双（三环己基锡）四氯邻苯二甲酸酯的合成、表征和晶体结构的测定

合成了双（三环己基锡）邻苯二甲酸酯Cl4C6（CO2Sn（C6H11）3）2,利用元素分析仪和IR表征了其结构。通过X-射线单晶衍射仪,测定了该配合物的晶体结构。该化合物晶体属单斜晶系,空间群P-1,a=14．5522（13）,b=13．3651（12）,c=34．006（3）（^°A）,β=97．8990（10）°,Z=4,V=6551．2（10）nm^3,R=0．0603,Rw=0．1287,S=1．185。该分子是通过苯环桥联的双核有机锡化合物,分子中的两个锡原子均为畸变的四面体构型。     

几种杂环有机锡(Ⅳ)Schiff碱配合物的合成与表征

通过二苄基二氯化锡与双缩Schiff碱反应，合成了8种新的杂环有机锡（Ⅵ）配合物．通过元素分析、红外光谱、紫外-可见光谱、核磁共振氢谱等物理化学测试，推测了它们的可能结构．结果证明，这些物质均为六配位有机锡化合物．     

有机锡对斜生栅藻(Scenedesmus obliquu)的毒性影响试验研究

有机锡对海洋环境有着很大的破坏作用,为此以一甲基氯化锡(CH3SnCl3)和二甲基氯化锡((CH3)2SnCl2)为代表,研究了不同浓度有机锡对斜生栅藻(Scenedesmus obliguus)的毒性影响,并且对两种有机锡的毒性进行了对比试验.结果表明,一甲基氯化锡和二甲基氯化锡对斜生栅藻的生长均有一定抑制作用,且二甲基氯化锡的毒性大于一甲基氯化锡.当有机锡浓度为200 μg·L-1时,对藻细胞的生长抑制达到20.4%;随着有机锡浓度的增加,抑制效应增大.     

Accumulation of organotin compounds and marine birnavirus detection in Korean ascidians

ABSTRACT:   Recently, a serious disease spread extensively in aquaculture sites of the ascidian Halocynthia roretzi in Korea. To understand circumstances of ascidians in Korean aquaculture sites, residue levels of organotin compounds were analyzed, and detection of a marine birnavirus (MABV) in tissues of H. roretzi was attempted. Korean H. roretzi showed high concentrations of butyltins (mono, di, and tributyltins), especially in the gill, hepatopancreas, and digestive tract. However, there was no significant difference in the residues of butyltins in the hepatopancreas between diseased and non-diseased ascidians. The positive rate of MABV detection was high in the hepatopancreas, but also no significant difference was observed between diseased and non-diseased individuals. These observations suggest that an accumulation of tributyltin and a latency of MABV in H. roretzi tissues does not directly relate to the occurrence of the disease.     

Degradation of organotin compounds in organic and mineral forest soils

Broad industrial application of organotin compounds (OTC) leads to their release into the environment. OTC are deposited from the atmosphere into forest ecosystems and may accumulate in soils. Here, we studied the degradation of methyltin and butyltin compounds in a forest floor, a mineral, and a wetland soil with incubation experiments at 20 °C in the dark. OTC degraded slowly in soils with half‐lives estimated from 0.5 to 15 years. The first order degradation rate constants of OTC in soils ranged from 0.05 to 1.54 yr^–1. The degradation rates in soils were generally in the order mono‐ ≥ di‐ > tri‐substituted OTC. Stepwise dealkylation was observed in all cases of di‐substituted OTC, but only in some cases of tri‐substituted OTC. Decomposition rates of OTC in the forest floor were higher than in wetland and mineral soils. Tetramethyltin in the gas phase was not detected, suggesting little tin methylation in the wetland soils. Slow degradation of OTC in soils might lead to long‐term storage of atmospherically deposited OTC in soils.     

有机锡聚合物的合成及应用

介绍有机锡聚合物的研究现状，重点介绍有机锡聚合物的合成方法及在海洋防污涂料、木材防腐保护、荧光染料、光化学反应、微晶学和聚合物改性等方面的应用。     

Behaviors and Effects of Organotin Compounds in the Environment

The pathways of organotin compounds entering the environment, mechanisms of tin methylation, bioaccumulation, transport and degradation of organotin compounds in the environment are summarized, and the toxicity and anticancer activity and ecological effects of organotin compounds are also discussed. Organotin compounds were applied in the industrial, the agricultural and antipollution dope for the shipping, with transport into water body. Microbes play an important role during tin methylation. Organotin compounds were decomposed by the water, the photo and microbe. TBT and TPT are very toxicity to halobios, and can be condensed by them, enrichment index is between 5 000 to 10 000, which strongly affect the ocean ecosystem. Development of environment-friendly dope for shipping, and studying organotin effect on halobios community and ocean ecosystem are suggested.     

有机锡化合物对环境的污染及其毒性

论述了船舶防污涂料中的有机锡化合物对海洋生物的影响：使性畸变、干扰钙代谢和抑制Na^＋／H^-交换;聚氯乙烯（PVC）稳定剂中的MMT、DMT、MBT和DBT对饮用水的污染;农用杀虫荆和杀菌荆中有机锡化合物对植物、水体的污染及最终通过食物链进入人体,对人体健康造成危害。     

管角螺性畸变现象的组织解剖学研究及扫描电镜观察

为了探讨管角螺性畸变过程中,生殖系统在形态和组织结构方面的变化,以及性畸变可能对其种群带来的不良影响,实验采用组织解剖学和扫描电镜的方法,研究了广东湛江、广西北海、钦州和防城港及越南胡志明市5个区域管角螺的未成熟和成熟正常雄、雌个体以及性畸变个体的生殖系统结构。结果显示,管角螺性畸变个体除具有正常的雌性生殖器官外,还有输精管和阴茎等雄性生殖器官,并且性畸变个体阴茎的位置、形状和输精管的组织结构与正常雄性个体的相似,管角螺性畸变现象仅见于成熟个体,高程度性畸变雌体的性腺发育受阻。性畸变率(IOI)结果显示,8批样中管角螺性畸变严重程度依次是北海1北海2湛江钦州1防城港近海越南胡志明市、钦州2和防城港白龙珍珠湾,其中北海的性畸变情况最为严重,性畸变率平均达到90%;北海种群的输精管发育指数(VDSI)也高于其他地区群体;并且北部湾管角螺的雌雄性比几乎都要小于1,总体呈现减少的趋势。研究表明,有机锡污染可能已对北部湾管角螺种群的延续造成威胁。     

Quality Criteria for Re-Use of Organotin-Containing Sediments on Land (7 pp)

Background, Aim and Scope   The use of organotin compounds as antifouling agents on ships is prohibited at EU level since 1 July 2003. Because of its persistence, the presence of organotin compounds in harbour sediment will however remain a problem for years. Dumping of dredged sediment in sea is subject to very strict quality criteria, stimulating the exploration of re-use alternatives, such as re-use on land. Within the TBT Clean project (EU LIFE Project 02/ENV/B/341) an assessment framework for re-use of organotin containing treated sediment on land as secondary granular building material was developed. Three scenarios were considered: free re-use on land, re-use above groundwater level with cover layer, and re-use under groundwater level (the latter two scenarios are referred to as restricted re-use). Receptors considered were humans, ecosystem and groundwater. Generic upper concentration limits and sediment leaching limits were calculated. Materials and Methods: Upper concentration limits were calculated with the Vlier-Humaan model. This model allows to calculate soil remediation values according to the Flemish legal framework. The focus of the methodology is the protection of human health, although a check for ecotoxicity was included in the project. The soil remediation value for residential land-use was selected within the scenario for free re-use; for restricted re-use (no direct contact possible), the soil remediation value for industrial land-use was selected. Leaching values were calculated with an analytical soil and groundwater transport model. The reference scenario behind the leaching criteria of the European Landfill Directive was modified to fit the project objectives. Default values for application height and length were used. The point-of-compliance was situated at 20 m distance in the groundwater. Physicochemical properties were taken from literature; sorption characteristics were taken from literature and were measured on 6 treated sediment samples during the project. Plant-uptake values were taken from the literature. Toxicological criteria were taken from EFSA. Results: The assessment framework provided an upper limit (SedUL) and an leaching value (SedLV) for each scenario, expressed as mg/kg dm in the sediment. Criteria were calculated for tributyltin (TBT) and dibutyltin (DBT); too few data were available for monobutyltin (MBT). The SedUL equalled 0.51 mg TBT/kg dm and 0.07 mg DBT/kg dm for free re-use and 195 mg TBT/kg dm and 205 mg DBT/kg dm for restricted re-use (two scenarios). For free re-use the SedLV was only limiting for TBT at Kd of < 2000 l/kg in the sediment. Under re-use above groundwater level with coverage SedLV values ranged from 6.9 – 29 mg TBT/kg dm and from 12 – 33.3 mg DBT/kg dm (Kd ranging from 100 – 10000 l/kg); under re-use below groundwater level SedLV values ranged from 0.007 – 0.77 mg TBT or DBT/kg dm (Kd ranging from 100 – 10000 l/kg). Discussion: Results are subject to large uncertainties because of variation in input data; the model output is sensitive to variation in plant uptake (SedUL for free re-use), Koc or Kd (SedUL for restricted re-use, SedLV for re-use with coverage), Henry's law coefficient (SedUL for restricted re-use); all these parameters show orders of magnitude variation. Conclusions: A feasible and consistent framework for evaluation of the re-use of treated organotin containing sediment was developed. However, the resulting quality criteria are still subject to large uncertainties, due to uncertainties in input data. Recommendations and Perspectives: High-quality data on plant uptake and soil sorption of organotin compounds, the influence of soil properties on these processes, and long-term terrestrial toxicity data are needed to refine the calculations. The quality criteria should be reviewed when these data become available.