基于被动采样技术的水体中有机锡污染筛查取证研究
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摘要
将三油酸甘油酯-醋酸纤维素复合膜(TECAM)用作被动采样器,开展水体中一甲基锡(MMT)、二甲基锡(DMT)、一丁基锡(MBT)、二丁基锡(DBT)、三丁基锡(TBT)、二苯基锡(DPhT)和三苯基锡(TPhT)等7种有机锡氯化物的富集实验,膜样品经甲醇/醋酸溶液提取、乙基化衍生和正己烷萃取等前处理后,用气相色谱-质谱法(GC-MS)进行定性和定量检测,得到水体中痕量有机锡污染的相关指纹信息。结果表明,7种目标化合物均可在TECAM膜上富集,48 h后均可达到平衡状态;有机锡富集能力差异较大,其TECAM膜/水分配系数(log KTECAM)与其辛醇-水分配系数(log Kow)呈现显著正相关性(r=0.97, n=7)。甲基锡富集能力较低,但可定性筛查;而苯基锡和丁基锡等5种目标化合物在TECAM膜上的被动采样速率在0.06～0.16 L·g~(-1)·d~(-1)范围变化,经反演所得其在水体中的时间加权平均浓度与传统的主动采样法所得浓度没有显著差异(P>0.05)。因此,基于TECAM被动采样技术可以实现水体中极性范围较广的痕量有机锡污染筛查取证。
The triolein-embedded cellulose acetate membrane(TECAM) as a passive sampler is used to enrich seven organotin compounds including monomethyltin(MMT), dimethyltin(DMT), monobutyltin(MBT), dibutyltin(DBT), tributyltin(TBT), diphenyltin(DPhT) and triphenyltin(TPhT) chlorides. Organotin compounds in the TECAM are extracted by methanol/acetic acid(9:1 V/V), and ethylated by sodium tetraethylborate followed by n-hexane extraction, and are then analyzed using a gas chromatography-mass spectrometer(GC-MS) to study its fingerprint information in water. The results show that all the seven target compounds can be enriched with TECAM withan equilibrium time of 48 hours. The enrichment capacities of TECAM towards organotin are quite different. Organotin's membrane/water partition coefficient(log KTECAM) is positively correlated with their octanol/water partition coefficient(log Kow)(r = 0.97, n = 7). Although the enrichment capacities of methyltin are low, they still can be qualitatively analyzed by this method, while the sampling rates of MBT, DBT, TBT, DPhT and TPhT vary in the range of 0.06-0.16 L·g~(-1)·d~(-1). Moreover, there is no significant difference between the time-weighted averaged concentration derived by TECAM and the average concentration obtained by active sampling(P > 0.05). The passive sampling technology based on TECAM can be used for forensic fingerprint of trace organotin pollutants with a wide range of polarities in water.
The triolein-embedded cellulose acetate membrane(TECAM) as a passive sampler is used to enrich seven organotin compounds including monomethyltin(MMT), dimethyltin(DMT), monobutyltin(MBT), dibutyltin(DBT), tributyltin(TBT), diphenyltin(DPhT) and triphenyltin(TPhT) chlorides. Organotin compounds in the TECAM are extracted by methanol/acetic acid(9:1 V/V), and ethylated by sodium tetraethylborate followed by n-hexane extraction, and are then analyzed using a gas chromatography-mass spectrometer(GC-MS) to study its fingerprint information in water. The results show that all the seven target compounds can be enriched with TECAM withan equilibrium time of 48 hours. The enrichment capacities of TECAM towards organotin are quite different. Organotin's membrane/water partition coefficient(log KTECAM) is positively correlated with their octanol/water partition coefficient(log Kow)(r = 0.97, n = 7). Although the enrichment capacities of methyltin are low, they still can be qualitatively analyzed by this method, while the sampling rates of MBT, DBT, TBT, DPhT and TPhT vary in the range of 0.06-0.16 L·g~(-1)·d~(-1). Moreover, there is no significant difference between the time-weighted averaged concentration derived by TECAM and the average concentration obtained by active sampling(P > 0.05). The passive sampling technology based on TECAM can be used for forensic fingerprint of trace organotin pollutants with a wide range of polarities in water.
引文
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[19] Parkerton T F, Stone M A, Letinski D J. Assessing the aquatic toxicity of complex hydrocarbon mixtures using solid phase microextraction[J]. Toxicology Letters, 2000,112(3):273-282
[20] Cole R F, Mills G A, Parker R, et al. Trends in the analysis and monitoring of organotins in the aquatic environment[J]. Trends in Environmental Analytical Chemistry,2015, 8:1-11
[21]何依芳,黄清辉,陈玲,等.南极菲尔德斯半岛近岸海洋生物体有机锡污染状况[J].环境科学学报, 2018, 38(3):1256-1262He Y F, Huang Q H, Chen L, et al. Organotin contamination in marine biota from the Fildes Peninsula Coast, Antarctic[J]. Acta Scientiae Circumstantiae, 2018, 38(3):1256-1262(in Chinese)
[22]卢阳.上海市集中式供应饮用水有机锡污染调查与健康风险评价[D].上海:同济大学, 2016:17-32Lu Y. Investigation and health risk assessment of organotin contaminations in Shanghai’s centralized supply drinking water[D]. Shanghai:Tongji University, 2016:17-32(in Chinese)
[23] Huckins J N, Petty J D, Orazio C E, et al. Determination of uptake kinetics(sampling rates)by lipid-containing semipermeable membrane devices(SPMDs)for polycyclic aromatic hydrocarbons(PAHs)in water[J]. Environmental Science&Technology, 1999, 33(21):3918-3923
[24] Huckins J N, Prest H F, Petty J D, et al. Overview and comparison of lipid-containing semipermeable membrane devices and oysters(Crassostrea gigas)for assessing organic chemical exposure[J]. Environmental Toxicology&Chemistry, 2010, 23(7):1617-1628
[25] Ke R H, Wang Z J, Huang S B, et al. Accurate quantification of freely dissolved organochlorine pesticides in water in the presence of dissolved organic matter using trioleinembedded cellulose acetate membrane[J]. Analytical and Bioanalytical Chemistry, 2007, 387(8):2871-2879
[26] Tang J F, Chen S, Xu Y P, et al. Calibration and field performance of triolein embedded acetate membranes for passive sampling persistent organic pollutants in water[J].Environmental Pollution, 2012, 164:158-163
[2] Zhang K G, Shi J B, He B, et al. Organotin compounds in surface sediments from selected fishing ports along the Chinese coast[J]. Chinese Science Bulletin, 2013, 58(2):231-237
[3] Chen C Z, Chen L, Huang Q H, et al. Organotin contami-nation in commercial and wild oysters from China:Increasing occurrence of triphenyltin[J]. Science of The Total Environment, 2019, 650:2527-2534
[4] Sousa A C A, Pastorinho M R, Takahashi S, et al. History on organotin compounds, from snails to humans[J]. Environmental Chemistry Letters, 2014, 12(1):117-137
[5] Hallas L E, Means J C, Cooney J J. Methylation of tin by estuarine microorganisms[J]. Science, 1982, 215(4539):1505-1507
[6] Jiang G B, Zhou Q F, He B, et al. Speciation analysis of organotin compounds in lard poisoning accident in Jiangxi Province, China[J]. Science in China, 2000, 43(5):531-539
[7] Hoch M. Organotin compounds in the environment—An overview[J]. Applied Geochemistry, 2001, 16(7):719-743
[8] Gonzalez-Toledo E, Compano R, Granados M, et al. Detection techniques in speciation analysis of organotin compounds by liquid chromatography[J]. Trends in Analytical Chemistry, 2003, 22(1):26-33
[9] Cole R F, Mills G A, Bakir A, et al. A simple, low cost GC/MS method for the sub-nanogram per litre measurement of organotins in coastal water[J]. Methods X, 2016,3:490-496
[10] Jiang G B, Liu J Y, Yang K W. Speciation analysis of butyltin compounds in Chinese seawater by capillary gas chromatography with flame photometric detection using in-situ hydride derivatization followed by headspace solid-phase microextraction[J]. Analytica Chimica Acta,2000, 421(1):67-74
[11] Namie s'nik J, Zabiegaa B, Kot-Wasik A, et al. Passive sampling and/or extraction techniques in environmental analysis:A review[J]. Analytical and Bioanalytical Chemistry, 2005, 381(2):279-301
[12] Flsvik N, Brevik E M, Berge J A. Organotin compounds in a Norwegian fjord. A comparison of concentration levels in semipermeable membrane devices(SPMDs), blue mussels(Mytilus edulis)and water samples[J]. Journal of Environmental Monitoring, 2002, 4(2):280-283
[13] Aguilar-Martínez R, Palacios-Corvillo M A, Greenwood R, et al. Calibration and use of the Chemcatcherpassive sampler for monitoring organotin compounds in water[J].Analytica Chimica Acta, 2008, 618(2):157-167
[14]许宜平,吕怡兵,李剑,等.新型醋酸纤维素复合膜的制备及其基本性能研究[J].高技术通讯, 2004, 14(1):89-94Xu Y P, Lv Y B, Li J, et al. The research on the preparation and fundamental properties of a new type of cellulose acetate composite membrane[J]. High Technology Letters, 2004, 14(1):89-94(in Chinese)
[15]周东星,许宜平,王子健.应用生物模拟采样法快速评估水中邻苯二甲酸酯的生物富集性[J].生态毒理学报,2015, 10(1):281-287Zhou D X, Xu Y P, Wang Z J. Rapid evaluation of bioconcentration potential for esters using a biomimetic sampler[J]. Asian Journal of Ecotoxicology, 2015, 10(1):281-287(in Chinese)
[16]柯润辉,孙立伟,陈珊,等.三油酸甘油脂-醋酸纤维素复合膜测定水中有机氯农药生物有效性[J].环境科学学报, 2007, 27(12):2019-2024Ke R H, Sun L W, Chen S, et al. Measuring the bioavailability of organochlorine pesticides in water using triolein embedded cellulose acetate membrane[J]. Acta Scientiae Circumstantiae, 2007, 27(12):2019-2024(in Chinese)
[17] Chen S, Ke R H, Huang S B, et al. Impact of dissolved humic acid on the bioavailability of acenaphthene and chrysene assessed by membrane-based passive samplers[J]. Chinese Science Bulletin, 2007, 52(19):2642-2648
[18]姚婷.大连湾与杭州湾海洋环境中PCBs和OCPs的残留状态及新型被动采样装置研究[D].辽宁:辽宁师范大学, 2014:28-38Yao T. The remain of PCBs and OCPs in marine of Dalian Bay and Hangzhou Bay and a study on new passive sampling device[D]. Liaoning:Liaoning Normal University, 2014:28-38(in Chinese)
[19] Parkerton T F, Stone M A, Letinski D J. Assessing the aquatic toxicity of complex hydrocarbon mixtures using solid phase microextraction[J]. Toxicology Letters, 2000,112(3):273-282
[20] Cole R F, Mills G A, Parker R, et al. Trends in the analysis and monitoring of organotins in the aquatic environment[J]. Trends in Environmental Analytical Chemistry,2015, 8:1-11
[21]何依芳,黄清辉,陈玲,等.南极菲尔德斯半岛近岸海洋生物体有机锡污染状况[J].环境科学学报, 2018, 38(3):1256-1262He Y F, Huang Q H, Chen L, et al. Organotin contamination in marine biota from the Fildes Peninsula Coast, Antarctic[J]. Acta Scientiae Circumstantiae, 2018, 38(3):1256-1262(in Chinese)
[22]卢阳.上海市集中式供应饮用水有机锡污染调查与健康风险评价[D].上海:同济大学, 2016:17-32Lu Y. Investigation and health risk assessment of organotin contaminations in Shanghai’s centralized supply drinking water[D]. Shanghai:Tongji University, 2016:17-32(in Chinese)
[23] Huckins J N, Petty J D, Orazio C E, et al. Determination of uptake kinetics(sampling rates)by lipid-containing semipermeable membrane devices(SPMDs)for polycyclic aromatic hydrocarbons(PAHs)in water[J]. Environmental Science&Technology, 1999, 33(21):3918-3923
[24] Huckins J N, Prest H F, Petty J D, et al. Overview and comparison of lipid-containing semipermeable membrane devices and oysters(Crassostrea gigas)for assessing organic chemical exposure[J]. Environmental Toxicology&Chemistry, 2010, 23(7):1617-1628
[25] Ke R H, Wang Z J, Huang S B, et al. Accurate quantification of freely dissolved organochlorine pesticides in water in the presence of dissolved organic matter using trioleinembedded cellulose acetate membrane[J]. Analytical and Bioanalytical Chemistry, 2007, 387(8):2871-2879
[26] Tang J F, Chen S, Xu Y P, et al. Calibration and field performance of triolein embedded acetate membranes for passive sampling persistent organic pollutants in water[J].Environmental Pollution, 2012, 164:158-163