有机锡分析方法的建立及东南沿海有机锡污染现状调查
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摘要
有机锡化合物对近海生态系统潜在的危害相当严重，但我国还没有制定出相应的法规和标准进行控制，这主要是由于没有便捷、灵敏的研究调查方法为制订相应的法规提供科学依据。
本课题选择利用顶空固相微萃取-气相色谱与火焰光度仪联用(SPME-GC-FPD)技术对海洋环境中的有机锡，特别是三丁基锡(TBT)进行检测。通过一系列实验建立起分析测定水样、底泥及生物样中有机锡含量的灵敏检测方法，并将该方法用于我国东南沿海港口的有机锡污染现状调查。其中，对于泥样和生物样尝试采用了超声处理以及酶解等预处理方法，结果证明能有效提高检测的灵敏度。
对我国东南沿海8个港口的调查结果表明，水样中TBT含量为低于检测限至9.83ng／L，泥样中为低于检测限至174.67ng／g(d.w)，生物样中为2.11-70.60ng／g(w.w)。其中北山湾站点水样中TBT含量低于检测限，生物样中含量最低，但该站点海产腹足类性畸变的调查表明疣荔枝螺已经发生性畸变。因此，我国东南沿海的有机锡污染是普遍和严重的，并已对生态系统构成了威胁。
有机锡污染物分布规律主要由地理环境因素决定，同一港口的港内样品中污染物含量明显高于港外样品。经t-test检验，各调查港口水样和泥样中的TBT和MBT(一丁基锡)含量在港内与港外存在显著差异。而且港口吞吐量与水域环境污染程度也呈显著正相关关系。
疣荔枝螺体内的TBT含量与其性畸变指数VDSI拟合所得S曲线表明，有机锡污染是疣荔枝螺性畸变的诱导因素，其VDSI指数可以作为有机锡污染的生物监测指标。
柘林湾柱状泥样中有机锡化合物垂直分布规律呈单峰型，峰值位于2-3cm深度，6cm以下有机锡化合物含量非常低，这为泥样的采集提供了一定理论依据。
Though organotins have caused serious potential damage to the coast ecosystem, there was no corresponding laws, regulations or restrictions to control them in china due to unavailability of sensitive and practical investigating methods.
Headspace solid phase microextraction combined with gas chromatography and flame photometric detector was adopted in the present study to determine the organotins, especially tributyltin, in oceanic environment. The sensitive methods for water, sediment and biotic samples were established based on a series of experiments, and then used to survey on occurrence of organotin pollution in harbors along the southeast coast of China. The results showed that the pretreatments of sediment and biotic samples with ultrasonic and enzymic hydrolysis could effectively enhance the sensitivity of determination.
The investigated results on 8 harbors along the southeast coast of China showed that the TBT concentrations were from less than detection limit to 9.83 ng/L in water samples, from less than detection limit to 174.67 ng/g(d.w) in sediment samples, and were 2.11-70.61 ng/g(w.w) in biotic samples. The TBT concentration in water sample from Beishan Bay was below detection limit, and was the lowest for biotic sample. However, study on imposex of marine Gastropod showed Thais clavigera in Beishan Bay was imposex. This indicated that occurrence of organotin along the southeast coast of china was universal and serious, and had given damage to the ecosystem.
The distribution of organotins in most of harbors was controlled by the geographic facters, such as organotins in all three kinds of samples from the inner harbors were higher than those of the outer harbors. T-test showed significant difference between the two groups of data (inner and outer harbors). Moreover, significant positive correlations were found between organotin concentrations and the throughput capacities of harbors.
The S-curve fitting to TBT concentrations and VDSI in Thais clavigera, indicated that the organotin pollution was a key driving force to imposex in Thais clavigera, and the VDSI of Thais clavigera was useful and practical for biomonitoring of organotins pollution.
The pattern of vertical distribution of organotin in sediment cores of Zhelin Bay was mono-peak. The peak located in 2-3 cm depth, organotin concentrations were very low below 6 cm depth. This provided an academic fundament for sampling of sediment.
本课题选择利用顶空固相微萃取-气相色谱与火焰光度仪联用(SPME-GC-FPD)技术对海洋环境中的有机锡，特别是三丁基锡(TBT)进行检测。通过一系列实验建立起分析测定水样、底泥及生物样中有机锡含量的灵敏检测方法，并将该方法用于我国东南沿海港口的有机锡污染现状调查。其中，对于泥样和生物样尝试采用了超声处理以及酶解等预处理方法，结果证明能有效提高检测的灵敏度。
对我国东南沿海8个港口的调查结果表明，水样中TBT含量为低于检测限至9.83ng／L，泥样中为低于检测限至174.67ng／g(d.w)，生物样中为2.11-70.60ng／g(w.w)。其中北山湾站点水样中TBT含量低于检测限，生物样中含量最低，但该站点海产腹足类性畸变的调查表明疣荔枝螺已经发生性畸变。因此，我国东南沿海的有机锡污染是普遍和严重的，并已对生态系统构成了威胁。
有机锡污染物分布规律主要由地理环境因素决定，同一港口的港内样品中污染物含量明显高于港外样品。经t-test检验，各调查港口水样和泥样中的TBT和MBT(一丁基锡)含量在港内与港外存在显著差异。而且港口吞吐量与水域环境污染程度也呈显著正相关关系。
疣荔枝螺体内的TBT含量与其性畸变指数VDSI拟合所得S曲线表明，有机锡污染是疣荔枝螺性畸变的诱导因素，其VDSI指数可以作为有机锡污染的生物监测指标。
柘林湾柱状泥样中有机锡化合物垂直分布规律呈单峰型，峰值位于2-3cm深度，6cm以下有机锡化合物含量非常低，这为泥样的采集提供了一定理论依据。
Though organotins have caused serious potential damage to the coast ecosystem, there was no corresponding laws, regulations or restrictions to control them in china due to unavailability of sensitive and practical investigating methods.
Headspace solid phase microextraction combined with gas chromatography and flame photometric detector was adopted in the present study to determine the organotins, especially tributyltin, in oceanic environment. The sensitive methods for water, sediment and biotic samples were established based on a series of experiments, and then used to survey on occurrence of organotin pollution in harbors along the southeast coast of China. The results showed that the pretreatments of sediment and biotic samples with ultrasonic and enzymic hydrolysis could effectively enhance the sensitivity of determination.
The investigated results on 8 harbors along the southeast coast of China showed that the TBT concentrations were from less than detection limit to 9.83 ng/L in water samples, from less than detection limit to 174.67 ng/g(d.w) in sediment samples, and were 2.11-70.61 ng/g(w.w) in biotic samples. The TBT concentration in water sample from Beishan Bay was below detection limit, and was the lowest for biotic sample. However, study on imposex of marine Gastropod showed Thais clavigera in Beishan Bay was imposex. This indicated that occurrence of organotin along the southeast coast of china was universal and serious, and had given damage to the ecosystem.
The distribution of organotins in most of harbors was controlled by the geographic facters, such as organotins in all three kinds of samples from the inner harbors were higher than those of the outer harbors. T-test showed significant difference between the two groups of data (inner and outer harbors). Moreover, significant positive correlations were found between organotin concentrations and the throughput capacities of harbors.
The S-curve fitting to TBT concentrations and VDSI in Thais clavigera, indicated that the organotin pollution was a key driving force to imposex in Thais clavigera, and the VDSI of Thais clavigera was useful and practical for biomonitoring of organotins pollution.
The pattern of vertical distribution of organotin in sediment cores of Zhelin Bay was mono-peak. The peak located in 2-3 cm depth, organotin concentrations were very low below 6 cm depth. This provided an academic fundament for sampling of sediment.
引文
[1] Alfred J. Vell, Bemardette Mintoff, Victor Axiak. Analytical aspects of the gas chromatographic determination of tributyltin and metabolites in environmental samples[J]. The Science of the Total Environment. 2000, 258:81-88
[2] Alzieu C, Thibaud Y, Heral M. Evaluation of sicks of using antifouling paints in the oyster culture basins[J], Rev Tray inst peches marit. 1980, 44(4): 301-348
[3] Asa Espmark Wibe, Trond Nordtug, Bjorn Munro Jenssen. Effects of bis(tributyltin)oxide on antipredator behavior in threespine stickleback Gasterosteus aculeatus [J]. Chemosphere. 2001, 44:475-481
[4] B S.Smith. Male characteristics on female mud snails caused by antifouling bottom paints[J]. Appl. Toxicol. 1981, 1:22-25
[5] B.Bauer, P.Fioroni, I.Ide, S.Liebe, J.Dehlmann, E.Stroben, B.Watermann. TBT effects on the famale gential system of Littorina Littorea: a possible indication of tributyltin pollution[J]. Hydroilogia. 1995, 309:15-27
[6] Blaber, S.J.M. The occurrence of a penis-like outgrowth behind the right tentacle in spent females of Nucella lapillus [L]. Proceedings of the Malacological Society of London. 1970, 39:231-23
[7] Blackmore G. Imposex in Thais clavigera (Neogastropoda) as an indicator of TBT (Tributyltin) bioailability in coastal waters of Hong Kong [J]. Moll Stud. 2000, 66:1～8
[8] C. Montigny, G. Lespes, M. Potin-Gautier. Matrix effects and selectivity of the detector in the deter- ruination of butyl- and phenyitins by gas chromatography-flame photometric detection[J]. Journal of Chromatography A. 1998, 819:221-230
[9] C.Carlier-Pinasseau, G.Lespes, M.Astruc. Validation of organotin compound determination in environmental samples using NaBEt_4,ethylation and GC-FPD[J]. Environmental technology. 1997, 18(12): 1179-1186
[10] C.Stewart, S.J. Mora. A review of the degradation of Tributyltin in the marine environment[J]. Environ. Technol. 1990, 11:565-570
[11] Caterina Pellegrino, Paolo Massanisso, Roberto Morabito. Comparison of twelve selected extraction methods for the determination of butyl- and phenyltin compounds in mussel samples[J]. Trends in Analytical Chemistry. 2000, 19:97-106
[12] Ch. Bancon-Montigny, G. Lespes, M. Potin-Gautier. Improved routine speciation of organotin com- pounds in environmental samples by pulsed flame photometric detection[J]. Journal of Chromatography A. 2000, 896:149-158
[13] Champ M.A. A review of organotin regulatory strategies, pending actions, related costs and benefits[J]. The Science of the Total Environment. 2000, 258: 21-71.
[14] Clark S, Ashby J, Craig P J. On-column hydride generation methed for the production of volatile of tin arsenic and antimony for the gas chromatographic analysis of dilute solutions[J]. Analyst. 1987, 112(12): 1781-1782
[15] D.Minchin, J.Oehlmann, C.B.Duggan, E.Stroben, M.Keatinge. Marine TBT antifouling contamination in Ireland following legislation in 1987[J]. Pollution Bulletin. 1995, 30:633-639
[16] Dirkx W M R, Lobinski R, Adams F C. Speciation analysis of organotin in water and sediments
by gas chromatography with optical spectrometric detection after extraction separation[J]. Analytical chemistry. 1994, 286:309-318
[17] E.Pelletier and C.Normandeau. Distribution of butyltin residues in mussels and sea stars of the St Lawrence estuary[J]. Environmental Technology. 1997, 18(12): 1203-1208
[18] Encarna Gonzlez-Toledo, Mario Benzi, Ramon Compaf, Merc Granados, Maria Dolors Prat. Speciation of organotin compounds in shellfish by liquid chromatography -fluorimetric detection[J]. Analytical chemistry. 2001,443: 183-190
[19] Eros Bacci, Carlo Gaggi. Organotin compounds in harbor and marina waters from the northern Tyrrhenian Sea[J]. Marine pollution. 1989, 20(6): 290-292.
[20] Esmeralda Millan, Janusz Pawliszyn. Determination of butyltin species in water and sediment by solid-phase microextraction-gas chromatography-flame ionization detection[J]. Journal of Chromatography A. 2000, 873:63-71.
[21] Fent K, Hunn J. Phenyltins in water, sediment, and biota of freshwater Marinas[J]. Environ Science Technology. 1991, 25(5): 956-963.
[22] G W. Bryan, P E.Gibbs. Comparison of the effectiveness of tributyitin chloride and five other organotin compounds in promoting the development of imposex in the dog-whelk Nucella lapillus[J]. Marine Biology. 1988, 68: 733-744.
[23] G. Lespes, V. Desauziers, C.Montigny, M.Potin-Gautier. Optimization of solid-phase microextraction for the speciation of buty- and phenyltins using experimental designs[J]. Journal of Chromatography A. 1998, 826: 67-76.
[24] Gibbs, P.E.,Bryan, G.W., Pascoe, P.L., Burt, G.R. The use of the dog whelk, Nucella lapillus, as an indicator of TBT contamination[J]. Journal of marine biological association of the United Kongdom. 1987, 67:507-523
[25] Gibbs.P.E.,Bryan. G.W. Reproductive failure in populations of the dog whelk, Nucella lapillus caused by imposex induced by TBT from antifouling paints. Journal of marine biological association of the United Kingdom[J]. 1986, 66: 767-777.
[26] Horiguchi T., Shiraishi H M, Shimizu M., Morita M., Effects of triphenyltin chloride and five other organotin compounds on the development of imposex in the rock shell, Thais clavigera[J]. Environmental Pollution. 1997, 95(1): 85-91
[27] Hyun Min Hwanga, Jae Ryoung Oh, Sung-Hyun Kahng, Kwang Woo Lee. Tributyltin compounds in mussels, oysters and sediments of Chinhae Bay, Korea[J]. Marine Environmental Research. 1999, 47:61-70
[28] J J.Cleary, Organotin and total tin in coastal waters of South-west England[J]. Marine Pollution Bulletin. 1985, 16:350-355
[29] J.L.Gomez-Ariza, E.Morales, I.Giraldez. Spatial distribution of butyltin and phenyltin compounds on the Huelva coast(southwest Spain) [J]. Chemosphere. 1998, 37(5): 937-950
[30] J.Oehlmann, E.Stroben, U.Schulte-Oehlmann, B.Bauer, P. Fioroni, B.Mardert. Tributyltin biomonitoring using prosobranchs as sentinel organisms[J]. Fresenius Journal of Analytical Chemistry. 1996, 354:540-545
[31] J.Oelhlmann, C.Bettin. TBT-induced imposex and the role of steroids in marine snails[J]. Malacol. Rev. Suppl. 1996, 6:157-161
[32] Jennie S.han, James H. weber. Speciation of methyl- and butyltin compounds and inorganic tin in oysters by hydride generation atomic absorotion spectrometry[J]. Analytical chemistry. 1988,
60(4): 316-319
[33] Jiang Gui-bin, Zhou Qun-fang. Direct Grignard pentylation of organotin-contaminated lard samples followed by capillary gas chromatography with flame photometricdetection[J]. Journal of Chromatography A. 2000, 886:197-205
[34] K.Elgethun, C.Neumann, P.Blake. Butyltins in shellfish, finfish, water and sediment from the Coos Bay estuary(Oregon, USA) [J]. Chemosphere. 2000, 41:953-964
[35] L.L.Liu, I.J.Suen. Organotins promoting the development of imposex in the oyster drill Thais clavigera[J]. Journal of the Fisheries Society of Taiwan. 1996, 23:149-154.
[36] Lobinki R, Dirkx W M R, Celemans M. Optimization of comprehensive speciation analysis of organotin compounds in environmental samples by capillary gas chromatography heliem microwave-induced plasma emission spectrometry[J]. Analytical chemistry. 1992, 64:159-165
[37] Lobinki R. Gas chromatography with element selective detection in speciation analysis: status and future prospects[J]. Analysis. 1994, 22:37-48
[38] M. Ceulemans, S. Slaets, F. Adams. Speciation of organotin in environmental sediment samples[J]. Talanta. 1998, 46:395-405
[39] M.D Molleret. Tributyltin in the environment-sources, fate and determination an assessment of present status and research needs[J]. Chemosphere. 1989, 18(9/10): 2015-2042
[40] Manuela A, Josep-Maria B, Ramon C. Analytical procedures for the determination of organotin compounds in sediment and biota: a critical review[J]. Journal of Chromatography A. 1997, 788:1-49
[41] Montserrat Sole. Effects of tributyltin on the MFO system of the clam Ruditapes decussata: a laboratory and field approach[J]. Comparative Biochemistry and Physiology. 2000, Part C 125: 93-101
[42] N.Sponer, P E.Gibbs, G W. Bryan, L J.Goad. The effect of tributyltin upon steroid titres in the female dogwhelk, Nucella lapillus, and the development of imposex[J]. Marine Environmental Research, 1991, 32:37-49
[43] Nicholas H. Snow. Solid-phase micro-extraction of drugs from biological matrices[J]. Journal of Chromatography A. 2000, 885:445-455
[44] Norunn Folsvik, John Arthur Berge, Einar M.Brevik, Marts Walday. Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella Lapillus) from Norway[J]. Chemospbere. 1999, 38(3): 681-691
[45] O Aboul Dahab. Tin compounds in sediments of Lake Maryut[J]. Egypt environmental pollution. 1990, 63:329-344
[46] Patricia Schubert, Inmaculada Fernandez-Escobar, Erwin Rosenberg, Josep-Maria Bayona. Evalu- ation of desulfurization procedures for the elimination of sulfur interferences in the organotin analy- sis of sediments[J]. Journal of Chromatography A. 1998, 810:245-251
[47] Pawliszyn J B. Solid-phase microextraction. Theory and pactice[M]. Wiley-VCH, Weinheim, Germary. 1997
[48] Peter F S, Aldis O V, Richard F L. Degradation of tributyltin in San Diego Bay, California, Waters[J]. Environmen Science Technology. 1986, 20(12): 1229-1235
[49] Philippe Quevauviller, Roberto Morabito. Evaluation of extraction recoveries for organometallic determinations in environmental matrices[J]. Trends in Analytical Chemistry. 2000, 19: 86-96
[50] Piver W T. Organotin compounds: industrial application and biological investigation[J]. Environ heathlth perspsct. 1973, 6:61-79
[51] R J Maguire, H Huneault. Determination of butyltin species in water by gas chromatography with flame photometric detection[J]. Journal of Chromatography A. 1981,209:458-462
[52] R.Saint-Louis, C.Gobeil, E.Pelletiier. Tributyltin and its degradation products in the St Lawrence estuary (Canada) [J]. Environmental Technology. 1997, 18(12): 1209-1218
[53] S M.Evans, T. Leksono, P. Mckinnell. Tributyltin pollution: A diminishing problem following legislation limiting the use of TBT-based anti-fouling paints[J]. Marine Pollution Bulletin. 1995, 30,14-21
[54] S. Diez, M. Abalos, J.M. Bayona. Organotin contamination in sediments from the Western Mediter- ranean enclosures following 10 years of TBT regulation[J]. Water Research. 2002, 36: 905-918
[55] S.Shawky, H.emons. Distributions pattern of organotin compounds at different trophiclevers of aquatic ecosystems[J]. Chemosphere. 1998, 36(3): 523-535
[56] Sara Graslund, Bengt-Erik Bengtsson. Chemicals and biological products used in south-east Asian shrimp farming, and their potential impact on the environment _ a review[J]. The Science of the Total Environment. 2001,280:93-131
[57] Shimsuke Tanabe. Butyltin Contamination in marine mammals - a review[J]. Marine Pollution Bulletin. 1999, 39:62-72
[58] Supelco Bulletin. 1999, 923
[59] T. Horiguchia, U, C. Hyeon-Seob, H. Shiraishia, Y. Shibataa, M. Somac, M. Moritaa, M. Shimizud. Field studies on imposex and organotin accumulation in the rock shell, Thais clavigera, from the Seto Inland Sea and the Sanriku region, Japan[J]. The Science of the Total Environment. 1998, 214:65-70
[60] T.C.Hung, W.K.Hsu, P.J. Mang, A.Chuang. Organotins and imposex in the rock shell, Thais clavigera, from oyster mariculture areas in Taiwan[J]. Environmental Pollution. 2001, 112: 145-152.
[61] T. Horiguchi, H.Shiraisbi, M.Shimizu, M.Morita. Effects of triphenyltin chloride and five other organotin compounds on the development of imposex in the rock shell, Thais clavigera[J]. Environmental Pollution. 1997, 95:85-91.
[62] T. Horiguchi. Imposex and organotin compounds in Thais clavigera and Thais. bronni in Japan[J]. J. Mar. Biol. Assoc. 1994, 74:651-669
[63] Thomas P. O' Connor. National distribution of chemical concentrations in mussels and oysters in the USA[J]. Marine Environmental Research. 2002, 53: 117-143
[64] U.Schulte-Oehlmann, J.Oehlmann, B.Bauer, P. Fioroni, U.S.Leffler. Toxico-kinetic and -dynamic aspects of TBT-induced imposex in Hydrobia ulvae compared with intersex in Littorina litterea[J]. Hydrobiologia. 1998, 378:215-225
[65] V.A.Macias-Carranza, J.V. Macisa-Zamora, J.A.Villaescusa-Celaya Ciencias. Organotin compounds in marine water and sediments from the port of Ensenada, Baja California, Mexico(Compuestos organoestansdos en agua y sedimentos marinos del Puerto de Ensenada, Baja California, Mexico)[J]. Ciencias Marinas. 1997, 23(3): 377-394
[66] W.J.Shim, S.H.Kahng, S.H. Hong, N.S.Kim, S.K.Kim, J.H.Shim. Imposex in the rock shell, Thais clavigera, as evidence of organotin contaminaton in the marine environment of
Korea[J]. Marine Environmental Research. 2000, 49:435-451.
[67] W. Schnaak, Th. Kuchler, M.Kujawa, K.-P. Henschel, D.Subenbach, R.Donau. Organic contaminants in aewage sludge and their ecotoxicological significance in the agricultural utilization of sewage sludge[J]. Chemosphere. 1997, 35(1/2): 5-11
[68] Wuping Liu, Hian Kee Lee. Chemical modification of analytes in speciation analysis by capillary electrophoresis, liquid chromatography and gas chromatography[J]. Journal of Chromatography A. 1999, 834:45-63
[69] Yolanda Morcillo, Cinta Porte. Monitoring of organotin compounds and their effects in marine molluscs[J]. Trends in Analytical Chemistry. 1998, 17(2): 109-116
[70] Z.Y. Li. Application of imposex as a biomonitor of tributyltin pollution[J].青岛海洋大学学报. 2001, 31: 480-486.
[71]2000年中国沿海港口货物吞吐量统计[J]．中国港口．2001，2：320
[72]蔡爱智．粤东柘林湾的泥沙来源与沉积环境[J]．厦门大学学报(自然科学版)．1994，33(4)： 515-520
[73]程作联．有机锡的环境化学[J]．海洋环境科学．1989，8(4)：41-47
[74]邓华．用聚乙二醇固定相分析中草药的HPLC新方法及相关技术研究[D]．2001，5．
[75]邓尚贵，章超桦．利用正交试验优化贻贝水解工艺[J]．水产学报．1997，21(2)：220-224
[76]D．阿那尼，黄玉瑶．氯化二丁基锡对雌性小鼠的生殖毒性[J]．环境科学学报．2000，20(6)：746-749
[77]胡春，王圣符．有机锡化合物的用途[J]．化学与粘合．1995，3：160-163
[78]胡冠九，徐明华．有机锡化合物的性质、环境污染来源及测定方法[J]．环境监测管理与技术．2000，1 2：14-16
[79]黄国兰，陈志琼，戴树桂．丁基锡化合物在水体悬浮颗粒物上的吸附行为研究[J]．环境科学学报．1998，18(2)：1 37-140
[80]黄国兰，孙红文，戴树桂．巯基棉预富集、气相色谱-原子吸收联用技术测定水样中丁基锡化合物[J]．中国环境科学．1997，17(3)：283-285
[81]黄业茹，施钧慧，任剑璋，全浩．海水及鲈鱼中有机锡的GC-MS分析[J]．1999，5(2)：70-73
[82]江桂斌，刘稷燕，周群芳，吴迪靖．我国部分内陆水域有机锡污染现状初探[J]．环境科学学报．2000，20(5)：636-638
[83]江桂斌，徐福正，何滨，刘稷燕，周群芳，郭磊，张福军，吴迪．有机锡化合物测定方法研究进展[J]．海洋环境科学．1999，18(3)：61-66
[84]江桂斌、刘稷燕．固相微萃取-气相色谱火焰光度检测丁基锡化合物[J]．化学通报(增刊)，1999，42．
[85]江桂斌．气相色谱-表面发射火焰光度检测法测定有机锡和有机锗化合物[J]．环境化学．1997，16(2)：103-108
[86]李春喜，王志和，王文林．生物统计学[M]．2000，第二版
[87]刘稷燕，江桂斌，徐明德，南极长城湾附近和台湾以南部分海域水样中丁基锡化合物分析[J]．环境科学学报．2002，3：267-269
[88]刘稷燕，江桂斌．顶空固相微萃取-气相色谱表面发射火焰光度检测法测定底泥中的丁基锡化合物[J]．分析化学．2001，2：158-160
[89]鲁晓翔，王绍树，张明春．酶法水解蚂蚁蛋白的研究[J]．天津商学院学报．1997，2：17-21
[90]全燮，陈硕，薛大明，赵雅芝，杨风林．海洋环境中有机锡分析方法研究进展[J]．海洋环境
科学．1996，2：62-67
[91]全燮，陈硕，薛大明，赵雅芝，杨风林．有机锡污染物在海洋沉积物中的迁移和转化[J]．海洋环境科学．1995，14(4)：21-26
[92]施华宏，黄长江，谢文勇．用疣荔枝螺性畸变监测海洋有机锡污染的方法初探[J]．海洋环境科学．2001，21(4)：37-41
[93]施华宏，黄长江．海产腹足类性畸变现象的形态特征[J]．台湾海峡．2001，20(4)：552-555
[94]施华宏，黄长江．全面禁止TBT防污漆保护海洋生态环境[J]．海洋环保．2001，5：61-65
[95]施华宏，黄长江．有机锡污染与海产腹足类性畸变[J]．生态学报．2001，21(10)：1711-1717
[96]王璋编．食品酶学[M]．北京：中国轻工业出版社．1 990，60-185
[97]王志民，袁永俊，张艳萍，刘芳，高健．水解动物蛋白(H A P)的酶法制备及应用[J]．四川工业学院学报．2000，2：93-94
[98]王志民，袁永俊，张艳萍．水解动物蛋白的酶法制备及应用[J]．食品工业科技．1998，(5)：12-14
[99]肖凯军，郭祀远，李琳，陈健，蔡妙颜，官家伦．鲨鱼鳍软骨的胰蛋白酶水解及其“蜂窝式”降解机制[J]．上海水产大学学报．2000，9(3)：219-225
[100]徐小白．典型化学污染物在环境中的变化及生态效应[M]．北京：科学出版社．1998，99-175
[101]杨东，王(?)．水解鱼蛋白及其功能特性的研究[J]．食品科学．1999，11：23-26
[102]杨文鸽，张芝芬．胰蛋白酶对蚌肉蛋白水解条件的研究[J]．食品工业科技．2002，22(2)：38-39
[103]袁东星，钟树明，杨东宁．厦门西港和闽江口表层沉积物中有机锡含量分布[J]．台湾海峡．2001，20(1)：91-95
[104]张康生，刘双进，赵忠宪．有机锡污染调控对策初步分析[J]．环境科学．1996，16(4)：293-296
[105]张龙翔，张庭芳，李令媛．生化实验方法和技术[M]．北京：高等教育出版社．1997，(第二版)，47-52
[106]张硕慧．T B T的污染及控制措施的分析[J]．交通环保． 2001，22(3)：30-33
[107]周名江，李正炎，颜天．海洋环境中的有机锡及其对海洋生物的影响[J]．环境科学进展．1994，2(4)：67-69
[108]周群芳，江桂斌．山东烟台海水样品中有机锡化合物的气相色谱-表面发射火焰光度法测定[J]．海洋学报．2000，22(8)：391-396
[2] Alzieu C, Thibaud Y, Heral M. Evaluation of sicks of using antifouling paints in the oyster culture basins[J], Rev Tray inst peches marit. 1980, 44(4): 301-348
[3] Asa Espmark Wibe, Trond Nordtug, Bjorn Munro Jenssen. Effects of bis(tributyltin)oxide on antipredator behavior in threespine stickleback Gasterosteus aculeatus [J]. Chemosphere. 2001, 44:475-481
[4] B S.Smith. Male characteristics on female mud snails caused by antifouling bottom paints[J]. Appl. Toxicol. 1981, 1:22-25
[5] B.Bauer, P.Fioroni, I.Ide, S.Liebe, J.Dehlmann, E.Stroben, B.Watermann. TBT effects on the famale gential system of Littorina Littorea: a possible indication of tributyltin pollution[J]. Hydroilogia. 1995, 309:15-27
[6] Blaber, S.J.M. The occurrence of a penis-like outgrowth behind the right tentacle in spent females of Nucella lapillus [L]. Proceedings of the Malacological Society of London. 1970, 39:231-23
[7] Blackmore G. Imposex in Thais clavigera (Neogastropoda) as an indicator of TBT (Tributyltin) bioailability in coastal waters of Hong Kong [J]. Moll Stud. 2000, 66:1～8
[8] C. Montigny, G. Lespes, M. Potin-Gautier. Matrix effects and selectivity of the detector in the deter- ruination of butyl- and phenyitins by gas chromatography-flame photometric detection[J]. Journal of Chromatography A. 1998, 819:221-230
[9] C.Carlier-Pinasseau, G.Lespes, M.Astruc. Validation of organotin compound determination in environmental samples using NaBEt_4,ethylation and GC-FPD[J]. Environmental technology. 1997, 18(12): 1179-1186
[10] C.Stewart, S.J. Mora. A review of the degradation of Tributyltin in the marine environment[J]. Environ. Technol. 1990, 11:565-570
[11] Caterina Pellegrino, Paolo Massanisso, Roberto Morabito. Comparison of twelve selected extraction methods for the determination of butyl- and phenyltin compounds in mussel samples[J]. Trends in Analytical Chemistry. 2000, 19:97-106
[12] Ch. Bancon-Montigny, G. Lespes, M. Potin-Gautier. Improved routine speciation of organotin com- pounds in environmental samples by pulsed flame photometric detection[J]. Journal of Chromatography A. 2000, 896:149-158
[13] Champ M.A. A review of organotin regulatory strategies, pending actions, related costs and benefits[J]. The Science of the Total Environment. 2000, 258: 21-71.
[14] Clark S, Ashby J, Craig P J. On-column hydride generation methed for the production of volatile of tin arsenic and antimony for the gas chromatographic analysis of dilute solutions[J]. Analyst. 1987, 112(12): 1781-1782
[15] D.Minchin, J.Oehlmann, C.B.Duggan, E.Stroben, M.Keatinge. Marine TBT antifouling contamination in Ireland following legislation in 1987[J]. Pollution Bulletin. 1995, 30:633-639
[16] Dirkx W M R, Lobinski R, Adams F C. Speciation analysis of organotin in water and sediments
by gas chromatography with optical spectrometric detection after extraction separation[J]. Analytical chemistry. 1994, 286:309-318
[17] E.Pelletier and C.Normandeau. Distribution of butyltin residues in mussels and sea stars of the St Lawrence estuary[J]. Environmental Technology. 1997, 18(12): 1203-1208
[18] Encarna Gonzlez-Toledo, Mario Benzi, Ramon Compaf, Merc Granados, Maria Dolors Prat. Speciation of organotin compounds in shellfish by liquid chromatography -fluorimetric detection[J]. Analytical chemistry. 2001,443: 183-190
[19] Eros Bacci, Carlo Gaggi. Organotin compounds in harbor and marina waters from the northern Tyrrhenian Sea[J]. Marine pollution. 1989, 20(6): 290-292.
[20] Esmeralda Millan, Janusz Pawliszyn. Determination of butyltin species in water and sediment by solid-phase microextraction-gas chromatography-flame ionization detection[J]. Journal of Chromatography A. 2000, 873:63-71.
[21] Fent K, Hunn J. Phenyltins in water, sediment, and biota of freshwater Marinas[J]. Environ Science Technology. 1991, 25(5): 956-963.
[22] G W. Bryan, P E.Gibbs. Comparison of the effectiveness of tributyitin chloride and five other organotin compounds in promoting the development of imposex in the dog-whelk Nucella lapillus[J]. Marine Biology. 1988, 68: 733-744.
[23] G. Lespes, V. Desauziers, C.Montigny, M.Potin-Gautier. Optimization of solid-phase microextraction for the speciation of buty- and phenyltins using experimental designs[J]. Journal of Chromatography A. 1998, 826: 67-76.
[24] Gibbs, P.E.,Bryan, G.W., Pascoe, P.L., Burt, G.R. The use of the dog whelk, Nucella lapillus, as an indicator of TBT contamination[J]. Journal of marine biological association of the United Kongdom. 1987, 67:507-523
[25] Gibbs.P.E.,Bryan. G.W. Reproductive failure in populations of the dog whelk, Nucella lapillus caused by imposex induced by TBT from antifouling paints. Journal of marine biological association of the United Kingdom[J]. 1986, 66: 767-777.
[26] Horiguchi T., Shiraishi H M, Shimizu M., Morita M., Effects of triphenyltin chloride and five other organotin compounds on the development of imposex in the rock shell, Thais clavigera[J]. Environmental Pollution. 1997, 95(1): 85-91
[27] Hyun Min Hwanga, Jae Ryoung Oh, Sung-Hyun Kahng, Kwang Woo Lee. Tributyltin compounds in mussels, oysters and sediments of Chinhae Bay, Korea[J]. Marine Environmental Research. 1999, 47:61-70
[28] J J.Cleary, Organotin and total tin in coastal waters of South-west England[J]. Marine Pollution Bulletin. 1985, 16:350-355
[29] J.L.Gomez-Ariza, E.Morales, I.Giraldez. Spatial distribution of butyltin and phenyltin compounds on the Huelva coast(southwest Spain) [J]. Chemosphere. 1998, 37(5): 937-950
[30] J.Oehlmann, E.Stroben, U.Schulte-Oehlmann, B.Bauer, P. Fioroni, B.Mardert. Tributyltin biomonitoring using prosobranchs as sentinel organisms[J]. Fresenius Journal of Analytical Chemistry. 1996, 354:540-545
[31] J.Oelhlmann, C.Bettin. TBT-induced imposex and the role of steroids in marine snails[J]. Malacol. Rev. Suppl. 1996, 6:157-161
[32] Jennie S.han, James H. weber. Speciation of methyl- and butyltin compounds and inorganic tin in oysters by hydride generation atomic absorotion spectrometry[J]. Analytical chemistry. 1988,
60(4): 316-319
[33] Jiang Gui-bin, Zhou Qun-fang. Direct Grignard pentylation of organotin-contaminated lard samples followed by capillary gas chromatography with flame photometricdetection[J]. Journal of Chromatography A. 2000, 886:197-205
[34] K.Elgethun, C.Neumann, P.Blake. Butyltins in shellfish, finfish, water and sediment from the Coos Bay estuary(Oregon, USA) [J]. Chemosphere. 2000, 41:953-964
[35] L.L.Liu, I.J.Suen. Organotins promoting the development of imposex in the oyster drill Thais clavigera[J]. Journal of the Fisheries Society of Taiwan. 1996, 23:149-154.
[36] Lobinki R, Dirkx W M R, Celemans M. Optimization of comprehensive speciation analysis of organotin compounds in environmental samples by capillary gas chromatography heliem microwave-induced plasma emission spectrometry[J]. Analytical chemistry. 1992, 64:159-165
[37] Lobinki R. Gas chromatography with element selective detection in speciation analysis: status and future prospects[J]. Analysis. 1994, 22:37-48
[38] M. Ceulemans, S. Slaets, F. Adams. Speciation of organotin in environmental sediment samples[J]. Talanta. 1998, 46:395-405
[39] M.D Molleret. Tributyltin in the environment-sources, fate and determination an assessment of present status and research needs[J]. Chemosphere. 1989, 18(9/10): 2015-2042
[40] Manuela A, Josep-Maria B, Ramon C. Analytical procedures for the determination of organotin compounds in sediment and biota: a critical review[J]. Journal of Chromatography A. 1997, 788:1-49
[41] Montserrat Sole. Effects of tributyltin on the MFO system of the clam Ruditapes decussata: a laboratory and field approach[J]. Comparative Biochemistry and Physiology. 2000, Part C 125: 93-101
[42] N.Sponer, P E.Gibbs, G W. Bryan, L J.Goad. The effect of tributyltin upon steroid titres in the female dogwhelk, Nucella lapillus, and the development of imposex[J]. Marine Environmental Research, 1991, 32:37-49
[43] Nicholas H. Snow. Solid-phase micro-extraction of drugs from biological matrices[J]. Journal of Chromatography A. 2000, 885:445-455
[44] Norunn Folsvik, John Arthur Berge, Einar M.Brevik, Marts Walday. Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella Lapillus) from Norway[J]. Chemospbere. 1999, 38(3): 681-691
[45] O Aboul Dahab. Tin compounds in sediments of Lake Maryut[J]. Egypt environmental pollution. 1990, 63:329-344
[46] Patricia Schubert, Inmaculada Fernandez-Escobar, Erwin Rosenberg, Josep-Maria Bayona. Evalu- ation of desulfurization procedures for the elimination of sulfur interferences in the organotin analy- sis of sediments[J]. Journal of Chromatography A. 1998, 810:245-251
[47] Pawliszyn J B. Solid-phase microextraction. Theory and pactice[M]. Wiley-VCH, Weinheim, Germary. 1997
[48] Peter F S, Aldis O V, Richard F L. Degradation of tributyltin in San Diego Bay, California, Waters[J]. Environmen Science Technology. 1986, 20(12): 1229-1235
[49] Philippe Quevauviller, Roberto Morabito. Evaluation of extraction recoveries for organometallic determinations in environmental matrices[J]. Trends in Analytical Chemistry. 2000, 19: 86-96
[50] Piver W T. Organotin compounds: industrial application and biological investigation[J]. Environ heathlth perspsct. 1973, 6:61-79
[51] R J Maguire, H Huneault. Determination of butyltin species in water by gas chromatography with flame photometric detection[J]. Journal of Chromatography A. 1981,209:458-462
[52] R.Saint-Louis, C.Gobeil, E.Pelletiier. Tributyltin and its degradation products in the St Lawrence estuary (Canada) [J]. Environmental Technology. 1997, 18(12): 1209-1218
[53] S M.Evans, T. Leksono, P. Mckinnell. Tributyltin pollution: A diminishing problem following legislation limiting the use of TBT-based anti-fouling paints[J]. Marine Pollution Bulletin. 1995, 30,14-21
[54] S. Diez, M. Abalos, J.M. Bayona. Organotin contamination in sediments from the Western Mediter- ranean enclosures following 10 years of TBT regulation[J]. Water Research. 2002, 36: 905-918
[55] S.Shawky, H.emons. Distributions pattern of organotin compounds at different trophiclevers of aquatic ecosystems[J]. Chemosphere. 1998, 36(3): 523-535
[56] Sara Graslund, Bengt-Erik Bengtsson. Chemicals and biological products used in south-east Asian shrimp farming, and their potential impact on the environment _ a review[J]. The Science of the Total Environment. 2001,280:93-131
[57] Shimsuke Tanabe. Butyltin Contamination in marine mammals - a review[J]. Marine Pollution Bulletin. 1999, 39:62-72
[58] Supelco Bulletin. 1999, 923
[59] T. Horiguchia, U, C. Hyeon-Seob, H. Shiraishia, Y. Shibataa, M. Somac, M. Moritaa, M. Shimizud. Field studies on imposex and organotin accumulation in the rock shell, Thais clavigera, from the Seto Inland Sea and the Sanriku region, Japan[J]. The Science of the Total Environment. 1998, 214:65-70
[60] T.C.Hung, W.K.Hsu, P.J. Mang, A.Chuang. Organotins and imposex in the rock shell, Thais clavigera, from oyster mariculture areas in Taiwan[J]. Environmental Pollution. 2001, 112: 145-152.
[61] T. Horiguchi, H.Shiraisbi, M.Shimizu, M.Morita. Effects of triphenyltin chloride and five other organotin compounds on the development of imposex in the rock shell, Thais clavigera[J]. Environmental Pollution. 1997, 95:85-91.
[62] T. Horiguchi. Imposex and organotin compounds in Thais clavigera and Thais. bronni in Japan[J]. J. Mar. Biol. Assoc. 1994, 74:651-669
[63] Thomas P. O' Connor. National distribution of chemical concentrations in mussels and oysters in the USA[J]. Marine Environmental Research. 2002, 53: 117-143
[64] U.Schulte-Oehlmann, J.Oehlmann, B.Bauer, P. Fioroni, U.S.Leffler. Toxico-kinetic and -dynamic aspects of TBT-induced imposex in Hydrobia ulvae compared with intersex in Littorina litterea[J]. Hydrobiologia. 1998, 378:215-225
[65] V.A.Macias-Carranza, J.V. Macisa-Zamora, J.A.Villaescusa-Celaya Ciencias. Organotin compounds in marine water and sediments from the port of Ensenada, Baja California, Mexico(Compuestos organoestansdos en agua y sedimentos marinos del Puerto de Ensenada, Baja California, Mexico)[J]. Ciencias Marinas. 1997, 23(3): 377-394
[66] W.J.Shim, S.H.Kahng, S.H. Hong, N.S.Kim, S.K.Kim, J.H.Shim. Imposex in the rock shell, Thais clavigera, as evidence of organotin contaminaton in the marine environment of
Korea[J]. Marine Environmental Research. 2000, 49:435-451.
[67] W. Schnaak, Th. Kuchler, M.Kujawa, K.-P. Henschel, D.Subenbach, R.Donau. Organic contaminants in aewage sludge and their ecotoxicological significance in the agricultural utilization of sewage sludge[J]. Chemosphere. 1997, 35(1/2): 5-11
[68] Wuping Liu, Hian Kee Lee. Chemical modification of analytes in speciation analysis by capillary electrophoresis, liquid chromatography and gas chromatography[J]. Journal of Chromatography A. 1999, 834:45-63
[69] Yolanda Morcillo, Cinta Porte. Monitoring of organotin compounds and their effects in marine molluscs[J]. Trends in Analytical Chemistry. 1998, 17(2): 109-116
[70] Z.Y. Li. Application of imposex as a biomonitor of tributyltin pollution[J].青岛海洋大学学报. 2001, 31: 480-486.
[71]2000年中国沿海港口货物吞吐量统计[J]．中国港口．2001，2：320
[72]蔡爱智．粤东柘林湾的泥沙来源与沉积环境[J]．厦门大学学报(自然科学版)．1994，33(4)： 515-520
[73]程作联．有机锡的环境化学[J]．海洋环境科学．1989，8(4)：41-47
[74]邓华．用聚乙二醇固定相分析中草药的HPLC新方法及相关技术研究[D]．2001，5．
[75]邓尚贵，章超桦．利用正交试验优化贻贝水解工艺[J]．水产学报．1997，21(2)：220-224
[76]D．阿那尼，黄玉瑶．氯化二丁基锡对雌性小鼠的生殖毒性[J]．环境科学学报．2000，20(6)：746-749
[77]胡春，王圣符．有机锡化合物的用途[J]．化学与粘合．1995，3：160-163
[78]胡冠九，徐明华．有机锡化合物的性质、环境污染来源及测定方法[J]．环境监测管理与技术．2000，1 2：14-16
[79]黄国兰，陈志琼，戴树桂．丁基锡化合物在水体悬浮颗粒物上的吸附行为研究[J]．环境科学学报．1998，18(2)：1 37-140
[80]黄国兰，孙红文，戴树桂．巯基棉预富集、气相色谱-原子吸收联用技术测定水样中丁基锡化合物[J]．中国环境科学．1997，17(3)：283-285
[81]黄业茹，施钧慧，任剑璋，全浩．海水及鲈鱼中有机锡的GC-MS分析[J]．1999，5(2)：70-73
[82]江桂斌，刘稷燕，周群芳，吴迪靖．我国部分内陆水域有机锡污染现状初探[J]．环境科学学报．2000，20(5)：636-638
[83]江桂斌，徐福正，何滨，刘稷燕，周群芳，郭磊，张福军，吴迪．有机锡化合物测定方法研究进展[J]．海洋环境科学．1999，18(3)：61-66
[84]江桂斌、刘稷燕．固相微萃取-气相色谱火焰光度检测丁基锡化合物[J]．化学通报(增刊)，1999，42．
[85]江桂斌．气相色谱-表面发射火焰光度检测法测定有机锡和有机锗化合物[J]．环境化学．1997，16(2)：103-108
[86]李春喜，王志和，王文林．生物统计学[M]．2000，第二版
[87]刘稷燕，江桂斌，徐明德，南极长城湾附近和台湾以南部分海域水样中丁基锡化合物分析[J]．环境科学学报．2002，3：267-269
[88]刘稷燕，江桂斌．顶空固相微萃取-气相色谱表面发射火焰光度检测法测定底泥中的丁基锡化合物[J]．分析化学．2001，2：158-160
[89]鲁晓翔，王绍树，张明春．酶法水解蚂蚁蛋白的研究[J]．天津商学院学报．1997，2：17-21
[90]全燮，陈硕，薛大明，赵雅芝，杨风林．海洋环境中有机锡分析方法研究进展[J]．海洋环境
科学．1996，2：62-67
[91]全燮，陈硕，薛大明，赵雅芝，杨风林．有机锡污染物在海洋沉积物中的迁移和转化[J]．海洋环境科学．1995，14(4)：21-26
[92]施华宏，黄长江，谢文勇．用疣荔枝螺性畸变监测海洋有机锡污染的方法初探[J]．海洋环境科学．2001，21(4)：37-41
[93]施华宏，黄长江．海产腹足类性畸变现象的形态特征[J]．台湾海峡．2001，20(4)：552-555
[94]施华宏，黄长江．全面禁止TBT防污漆保护海洋生态环境[J]．海洋环保．2001，5：61-65
[95]施华宏，黄长江．有机锡污染与海产腹足类性畸变[J]．生态学报．2001，21(10)：1711-1717
[96]王璋编．食品酶学[M]．北京：中国轻工业出版社．1 990，60-185
[97]王志民，袁永俊，张艳萍，刘芳，高健．水解动物蛋白(H A P)的酶法制备及应用[J]．四川工业学院学报．2000，2：93-94
[98]王志民，袁永俊，张艳萍．水解动物蛋白的酶法制备及应用[J]．食品工业科技．1998，(5)：12-14
[99]肖凯军，郭祀远，李琳，陈健，蔡妙颜，官家伦．鲨鱼鳍软骨的胰蛋白酶水解及其“蜂窝式”降解机制[J]．上海水产大学学报．2000，9(3)：219-225
[100]徐小白．典型化学污染物在环境中的变化及生态效应[M]．北京：科学出版社．1998，99-175
[101]杨东，王(?)．水解鱼蛋白及其功能特性的研究[J]．食品科学．1999，11：23-26
[102]杨文鸽，张芝芬．胰蛋白酶对蚌肉蛋白水解条件的研究[J]．食品工业科技．2002，22(2)：38-39
[103]袁东星，钟树明，杨东宁．厦门西港和闽江口表层沉积物中有机锡含量分布[J]．台湾海峡．2001，20(1)：91-95
[104]张康生，刘双进，赵忠宪．有机锡污染调控对策初步分析[J]．环境科学．1996，16(4)：293-296
[105]张龙翔，张庭芳，李令媛．生化实验方法和技术[M]．北京：高等教育出版社．1997，(第二版)，47-52
[106]张硕慧．T B T的污染及控制措施的分析[J]．交通环保． 2001，22(3)：30-33
[107]周名江，李正炎，颜天．海洋环境中的有机锡及其对海洋生物的影响[J]．环境科学进展．1994，2(4)：67-69
[108]周群芳，江桂斌．山东烟台海水样品中有机锡化合物的气相色谱-表面发射火焰光度法测定[J]．海洋学报．2000，22(8)：391-396