard deviation were 103.9?±?7.9 and 99.40?±?9.9% for glyphosate and AMPA, respectively. The validation certified that the method was precise, accurate, linear, and selective, with a limit of quantification of 1.09 and 0.29?μg L^?1 for glyphosate and AMPA, respectively. The optimized methodology reached the concentration factor of 250 times and was successfully applied to analyze water samples from hydroponic cultivation of the eucalyptus seedlings. The results showed that the exudation process occurs at glyphosate doses starting from 2?L ha^?1.     

Solid phase extraction with silicon dioxide microsphere adsorbents in combination with gas chromatography-electron capture detection for the determination of DDT and its metabolites in water samples

The goal of the present study was to investigate the feasibility of silicon dioxide (SiO₂) microspheres without special modification to enrich dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p′-dichlorodiphenyl-2,2-dichloroethylene (p,p′-DDD) and p,p′-dichlorodiphenyldichloroethylene (DDE) in combination with gas chromatography-electron-capture detection. The experimental results indicated that an excellent linear relationship between the recoveries and the concentrations of DDT and its main metabolites was obtained in the range of 0.2–30 ng mL^?1 and the correlation coefficients were in the range of 99.96–99.99%. The detection limits based on the ratio of signal to the baseline noise (S/N = 3) were 2.2, 2.9, 3.8 and 4.1 ng L^?1 for p,p′-DDD, p,p′-DDT, o,p′-DDT, and p,p′-DDE, respectively. The precisions of the proposed method were all below 10% (n = 6). Four real water samples were utilized for validation of the proposed method, and satisfactory spiked recoveries in the range of 72.4–112.9% were achieved. These results demonstrated that the developed method was a simple, sensitive, and robust analytical method for the monitoring of pollutants in the environment.