液相色谱-串联质谱法测定水体、沉积物及土壤中全氟化合物

建立了水、沉积物及土壤中13种全氟化合物(PFCs)的富集、净化、浓缩的前处理方法及快速液相色谱三重四级杆串联质谱的分析方法。9种全氟羧酸、2种典型全氟磺酸、2种磺酰铵衍生前体物的响应因子与质量浓度的线性关系良好。添加回收实验表明,13种全氟化合物在水、土壤和沉积物中的回收率为52.3%~119.3%,变异系数为2.3%~19.4%,方法检出限分别为0.015~0.472 ng/L、0.012~0.875 ng/g、0.004~0.743 ng/g。该法成功应用于实际样品的测定,沉积物和土壤中分别检测到3种和10种全氟化合物。     

高效液相色谱串联质谱法测定某市污水处理厂进出水中的全氟化合物

通过建立直接进样-高效液相色谱串联质谱（HPLC-MS/MS）测定污水处理厂进出水中的10种全氟化合物的方法,了解污水厂进出水中全氟化合物污染情况。10种目标分析物在10~500 ng/L范围内具有良好的线性关系,方法检出限为2.3~8.3 ng/L,精密度为2.1%~7.1%,加标回收率为60.6%~91.7%。应用该方法测定某市典型污水厂进出水中的全氟化合物,进水中全氟化合物质量浓度为90.9~206 ng/L,主要污染物是PFOA、PFHxS和PFBS;出水中全氟化合物的质量浓度为67.4~158 ng/L,环境排放量为6.7~22.9 g/d,主要污染物是PFOA和PFHxS。结果表明,该方法能很好地适用于复杂基质中10种全氟化合物的检测。     

环境中“新型”持久性有机污染物的质谱分析

“新型”持久性有机污染物逐渐受到环境科研工作者的重视,这类物质包括溴代阻燃剂、全氟化合物、多氯萘、多氯代正构烷烃和药物以及个人护理用品等,综述了目前对这类环境污染物的检测分析技术。     

在线固相萃取-液相色谱-串联质谱法直接测定水中15种全氟烷基化合物

通过优化样品保存、前处理、分析条件,建立了水中15种典型全氟烷基化合物(PFASs)在线固相萃取-液相色谱-串联质谱分析方法,并对饮用水水源地和末梢水中PFASs进行定量检测。水样过膜后,准确移取700 μL水样、300 μL甲醇至1.5 mL聚丙烯进样瓶,并加入同位素内标后直接进样800 μL至在线固相萃取流路,进行萃取富集,再通过十通阀切换将洗脱的PFASs转移至分析流路进行分离,质谱检测,内标法定量。方法分析总时长22 min,15种全氟烷基化合物的方法检出限为0.31~1.20 ng/L,纯水高、中、低浓度加标样品回收率为70%~115%,相对标准偏差为0.2%~14.0%(n=6)。经实际样品验证,该方法与传统手动固相萃取方法分析结果基本一致。结果表明,该方法操作简单、自动化程度高、有机试剂用量少、灵敏度高、方法稳定,可满足地表水和末梢水中PFASs的快速测定。     

固相萃取-UPLC-MS/MS法测定水中全氟化合物

水样中全氟辛酸、全氟辛烷磺酸钾、全氟丁酸、全氟丁烷磺酸经弱阴离子交换固相萃取柱富集净化后,用超高效液相色谱-串联质谱法测定。通过优化样品前处理条件和仪器条件,使4种全氟化合物在0.05μg/L~10.0μg/L范围内线性良好,相关系数为0.998 9~0.999 9,方法检出限为0.27 ng/L~0.96 ng/L。空白水样3个质量浓度水平的加标回收率为73.1%~91.3%,6次测定结果的RSD为7.4%~14.3%。     

大伙房水库多介质中全氟化合物赋存特征、源解析及健康风险评估

大伙房水库属于全国城市供水九大重点水源地之一,作为辽宁省重要的饮用水水源地,库区水质直接影响该区域人民饮水安全及身体健康。对大伙房水库表层水体、沉积物和鱼类样品中全氟化合物（PFAS）的赋存特征及可能的来源进行分析,并运用健康风险商值法评估PFAS的潜在健康风险。结果表明,库区表层水体中ρ（ΣPFAS）为1.18~8.19 ng/L,主要污染物为全氟辛酸及其盐类化合物（PFOA）和全氟戊基羧酸（PFPA）,其浓度水平随时间呈下降趋势;沉积物中只检出3种污染物,分别为PFOA、全氟十一烷基羧酸（PFUnA）和全氟十二烷基羧酸（PFDoDA）,ω（ΣPFAS）为0.16~0.48 ng/g;不同鱼类样品中ω（ΣPFAS）由高到低依次为：武昌鱼（2.49 ng/g）>鲤鱼（2.30 ng/g）>白鲢（2.02 ng/g）>花鲢（2.01 ng/g）,主要污染物均为PFPA。基于主成分分析与相关性分析可知,大伙房水库库区的PFAS主要来自采矿、电镀、涂料等工业污染废水和生活污水;健康风险评估结果表明,表层水体和鱼类样品中的PFAS不存在健康风险。     

水溶剂加速萃取-超高效液相色谱串联质谱测定土壤中全氟羧酸

采用水溶剂加速萃取-超高效液相色谱串联质谱法（UPLC-MS/MS）建立了土壤中6种全氟羧酸（PFCs）的分析方法,并对色谱分析条件、水溶剂萃取条件、固相萃取柱净化条件及实验材料选择等进行了优化。结果表明,以ACQUITY UPLC BEH C18色谱柱为分离柱,2.0 mmol/L乙酸铵水溶液为流动相A,甲醇为流动相B,梯度洗脱下可在9 min内完成6种PFCs的测试,检出限为0.03~0.4 μg/kg。对实际土壤样品进行测定,加标回收率为90.7%~118%,相对标准偏差为5.6%~18.0%,精密度和准确度均较好。该方法前处理过程简单、易操作,仪器检测效率高、结果准确,能够满足土壤中PFCs的检测要求。     

杭州夏季一次降雨过程雨水中全氟化合物及主要化学组分的变化特征

采用分段采样的方式收集杭州市2018年8月2日—3日一场降水样品,测定其中16种全氟化合物（PFCs）及主要化学组分浓度。结果发现,此次降雨过程水样的pH值范围为5.04～5.32,均为弱酸性降水,酸雨类型为复合型,检出的主要阳离子为NH+4,主要阴离子为SO2-4和NO-3;样品中检出7种中短链PFCs,包括2种全氟烷基磺酸（PFSAs）和5种全氟烷基羧酸（PFCAs）,ΣPFCs质量浓度范围为4.41 ng/L～25.2 ng/L,主要污染因子全氟辛酸（PFOA）质量浓度范围为096 ng/L～13.1 ng/L;降雨过程对大气污染清除作用的统计结果表明,区域大气环境中的主要化学组分及除全氟丁酸（PFBA）之外的PFCs污染主要吸附在云下大气颗粒物上;雨水中各污染因子浓度变化特征及相关性统计结果提示,杭州市大气中PFCAs和PFSAs两类PFCs可能来自不同的污染源。     

N—亚硝胺的确证技术

N—亚硝胺是一种强致癌物。在空气、水、土壤及食品等环境样品中含有痕量的这种化合物。因此,对这种化合物的检测关系到人体健康的一件技术工作。对N—亚硝胺的分析方法还存在着不易确证等技术难题。当前多采用GC—MS法(气相色谱—质谱法)和HPLC—MS法(液相色谱—质谱法)。MS法是确证N-亚硝胺的唯一较可靠的分析方法。但是,由于该法操作复杂,仪器设备昂贵,使得很多实验室无能为力。可是,近十年来,N—亚硝胺的确证技术已发展为验证N—亚硝胺的表观存在了。下面介绍的几种在大多数情况下是可靠的方法:     

更正

正本刊2013年第5卷第5期刊登文章《HPLC-ESI-MS测定地表水中典型全氟化合物方法》一文,基金资助项目为:国家教育部博士点基金(20100091120013);国家自然科学基金(21007022);江苏省环境监测科研基金(0918);江苏省自然科学基金(BK2010384)及江苏省环保科研基金(201128),特此更正。     

Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate

The occurrence and fate of polyfluoroalkyl compounds (PFCs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. PFCs comprise a diverse group of chemicals that are widely used as processing additives during fluoropolymer production and as surfactants in consumer applications for over 50 years. PFCs are known to be persistent, bioaccumulative and have possible adverse effects on humans and wildlife. As a result, perfluorooctane sulfonate (PFOS) has been added to the persistent organic pollutants (POPs) list of the Stockholm Convention in May 2009. However, their homologues, neutral precursor compounds and new PFCs classes continue to be produced. In general, several PFCs from different classes have been detected ubiquitously in the aqueous environment while the concentrations usually range between pg and ng per litre for individual compounds. Sources of PFCs into the aqueous environment are both point sources (e.g., wastewater treatment plant effluents) and nonpoint sources (e.g., surface runoff). The detected congener composition in environmental samples depends on their physicochemical characteristics and may provide information to their sources and transport pathways. However, the dominant transport pathways of individual PFCs to remote regions have not been conclusively characterised to date. The objective of this article is to give an overview on existing knowledge of the occurrence, fate and processes of PFCs in the aquatic environment. Finally, this article identifies knowledge gaps, presents conclusions and recommendations for future work.     

Distribution of perfluorinated compounds in water, sediment, biota and floating plants in Baiyangdian Lake, China

The distribution of perfluorinated compounds (PFCs) in Baiyangdian Lake, China, was determined in this study. Perfluorooctanoic acid (PFOA) was the dominant PFC in lake water (1.70-73.5 ng L(-1), median 9.72 ng L(-1)), while perfluorooctane sulfonate (PFOS) was the dominant PFC in sediments (0.06-0.64 ng g(-1) dry wt, median 0.19 ng g(-1) dry wt) and in aquatic animals (0.57-13.7 ng g(-1) wet wt, median 2.56 ng g(-1) wet wt). Significant differences in PFC levels were observed among various aquatic animals. We also determined, for the first time, the PFC levels in floating plants, including Ceratophyllum demersum L., Hydrocharis dubia (Bl.) Backer and Salvinia natans (L.), and we found that PFOA and PFNA were the dominant PFCs in these plants. Furthermore, floating plants were observed to have different composition profiles compared to aquatic animals. Geographical differences in PFC levels were also observed, with higher PFC levels in samples from the north part of Baiyangdian Lake than those in the south. The differences in human and industrial activities in different parts of the lake and the discharged wastewater from the Fuhe River may be the major contributors for these geographical differences.     

Occurrence of perfluorosulfonates and other perfluorochemicals in dust from selected homes in the city of Ottawa, Canada

A series of perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been recently measured in a variety of environmental samples and biological matrices. In order to better understand the human exposure routes of these chemicals, levels of PFOS, PFOA, perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonamide (PFOSA) in house dust samples were investigated. The data revealed a correlation between the concentrations of PFCs and the percentage of carpeting in the house; older houses tended to have less carpeting, hence lower levels of these perfluorinated compounds in their dust.     

Contamination by perfluorinated compounds in water near waste recycling and disposal sites in Vietnam

There are very few reports on the contamination by perfluorinated chemicals (PFCs) in the environment of developing countries, especially regarding their emission from waste recycling and disposal sites. This is the first study on the occurrence of a wide range of PFCs (17 compounds) in ambient water in Vietnam, including samples collected from a municipal dumping site (MD), an e-waste recycling site (ER), a battery recycling site (BR) and a rural control site. The highest PFC concentration was found in a leachate sample from MD (360 ng/L). The PFC concentrations in ER and BR (mean, 57 and 16 ng/L, respectively) were also significantly higher than those detected in the rural control site (mean, 9.4 ng/L), suggesting that municipal solid waste and waste electrical and electronic equipment are potential contamination sources of PFCs in Vietnam. In general, the most abundant PFCs were perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUDA; <1.4–100, <1.2–100, and <0.5–20 ng/L, respectively). Interestingly, there were specific PFC profiles: perfluoroheptanoic acid and perfluorohexanoic acid (88 and 77 ng/L, respectively) were almost as abundant as PFOA in MD leachate (100 ng/L), whereas PFNA was prevalent in ER and BR (mean, 17 and 6.2 ng/L, respectively) and PFUDA was the most abundant in municipal wastewater (mean, 5.6 ng/L), indicating differences in PFC contents in different waste materials.     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

A pilot study on the determination of perfluorooctanesulfonate and other perfluorinated compounds in blood of Canadians

A pilot study was conducted to provide preliminary data on the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonamide (PFOSA) in the blood of Canadians. A set of 56 human serum samples was collected from non-occupationally exposed Canadians and analyzed by microbore HPLC-negative ion electrospray tandem mass spectrometry. PFOS was the main component of perfluorinated organic compounds (PFCs) and was detected in all 56 blood specimens at an average concentration of 28.8 ng mL(-1) and a range from 3.7 to 65.1 ng mL(-1). The concentration of PFOA was an order of magnitude lower than that of PFOS and was found only in 16 samples (29%) at concentrations above the limit of quantification (LOQ). PFOSA was not detected at levels above the method detection limit (MDL) in any of the samples. The levels of PFCs observed in the sample group of non-occupationally exposed humans in Canada were similar to the levels reported in a previous US study with a similar sample pool size. Two distinct PFOS isomers in human serum were identified by accurate mass determination.     

Perfluoroalkyl compounds (PFCs) in wildlife from an urban estuary

Previous research has documented the bioaccumulation of perfluoroalkyl compounds (PFCs) in apex predators in remote locations but few studies have evaluated urban estuaries. To assess the importance of PFCs in San Francisco Bay, two apex predators in the San Francisco Bay, double-crested cormorants (Phalacrocorax auritus) and Pacific harbor seals (Phoca vitulina richardii), were sampled. Prey fish (Atherinops affinis and Menidia audens) were also evaluated to better understand potential sources of PFCs to the foodweb. Perfluorooctane sulfonate (PFOS) was the primary PFC detected in cormorant eggs, small fish and harbor seal serum. PFOS detected in San Francisco Bay seal serum was typically an order of magnitude higher than those at the reference site. PFOS concentrations were highest in seals and cormorant eggs from the highly urbanized southern portion of the Bay. PFOS in eggs from the southern part of the Bay remained relatively constant between 2006 and 2009 despite the phase-out of perfluorosulfonyl-based compounds nationally. In addition, these levels exceed the avian predicted no effects concentration of 1.0 μg mL(-1). Concentrations of the remaining PFCs measured were substantially lower than those of PFOS.     

Iodide-assisted total lead measurement and determination of different lead fractions in drinking water samples

Lead and its compounds are toxic and can harm human health, especially the intelligence development in children. Accurate measurement of total lead present in drinking water is crucial in determining the extent of lead contamination and human exposure due to drinking water consumption. The USEPA method for total lead measurement (no. 200.8) is often used to analyze lead levels in drinking water. However, in the presence of high concentration of the tetravalent lead corrosion product PbO(2), the USEPA method was not able to fully recover particulate lead due to incomplete dissolution of PbO(2) particles during strong acid digestion. In this study, a new procedure that integrates membrane separation, iodometric PbO(2) measurement, strong acid digestion and ICP-MS measurement was proposed and evaluated for accurate total lead measurement and quantification of different lead fractions including soluble Pb(2+), particulate Pb(II) carbonate and PbO(2) in drinking water samples. The proposed procedure was evaluated using drinking water reconstituted with spiked Pb(2+), spiked particulate Pb(II) carbonate and in situ formed or spiked PbO(2). Recovery tests showed that the proposed procedure and the USEPA method can achieve 93-112% and 86-103% recoveries respectively for samples containing low PbO(2) concentrations (0.018-0.076 mg Pb per L). For samples containing higher concentrations of PbO(2) (0.089-1.316 mg Pb per L), the USEPA method failed to meet the recovery requirement for total lead (85-115%) while the proposed method can achieve satisfactory recoveries (91-111%) and differentiate the soluble Pb(2+), particulate Pb(II) carbonate and PbO(2).     

水体中磺胺、四环素、喹诺酮类抗生素检测方法

建立了固相萃取-高效液相色谱-串联质谱法(SPE-HPLC-MS/MS)同时检测水体中3类15种抗生素的分析方法。水样用Oasis HLB固相萃取小柱净化富集。通过对比水样在不同pH条件下的回收率,优化了环境水样中抗生素固相萃取过程中的前处理条件。采用甲醇和0.1%甲酸溶液作为流动相,经过梯度洗脱进行分离,在HPLC-MS/MS多反应监测模式下进行定性定量分析。结果表明,环境水体中15种抗生素的检出限和定量下限分别为0.12~1.6 ng/L和0.2~3.0 ng/L,自来水加标回收率为34.9%~102.5%(pH=4)。用该方法对海河流域13个地表水水样进行了初步检测,结果表明,部分抗生素普遍存在于地表水体中。其中,磺胺甲基异NFDA1唑检出频率最高,在13个地表水样品中均有检出。