Determination of haloacetic acids in hospital e uent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

我国淡水环境中卤乙酸类消毒副产物的预测无效应浓度研究

新型冠状病毒肺炎（COVID-19,简称“新冠肺炎”）疫情期间,消毒剂超量使用,导致大量DBPs（disinfection by-products,消毒副产物）进入自然水体,可能对水生态环境产生不良影响.以5种HAAs（卤乙酸类）消毒副产物（一氯乙酸、二氯乙酸、三氯乙酸、一溴乙酸和二溴乙酸）为研究目标,基于筛选的本土水生生物的毒性数据,采用欧盟《风险评价技术指导文件》中的评估系数法和平衡分配法分别推导了5种HAAs在水体和沉积物两种介质中的PNEC（预测无效应浓度）值.结果表明:5种HAAs对水生生物的急、慢性毒性大小顺序均为一溴乙酸>一氯乙酸>二氯乙酸>三氯乙酸>二溴乙酸;5种HAAs（一氯乙酸、二氯乙酸、三氯乙酸、一溴乙酸和二溴乙酸）的PNEC_w（水体的预测无效应浓度）分别为0.025、0.030、0.060、0.016和1.956 mg/L,PNEC_s（沉积物的预测无效应浓度）分别为0.021、0.026、0.057、0.013和1.679 mg/kg（以湿质量计）.研究显示,污水处理厂出水中排放的DBPs对水生态环境可能造成潜在的风险和危害,应加强对污水处理厂出水中5种HAAs的监测和去除,从而减少排入到自然水体中的HAAs含量.      

膜生物反应器处理城市污水的后续次氯酸钠消毒研究

针对膜生物反应器（membrane bioreactor,MBR）处理城市污水的后续次氯酸钠消毒,分别开展了不同氯的投加剂量对指示微生物（总大肠菌群和粪大肠菌群）的灭活效果、消毒副产物（disinfection by-products,DBPs）生成量以及消毒后出水发光菌急性毒性研究.结果表明,在工程应用中MBR处理工...     

北京市饮用水中溴酸盐、卤代乙酸及高氯酸盐研究

调查了北京市饮用水厂源水及出厂水中消毒副产物溴酸盐、卤代乙酸及典型污染物高氯酸盐的污染现状,研究了其来源及环境影响因素.结果表明,北京市饮用水中基本不含溴酸盐;含有5种卤代乙酸和高氯酸盐.饮用水加氯消毒是产生卤代乙酸的主要原因.在所调查水厂出厂水中卤代乙酸的平均浓度为42.1～149.5μg/L;其中含氯卤代乙酸占总量的90%以上.5种卤代乙酸的含量顺序为三氯乙酸>二氯乙酸>氯溴乙酸>二溴乙酸>一溴二氯乙酸.饮用水中卤代乙酸受季节影响较大,9月份浓度最高,4月份浓度最低.高氯酸盐主要存在于以地下水为源水的水厂中,受地下水污染影响较大.各水厂出厂水中高氯酸盐含量为0.1～6.8μg/L.饮用水中高氯酸盐在11月份含量最高,7月份含量最低.     

5种颗粒活性炭对水中卤乙酸的等温吸附试验

通过等温吸附实验,考察了5种不同类颗粒活性炭(GAC)对消毒副产物卤乙酸(HAAs)中致癌风险较高的二氯乙酸、三氯乙酸的吸附行为.结果表明:二氯乙酸、三氯乙酸的吸附行为符合Langmuir等温式;进口活性炭A对二氯乙酸饱和吸附量是3种国产活性炭的4.4～5.7倍,是另一种进口活性炭B的3.8倍;对三氯乙酸的饱和吸附量是3种国产活性炭的4.0～5.4倍,是另一种进口活性炭B的2.6倍.针对进口活性炭A开展的进一步研究结果表明,二氯乙酸、三氯乙酸2组分的相对吸附量与2组分的相对浓度成正比关系,二氯乙酸吸附容量变化对平衡浓度的敏感程度不如三氯乙酸.     

SPE-RRLC-MS/MS法测定制药废水中青霉素G

建立了利用固相萃取-高分离度快速液相色谱-串联质谱(SPE-RRLC-MS/MS)测定制药废水中青霉素G残留的方法。水样以30%硫酸锌+20%亚铁氰化钾作为沉淀剂沉淀蛋白质后,上清液采用Oasis HLB固相萃取柱富集和净化,以0.01 mol/L乙酸铵溶液(加0.1%甲酸)+乙腈作为流动相进行等度洗脱,经Agilent Plus C18柱分离后,在串联质谱ESI(+)源下进行MRM检测。该方法的青霉素G检出限(S/N=3)为0.02μg/L,目标物在0.0020～1.0 mg/L范围内线性关系良好,线性相关系数为0.9997。在0.20,1.0,2.0μg/L添加水平平均回收率为74.6%～101.4%,相对标准偏差为4.49%～8.17%。该方法灵敏度高、重现性好、定性定量准确,可满足制药废水中青霉素G残留检测的要求。     

GC-ECD测定地表水中的硝基苯类和氯苯类化合物

文章分别以液液萃取法和固相萃取法作为预处理方法,建立了地表水中12种硝基苯类和氯苯类化合物的气相色谱-电子捕获检测器(GC-ECD)分析检测方法,其中包括1,2-二硝基苯、1,3-二硝基苯、1,4-二硝基苯,2-硝基氯苯、3-硝基氯苯、4-硝基氯苯、1,2,3,4-四氯苯、1,2,3,5-四氯苯、1,2,4,5-四氯苯、2,4-二硝基甲苯、2,4-二硝基氯苯、2,4,6-三硝基甲苯。通过对实验条件的优化,对100 mL水样的方法检出限为液液萃取0.05⁰.15μg/L,固相萃取0.100.15μg/L,固相萃取0.10⁰.16μg/L范围内,加标回收率分别为80.7%0.16μg/L范围内,加标回收率分别为80.7%⁸8.0%和74.2%88.0%和74.2%¹01%,相对标准偏差分别在1.8%101%,相对标准偏差分别在1.8%⁵.3%和3.7%5.3%和3.7%⁵.5%之间。应用所建立的方法,对上海市地表水样进行监测分析,12种目标物质仅检出硝基氯苯,浓度为ND5.5%之间。应用所建立的方法,对上海市地表水样进行监测分析,12种目标物质仅检出硝基氯苯,浓度为ND⁰.52μg/L,样品加标回收率为液液萃取72.5%0.52μg/L,样品加标回收率为液液萃取72.5%⁸1.9%,固相萃取67.0%81.9%,固相萃取67.0%⁹1.0%。     

饮用水中卤氧化物离子色谱分析方法研究

直接大体积进样,建立生活饮用水中卤氧化物溴酸盐(BrO3-)、亚氯酸盐(ClO2-)、氯酸盐(ClO3-)含量的离子色谱(IC)法。优化的色谱条件为:Metrosep A Supp 7(250 mm)色谱柱配以Metrosep A Supp1保护柱,淋洗液为3.6 mmol/L Na2CO3与1.0 mmol/L NaHCO3;流速为0.6mL/min;进样量为100μL,抑制型电导检测器。方法结果显示:卤氧化物与常见共存阴离子完全分离,标准曲线在(5.0～400)μg/L范围内具有良好的线性关系(r>0.999),精密度高(相对标准偏差RSD<5.0%),样品加标平均回收率在90.8%~105%之间。按S/N=3,BrO3-、ClO2-、ClO3-的检出限分别为(0.9、0.7、1.0)μg/L。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,适合于饮用水中消毒副产物中溴酸盐、亚氯酸盐、氯酸盐的同时测定。     

气相色谱法测定水中九种卤代乙酸类化合物研究

建立了液-液萃取气相色谱-双柱-双检测器法测定水中九种卤代乙酸类化合物的检测方法.40 ml水样经4 ml甲基叔丁基醚两次萃取,萃取液经10%硫酸-甲醇50℃衍生后,用气相色谱电子捕获检测器检测.方法检出限为0.6~1.0μg/L,加标回收率75.9%~111%,6次测定的相对标准偏差≤16%.两次萃取显著提高了一氯乙酸和一溴乙酸的回收率,双柱-双检测器有效排除实际样品中假阳性结果,检测结果更准确可靠.     

全国自来水厂卤乙酸浓度调查、风险评估与标准建议

采用高特异性和高灵敏度的UPLC-MS/MS方法对中国34个城市的117个自来水厂出水中9种卤乙酸进行检测,其中二氯乙酸和三氯乙酸的检出率和检出浓度最高,检出率分别为78.6%和81.2%,平均浓度分别为3.47μg/L和3.31μg/L.风险评价结果表明,二氯乙酸导致我国饮用水致癌风险的期望值为5.72′10-6,处于较低风险水平;全国只有1.7%水厂出水TCAA浓度超过20μg/L的健康指导值.在风险评价的基础上结合我国水厂的卤乙酸浓度数据,建议我国饮用水的二氯乙酸和三氯乙酸标准分别修改为16μg/L和20μg/L.     

我国地表水中典型DBPs的暴露水平及生态风险

氯消毒过程中可能生成有毒有害的副产物,会对水生态系统和环境健康产生直接和间接的次生危害.三卤甲烷（THMs）和卤乙酸（HAAs）是地表水中检出率最高的消毒副产物（DBPs）,其毒性效应受到广泛关注.本文检索整理了三氯甲烷（TCM）、三溴甲烷（TBM）、二氯乙酸（DCAA）和三氯乙酸（TCAA）在我国地表水暴露浓度和对水生生物的毒性效应浓度,了解我国重点流域地表水环境中TCM、TBM、DCAA和TCAA的浓度水平,分别利用急、慢性毒性数据推导预测无效应浓度（PNEC）,并使用风险商（RQ）和概率生态风险评价法（PERA）对我国重点流域水环境中TCM、TBM、DCAA和TCAA进行多层次生态风险评估.结果表明,我国地表水环境中TCM、TBM、DCAA和TCAA暴露浓度范围为n.d.~51μg/L.以致死和生长、繁殖等为测试终点的急、慢性毒性数据,构建物种敏感度分布（SSD）曲线,推导出TCM、TBM、DCAA和TCAA的PNEC值分别为0.586,0.857,0和44.880mg/L;0.006,0.064,0.956和0.012mg/L.基于急、慢性毒性数据计算出的RQ小于1.我国重点流域中TCM和TCAA对1%的水生生物造成生长、繁殖等慢性毒性影响的概率分别为78.86%和20.61%,存在潜在的生态风险.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary e uent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Formation potentials of typical DBPs and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

饮用水中溴酸盐、亚氯酸盐、氯酸盐、溴离子的离子色谱测定法

本文选用DIONEX ICS-2000型离子色谱仪,进样量100μL。水样中的阴离子随氢氧根淋洗液进入阴离子交换分离系统,根据分析柱对各离子的亲和力不同进行分离。结果溴酸盐、亚氯酸盐、氯酸盐、溴离子的检出限分别为：5.0μg/L、4.0μg/L、5.0μg/L、4.4μg/L;标准偏差〈5%;样品加标回收率在87.5%-95.5%。结论该方法操作简单,分析快速,灵敏度高,重现性好,能够准确检测水中卤氧化物。     

PSE-UPLC-MS/MS法测定污泥中9种药物与个人护理品

利用加压溶剂萃取法(PSE)提取、固相萃取法净化并结合超高效液相色谱-串联四极杆质谱仪(UPLC-MS/MS)检测,建立了污水处理厂污泥中7个药剂类别的9种药物与个人护理品(舒必利、咖啡因、美托洛尔、氯霉素、萘啶酸、卡马西平、驱蚊胺、氯贝酸、苯扎贝特)的分析检测方法.在萃取方法中,对加压溶剂萃取的污泥质量和溶剂进行了优化;在净化方法中,对固相萃取柱种类、固相萃取柱容量、洗脱溶剂和洗脱量进行了优选.结果表明,方法检出限(以干质量计,下同)在2.7～65.0 pg/g范围内,加标回收率在67.0%～130%之间,相对标准偏差均小于25%(即标准偏差小于25 μg/L).应用所建立的分析方法,对北京某污水处理厂的脱水污泥进行了测定,9种目标物质含量为nd(未检出)～50.5 ng/g,其中,舒必利、咖啡因、卡马西平、驱蚊胺和氯贝酸在2010年春、夏季2次采样均有检出.      

气相色谱氮磷检测器法测定饮用水中19种苯胺类化合物

建立了气相色谱氮磷检测器法(GC-NPD)测定饮用水中19种苯胺类化合物。结果表明,19种苯胺类化合物的方法检出限在0.06⁰.45μg/L之间,其线性定量范围均为0.050.45μg/L之间,其线性定量范围均为0.05¹0.0 mg/L,相关系数(R)在0.995 110.0 mg/L,相关系数(R)在0.995 1⁰.999 8之间;方法平均加标回收率在70.7%0.999 8之间;方法平均加标回收率在70.7%¹08.2%之间,RSD(n=6)为2.9%108.2%之间,RSD(n=6)为2.9%¹8.5%。该法灵敏度高,快速准确,用于实际水样测定的结果令人满意。     

吹脱捕集气相色谱法分析水中挥发性卤代烃

建立了吹脱捕集气相色谱法测定水中7种挥发性卤代烃的分析方法。对色谱条件、吹脱时间、实验用水等进行了探讨,同时对分析参数如线性相关性、相对标准偏差、最低检出限及加标回收率进行了评价。结果表明,采用吹脱捕集气相色谱法,在1.0μg/L～20.0μg/L范围内,7种卤代烃的质量浓度和峰面积呈良好的线性关系;10.0μg/L的7种挥发性卤代烃标准溶液经重复7次测定,其相对标准偏差为1.30%～8.71%;水样的加标回收率在86.3%～110%之间;最低检出限在0.17μg/L～0.96μg/L之间,该方法已成功地应用于饮用水和地表水中挥发性卤代烃的定性定量测定,结果令人满意。     

Formation potential and analysis of 32 regulated and unregulated disinfection by-products: Two new simplified methods

Water disinfection is an essential process that provides safe water by inactivating pathogens that cause waterborne diseases. However, disinfectants react with organic matter naturally present in water, leading to the formation of disinfection by-products (DBPs). Multi-analyte methods based on mass spectrometry (MS) are preferred to quantify multiple DBP classes at once however, most require extensive sample pre-treatment and significant resources. In this study, two analytical methods were developed for the quantification of 32 regulated and unregulated DBPs. A purge and trap (P&T) coupled with gas chromatography mass spectrometry (GC-MS) method was optimized that automated sample pre-treatment and analyzed volatile and semi-volatile compounds, including trihalomethanes (THMs), iodinated trihalomethanes (I-THMs), haloacetonitriles (HANs), haloketones (HKTs) and halonitromethanes (HNMs). LOQs were between 0.02-0.4 µg/L for most DBPs except for 8 analytes that were in the low µg/L range. A second method with liquid chromatography (LC) tandem mass spectrometry (MS/MS) was developed for the quantification of 10 haloacetic acids (HAAs) with a simple clean-up and direct injection. The LC-MS/MS direct injection method has the lowest detection limits reported (0.2-0.5 µg/L). Both methods have a simple sample pre-treatment, which make it possible for routine analysis. Hyperchlorination and uniform formation conditions (UFC) formation potential tests with chlorine were evaluated with water samples containing high and low TOC. Hyperchlorination formation potential test maximized THMs and HAAs while UFC maximized HANs. Ascorbic acid was found to be an appropriate quencher for both analytical methods. Disinfected drinking water from four water utilities in Alberta, Canada were also evaluated.     

金刚石膜电极消毒处理医院污水的试验研究

以掺硼金刚石(BDD)作电极的自制电解槽装置处理医院污水的消毒效果。在全回流处理模式下消毒处理医院废水,采用多管发酵法测定粪大肠菌群数。掺硼金刚石(BDD)作电极,在电极间距为2mm、医院污水Cl-浓度为200mg/L、pH值在7.0～8.0范围内、电流密度8mA/cm2、接触时间≥9s的条件下,对医院污水粪大肠菌群的去除率最佳,出水满足《医疗机构污水排放标准值》粪大肠菌群数均不得超过500MPN/L。掺硼金刚石(BDD)作电极的自制电解槽装置处理医院污水不需要添加化学药剂,对粪大肠菌群消毒效果好。     

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.