Analysis of bromate in drinking water using liquid chromatography-tandem mass spectrometry without sample pretreatment

An analytical method for determining bromate in drinking water was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The (18)O-enriched bromate was used as an internal standard. The limit of quantification (LOQ) of bromate was 0.2 μg/L. The peak of bromate was separated from those of coexisting ions (i.e., chloride, nitrate and sulfate). The relative and absolute recoveries of bromate in two drinking water samples and in a synthesized ion solution (100 mg/L chloride, 10 mg N/L nitrate, and 100 mg/L sulfate) were 99-105 and 94-105%, respectively. Bromate concentrations in 11 drinking water samples determined by LC-MS/MS were <0.2-2.3 μg/L. The results of the present study indicated that the proposed method was suitable for determining bromate concentrations in drinking water without sample pretreatment.     

Determination of trace concentrations of bromate in municipal and bottled drinking waters using a hydroxide-selective column with ion chromatography

The International Agency for Research on Cancer determined that bromate is a potential human carcinogen, even at low micro/l levels in drinking water. Bromate is commonly produced from the ozonation of source water containing naturally occurring bromide. Traditionally, trace concentrations of bromate and other oxyhalides in environmental waters have been determined by anion exchange chromatography with an IonPac AS9-HC column using a carbonate eluent and suppressed conductivity detection, as described in EPA Method 300.1 B. However, a hydroxide eluent has lower suppressed background conductivity and lower noise compared to a carbonate eluent and this can reduce the detection limit and practical quantitation limit for bromate. In this paper, we examine the effect of using an electrolytically generated hydroxide eluent combined with a novel hydroxide-selective anion exchange column for the determination of disinfection byproduct anions and bromide in municipal and bottled drinking water samples. EPA Methods 300.1 B and 317.0 were used as test criteria to evaluate the new anion exchange column. The combination of a hydroxide eluent with a high capacity hydroxide-selective column allowed sub-microg/l detection limits for chlorite, bromate, chlorate, and bromide with a practical quantitation limit of 1 microg/l bromate using suppressed conductivity detection and 0.5 microg/l using postcolumn addition of o-dianisidine followed by visible detection. The linearity, method detection limits, robustness, and accuracy of the methods for spiked municipal and bottled water samples will be discussed.     

超高效液相色谱-串联质谱法同时测定塑料包装矿泉水中11种双酚类化合物

建立了同时测定塑料包装矿泉水中11种双酚类化合物的超高效液相色谱-串联质谱（UPLC-MS/MS）分析方法。以真空冷冻干燥的方法对样品进行前处理。使用Waters ACQUITY UPLC BEH C₁₈色谱柱（100 mm×2.1 mm,1.7 μm）进行分离,以甲醇和0.1%（v/v）氨水为流动相对目标物进行梯度洗脱。在电喷雾负离子模式及多反应监测（MRM）模式下进行定性和定量分析。结果表明,11种双酚类化合物在线性范围内线性关系良好,线性相关系数（R²）均大于0.997;目标物的检出限为0.01~1.00 μg/L;3个加标水平下的回收率为75.3%~102.1%,相对标准偏差为1.5%~8.9%。本方法准确、简便、快速,可用于塑料包装矿泉水中双酚类化合物的实际检测。     

Determination of Bromate in Bottled Drinking Water from Saudi Arabian Markets by HPLC/ICP-MS

The determination of bromate BrO₃ ^? in 50 different bottled drinking water samples collected from Saudi Arabian markets has been investigated using liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS). For analysis, samples were injected directly without any further pretreatment or dilution, using only a 50 μL injection volume. The method showed: detection limit of 0.5 μg/L, limit of quantification of 1.0 μg/L, 1.0 ? 200.0 μg/L linearity range (r² = 0.9998), relative standard deviation (%RSD) for reproducibility (inter-day precision) values of 14% and 4% for low and high concentration levels (10,100 μg/L), respectively. The results obtained for bromate showed that 30% of the samples are acceptable as US EPA standards (10 μg/L), 40% of the samples are acceptable as Gulf (Saudi Arabia) standards (25 μg/L), and almost 60% of the samples exceed the allowable limits for bromate in bottled drinking water.     

抑制型电导检测离子色谱法测定饮用水中的痕量溴酸盐

建立一种直接进样测定饮用水中痕量溴酸盐的电导检测离子色谱法。选用Metrosep A Supp 5阴离子交换分离柱,碳酸盐淋洗液。抑制型电导检测采用化学抑制器和CO2抑制器顺序双抑制系统。实验结果显示,溴酸根阴离子与常见共存阴离子完全分离,溴酸盐含量在5~100 μg/L范围内具有良好的线性(r=0.9999),精密度高(相对标准偏差（RSD）<4%),方法的检出限为0.50 μg/L,样品加标平均回收率为96.1%~107%。该方法操作简单,分离效果好,可与常见阴离子实现同时分析,灵敏度高,重现性好,可作为饮用水中溴酸盐的标准测定方法。     

离子色谱法测定饮用水中痕量溴酸盐

建立了一种利用离子色谱法测定饮用水中痕量溴酸盐(BrO<,3><'->)的方法.色谱条件为:IonPac AS19(250mm x4 mm)色谱柱分离,KOH 梯度淋洗,流速1.0 mL/min,抑制电导检测,外标法定量.BrO<,3><'->浓度在2.0～100μg/L范围内有良好的线性,检出限为0.3 ng/mL,...     

在线固相萃取-超高效液相色谱-三重四极杆质谱法测定水源水和饮用水中107种典型农药及代谢产物

为进行我国水体中农药风险监测,针对水体中农药种类多、浓度低的特点,建立了在线固相萃取-超高效液相色谱-串联质谱法快速筛查和检测水源水及饮用水中107种典型农药及代谢产物(有机磷类、有机氮类、有机杂环类、氨基甲酸酯类、酰胺类、苯甲酰脲类、新烟碱类等)的方法。样品经0.22 μm孔径亲水性聚四氟乙烯滤膜过滤后,通过自动进样器取5 mL样品注入在线固相萃取系统,经X Bridge C₁₈在线固相萃取柱吸附后用纯水淋洗,以乙腈和0.1%甲酸水溶液为流动相对在线固相萃取柱梯度洗脱后再经ACQUITY HSS T₃色谱柱分离,采用电喷雾离子源正离子及负离子模式分析检测,外标法定量。以水源水及饮用水作为基质,对其准确度和精密度进行方法学验证,结果表明:107种农药及代谢产物在不同范围内线性关系良好(r²>0.995),方法检出限(LOD, S/N=3)为0.03~1.5 ng/L,定量限(LOQ, S/N=10)为0.1~5.0 ng/L。将目标分析物在1、20、50 ng/L水平下加标,水源水和饮用水中的加标回收率分别为60.6%~119.8%和61.2%~119.0%,相对标准偏差(RSD, n=6)分别为0.3%~18.6%和0.4%~17.1%。用该方法测定水源水和饮用水中的农药残留,结果显示,酰胺类、三嗪类除草剂、三唑类杀菌剂与烟碱类、氨基甲酸酯类杀虫剂有较高的检出率,其中水源水中检出含量为0.1~97.1 ng/L,饮用水中检出含量为0.1~93.6 ng/L。该方法适用于水源水和饮用水中107种典型农药及代谢产物的痕量分析测定,有效提高了水体中农药类物质的检测效率,实际应用价值较高。     

Determination of bromate ion in drinking water by capillary zone electrophoresis with direct photometric detection

Bromate ion in drinking water was determined by capillary zone electrophoresis (CZE) with direct photometric detection. Bromate ion in the sample solution was introduced and concentrated into the capillary by electrokinetic injection for 50s at -10 kV. Electrophoretic separation was made at an applied voltage of -25 kV and bromate ion was detected at wavelength 193 nm, at which the baseline was stabilized with less UV-absorbing acidic phosphate buffer. Bromate ion was detected within 5 min in the electropherogram. By increasing the electric conductivity in the migrating solution with 10 mM Na2SO4, a limit of detection (LOD) of 9 x 10(-10)M (0.1 microg/L BrO3-) was achieved. The proposed method was applied to the analysis of tap water and river water samples, but bromate ion was not detected. Because the practical samples contain relatively large amount of foreign ionic substances, the tap water sample was diluted to avoid the matrix ions. Bromate ion added in a tap water at the concentration of 8 x 10(-8)M was quantitatively recovered by diluting it 1/10.     

UPLC-MS/MS同时测定水质中诺氟沙星和氧氟沙星

建立了超高效液相色谱―串联质谱/质谱法(HPLC-MS/MS)同时测定水质中诺氟沙星和氧氟沙星的分析方法。试样经HLB柱净化和C18柱分离,采用电喷雾离子源(ESI),正离子扫描,多反应监测(MRM)模式进行检测,外标法定量。结果表明,诺氟沙星和氧氟沙星在2~100?g/L浓度范围内线性关系良好,空白样品加标回收率均大于85%,相对标准偏差小于10%,诺氟沙星和氧氟沙星方法检出限(LOD)均为0.5 ng/m L,定量限为2 ng/m L。该方法准确、灵敏、操作相对简便,适用于同时测定水质中诺氟沙星和氧氟沙星。     

饮用水中痕量溴酸盐分析方法的研究进展

溴酸盐是用臭氧对饮用水进行消毒时产生的一种副产物,是一种潜在的致癌物。本文介绍了溴酸盐的形成、危害以及分析方法等,并着重对近年来溴酸盐的分析方法进行了详细的综述。     

Sulphonamide Residues in Italian Surface and Drinking Waters: A Small Scale Reconnaissance

The occurrence of antibiotics in the aquatic environment is an important emerging issue due to potential adverse effect of these compounds on ecosystem and human health. For a correct environmental risk assessment there is a need for appropriate analytical methods for monitoring antibiotic residues in a variety of water matrices. This paper describes a method for the determination of eleven sulphonamide compounds in surface and drinking waters using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Recoveries of the analytes in both surface and drinking water matrices at different fortification levels, always exceed 87%; the limits of quantification in surface water samples are between 0.005 and 0.021 μg L⁻¹ depending on the compound, and the interday method precision is less than 12%. Matrix effects were evaluated in drinking and surface water samples. The method has been applied to a small scale reconnaissance of river, lake, mineral and municipal water samples; results indicate the occurrence of sulphonamides in some surface and mineral waters analyzed.     

Trace analysis of bromate in drinking waters by means of on-line coupling IC-ICP-MS

The on-line-coupling of ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool for the determination of bromate in drinking waters. The use of a high-capacity and high-performance anion-exchanger combined with an NH₄NO₃-based elution system allows the determination of bromate in almost every water sample without any sample pretreatment. The method detection limits in the water samples investigated are 50 to 65 ng/L or 44 to 58 pg bromate, respectively. Considering sensivity as well as imprecision (5% at 500 ng/L bromate) and short analysis times (8 to 15 min per sample including sample uptake), the described IC-ICP-MS coupling is well suited for precise routine analyses of bromate in drinking waters at the sub μg/L level.     

微波浓缩-离子法测定饮用水中的痕量溴酸根和高氯酸根

 建立了一种简便的用于浓缩水中痕量BrO3 -和ClO4 -的样品前处理方法。水样经OnGuardAg柱过滤 ,用微波炉在 15min内可浓缩 2 0倍 ,所测离子的回收率均高于 90 %。又采用IonPacAS16型亲水性柱 ,用 15 0 μL定量环 ,以NaOH为流动相、梯度淋洗方式 ,在 35min内测定了包括BrO3 -和ClO4 -在内的 8种离子。BrO3 -和ClO4 -的检测限分别为 0 10 μg/L和 0 2 0 μg/L。该方法在实际应用中有较大的参考价值。     

柱后衍生离子色谱法同时测定瓶装水中的碘酸根、亚氯酸根和溴酸根

水中的碘酸根、亚氯酸根和溴酸根是重要的消毒副产物,主要通过大体积浓缩后直接电导检测,或通过柱前或柱后化学反应将目标物转化成容易检测的物质后检测。本方法采用大体积进样柱后衍生紫外检测的分析方法,通过条件优化获得了较高的灵敏度和信噪比。利用一套自动分析系统,可以满足饮用水中痕量碘酸根、亚氯酸根、溴酸根的同时监测。碘酸根、亚氯酸根和溴酸根的检出限分别为0.5,0.4,0.1 μg/L。对于不同的加标样品,碘酸根、亚氯酸根和溴酸根的回收率分别为70.8%~98.0%,92.4%~100%和93.2%~104.1%。该方法应用于北京市场上的瓶装饮用水分析,结果显示瓶装纯净水中的碘酸根、亚氯酸根、溴酸根浓度均低于检出限,而瓶装矿泉水中碘酸根、溴酸根的最高含量分别达到9.4 μg/L和78.4 μg/L。     

Analysis of p-chlorobenzoic acid in water by liquid chromatography-tandem mass spectrometry

para-Chlorobenzoic acid (p-CBA) is typically used as a probe compound to indirectly quantify hydroxyl radicals formed during advanced oxidation processes used in drinking water and wastewater treatment. A method has been developed for the sensitive analysis of p-CBA in water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A reporting limit in water of 100 ng/L was determined for the method, which is 40-fold lower than the 4.0 microg/L reporting limit of the widely used liquid chromatography with UV detection (LC-UV) method. The method was found to be robust in difficult matrices such as wastewater and highly selective, unlike LC-UV which relies on non-specific detection at 234 nm. The detection of p-CBA below 1 microg/L during bench-scale ozonation of wastewater after hydrogen peroxide addition was demonstrated. Duplicate samples were analyzed by LC-MS/MS and LC-UV and results were found to be comparable at concentrations quantifiable by both methods.     

Chloride interference in the determination of bromate in drinking water by reagent free ion chromatography with mass spectrometry detection

Bromate, a well known by-product of the ozonation of drinking water, has been included among the substances which have to be monitored in the drinking water according to the last EC Directive 251/98 on potable water with a regulated limit of 10 microg l(-1). The need of performing routine analysis at this limit is a driving force for the developing of new simple and sensitive methods of detection, which should be also able to overcome the effect of matrix composition. This work explored the use of mass spectrometry detection with electrospray ionisation hyphenated to a reagent free ion chromatograph with hydroxide gradient elution for the determination of bromate in drinking water. The use of a high capacity hydroxide selective column operated in gradient mode allowed to avoid the interference by carbonate peak, which moved to longer retention times. The effect of increasing chloride concentrations from 0 to 250 mg l(-1), which is the guideline limit for drinking water in Directive 251/98/EC, was to decrease absolute mass spectrometric response and chromatographic efficiency and, on the consequence, to increase the effective detection limits. The effect of the chloride concentration on the detection of bromate is discussed.     

Development and validation of a liquid chromatography tandem mass spectrometry method for the analysis of β-agonists in animal feed and drinking water

A reproducible, sensitive and selective multiresidue analytical method for seven β-agonists: clenbuterol (CBT), clenpenterol (CPT), ractopamine (RTP), brombuterol (BBT), mabuterol (MBT), mapenterol (MPT), and hydroxymethylclenbuterol (HMCBT) was developed and validated by using liquid chromatography tandem mass spectrometry (LC–MS/MS) in feed and drinking water samples. The validation was achieved according to the criteria laid down in the Commission Decision 2002/657/EC, however it was necessary to use minimum required performance limits (MRPLs) proposed by the Community Reference Laboratories (CRLs) due to the lack of maximum residue limits (MRLs) for β-agonists. By setting up these MRPLs, allows controlling their use in safe mode, since β-agonists are commonly used in veterinary medicine sometime in a fraudulent manner, for increasing the weigh of animals. Values set for both matrices studied are 50 μg/kg for animal feed, and a range from 0.2 to 10 μg/L for drinking water. CCα values calculated were under the MRPLs suggested; for drinking water the lowest value obtained was 0.12 μg/L, and for animal feed 0.87 μg/kg. Values for CCβ were ranged from 0.08 to 0.13 μg/L in drinking water and from 0.5 to 0.92 μg/kg in animal feed samples. The excellence values obtained, allowed us to conclude that the proposed analytical method is capable to control the β-agonists studied in both matrices and that it can be successfully applied and used as a routine method in laboratories of residue analysis of veterinary food control.     

超高效液相色谱串联质谱快速测定饮用水中9种N-亚硝胺的新方法

N-亚硝胺是潜在的人类致癌物,是近年来关注的一类饮用水消毒副产物,同时也是环境分析研究的热点.本文建立了超高效液相色谱(UPLC)串联质谱快速测定饮用水中9种N-亚硝胺的新方法,讨论了色谱柱和流动相对分离9种N-亚硝胺的影响,优化了多级反应质谱(MRM,MS/MS)条件.二甲基亚硝胺-d6为贮存和回收率内标,亚硝基二丙...     

Sensitive Determination of Five Priority Haloacetic Acids by Electromembrane Extraction with Capillary Electrophoresis

A method for sensitive determination of five priority haloacetic acids in drinking water has been developed for the first time based on electromembrane extraction (EME) prior to CZE with capacitively coupled contactless conductivity detection (CZE‐C⁴D). The target analytes were extracted from 10 mL of the sample solution (donor phase), through the supported liquid membrane (using a polypropylene membrane supporting 1‐octanol), and into 10 µL of 50 mmol/L NaAc solution (acceptor phase). The extracted solution was directly analyzed by CZE‐C⁴D without derivatization. Several factors that affect separation, detection and extraction efficiency were investigated. Under the optimum conditions, five haloacetic acids (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid) could be well separated from other components coexisting in water samples within 23 min, exhibiting a linear calibration over two orders of magnitude (r?0.9943); the enrichment factors at 430–671 were obtained in a 30 min of extraction, and the limits of detection were in the range of 0.17–0.61 ng/mL. The intraday relative standard deviations for peak areas investigated at 10 ng/mL were between 1.2% and 9.7% for the combined EME‐CZE‐C⁴D procedure. This approach offers an attractive alternative to the officially proposed method for purified drinking water analysis, which requires derivatization procedure prior to gas chromatography analysis.     

超高效液相色谱-电喷雾串联质谱法测定生活饮用水中49种药物及5种代谢物

建立了超高效液相色谱-电喷雾串联质谱(UPLC-ESI MS/MS)分析生活饮用水中54种药物的方法。采用HLB固相萃取柱对水样中的目标化合物进行富集净化,以5 mL甲醇洗脱;洗脱液用氮气吹至近干,用0.4 mL 0.1%甲酸水溶液定容,上机分析;ACQUITY UPLC^TMBEH C₁₈柱用作色谱分离,以0.1%甲酸水溶液-甲醇为流动相进行梯度洗脱;多反应监测(MRM)模式进行检测;目标药物使用基质外标法定量。54种药物在自备井水、市政末梢水和地表水中的加标回收率分别为58.7%~104.4%、53.1%~109.5%和50.7%~118.8%,相对标准偏差(n=6)分别为0.3%~12.8%、1.0%~15.5%和0.4%~19.3%;方法定量限为0.002~5.000 ng/L。将建立的方法应用于北京部分自备井水、市政末梢水和地表水样品的分析,结果在自备井水样中检出26种药物。