气相色谱—表面发射光焰光度检测法测定有机锡和有机锗化合物

本文将自行研制的ＧＣ－ＦＰＤ系统用于有机锡和有机锗的形态分析，在最佳测定条件下，使用ＨＰ－１毛细管色谱柱和柱减法是样方法，成功地分离了九种有机锡化俣物和四种有机锗化合物，分别对样品的萃取、衍生方法以及仪器测定条件的优化等进行了讨论，并用本文所建方法分离和测定了环境样品中的有机锡化合物。     

大气飘尘中硝基多环芳烃的高效液相色谱分析

叙述了用高效液相色谱分析大气飘尘中硝基多环芳烃化合物的方法。对硅胶柱层析预分离、硝基多环芳烃的还原反应、液-液萃取分离、液相色谱条件和响应线性范围进行了研究。在所选的荧光检测波长下,1-硝基芘和2-硝基芴的最小可测量约为20×10~(-12)g.在国内首次测定了大气飘尘样品中的1-硝基芘含量,两种试样的测定值分别为0.11和1.4ug/1000m~3。     

使用底栖和浮游桡足类生物测试评估沉积物修复方案的效果

三丁基锡（TBT）是一种常见于船舶防污涂料中的有机锡化合物。尽管该化学物已于2008年被禁用,但在ports和港口等海上交通区域仍可检出致毒水平（浓度）的TBT。一项补救方案在新西兰的一个港口实施,以将TBT和铜的浓度降低到可接受的（浓度）值。这项研究使用分析化学和桡足类生物测试相结合的方法评估了该方案的有效性。在港口内的三个空间梯度上采集沉积物和水样,并在修复前后测定了有机锡和金属含量。利用底栖和浮游桡足类生物测试估算了沉积物和淘析样品的毒性。虽然底泥样品的急性毒性在修复后减少,但对底栖桡足类的繁殖率仍有影响。本研究所采用的方法有望评估沿海地区修复过程的效果。     

快速液相色谱-串联质谱法测定环境空气中的全氟化合物

不同研究报道的空气中离子型全氟化合物(PFCs)的分析方法各不相同,本文的目的在于对比和优化不同分析条件。通过对比不同流动相(甲醇和乙腈)、不同色谱柱(C8和C18)、不同梯度洗脱条件下目标化合物的分离效果,确定了以甲醇为流动相、C18色谱柱为分离柱和最佳梯度淋洗液分离的仪器分析条件。比较了甲醇和正已烷/丙酮混合溶剂萃取气相(PUF)和颗粒相(GFF)样品的效果,确定以甲醇为萃取溶剂。建立了空气中PFCs的LC-MS/MS优化分析方法,方法线性范围在0.1~50 ng·m L~(-1)之间,PUF与GFF样品方法检出限分别为0.02~0.35 pg·m~(-3)和0.02~0.26 pg·m~(-3)。同时将方法用于大气实际样品分析。     

热解法分离大气颗粒物中几种主要铵盐

本文实验了分离大气颗粒物样品中硫酸铵、硝酸铵、氯化铵的热解方法．在70℃的条件下,经过3h,硝酸铵和氯化铵就已基本挥发完全,而硫酸铵没有明显的损失．利用该方法,分离测定了一些大气颗粒物样品中的硫酸铵、硝酸铵、氯化铵及相应的其它金属盐．实验表明,热解法对于分离表征大气颗粒物中的铵盐是简单和实用的．     

废水反硝化生物反应器中喹啉降解细菌的分离与特性

杂环化合物喹啉是焦化等工业废水中的一种难降解化合物.有关喹啉微生物降解的研究还很有限,分离筛选多样的喹啉降解细菌,对认识喹啉的降解机制和强化废水中喹啉的降解具有重要意义.本研究通过富集和多种分离条件的培养,从焦化废水活性污泥及唪啉驯化的生物膜样品中分离获得56株与喹啉降解相关的菌株,以16S rDNA双酶切方法进行ARDRA分型,将这些菌株分为12个OTU.选取部分代表菌株进行16S rDNA测序分析,表明分离所获得的菌株主要是Ochrobactrum、Bacillus、Pseudomonas和Rhodococcus属的微生物.通过对部分菌株测定其喹啉降解能力.发现大部分菌株都能以喹啉为唯一碳源进行生长并高效降解喹啉,极少数菌株不能单独降解喹啉.降解喹啉的Ochrobactrum属菌株还未见报道.     

使用ACQUITY UPLC H-Class和Xevo TQD液相/串联质谱仪进行水中药物和个人护理产品(PPCP)的多残留分析

近年来,水体中存在的药物和个人护理产品(PPCP)残留在全世界范围内都受到了越来越多的关注.这些新型污染物对人类健康的影响以及它们对环境的潜在影响尚未被完全了解.随着人们的关注持续增长,全世界许多政府机构开始资助相关的研究,评估PPCP是否会导致有害的生态效应.许多已发表的文章都提到,在河流和溪流中存在万亿分之一(×10-12)水平的PPCP,因此需要能够检测这些痕量化合物的方法.除了需要检测低水平的PPCP,另一个主要挑战在于化合物种类和结构广泛的化学多样性.另外,水样品的复杂性还要求分析方法能够适用于样品多样性.本文介绍了井水和地表水样品中78种PPCP(包括酸性化合物、碱性化合物和中性化合物)的提取、分离和检测.     

加压流体萃取-硅酸镁柱净化-气相色谱质谱法同时测定土壤中有机氯农药和多环芳烃

本研究通过对仪器定性定量、样品萃取和萃取液净化等环节的条件优化实验,建立了同时测定土壤中8种有机氯农药和15种多环芳烃的加压流体萃取-硅酸镁柱净化-气相色谱质谱分析方法.化合物方法检出限在0.4—3.2μg·kg~(-1)之间,测定下限在1.6—12.8μg·kg~(-1)之间;对化合物含量为0.1 mg·kg~(-1)和0.5 mg·kg~(-1)的土壤加标样品分别进行6次平行分析,回收率在61%—119%之间,测定结果的RSD在2.8%—21%之间;对相关土壤标准物质进行分析,测定结果均在化合物认定值与不确定度范围内.与其他方法相比,本法减少了萃取环节共萃物、降低了净化环节对干扰物的洗脱、有效排除了假阳性,且显著提高了工作效率.     

GC-MS-MS测定蔬菜中八种有机磷农药

用GC-MS-MS同时测定蔬菜中的甲拌磷、二嗪农、甲基对硫磷、毒死蜱、倍硫磷、喹硫磷、杀扑磷和亚胺硫磷.对各个化合物的特征离子对、碰撞电压进行了优化,并阐述了优化反应监测模式(MRM)条件的过程和方法,同时分析了各个化合物的线性范围和最低检出限.将该方法用于蔬菜样品的检测,测得加标回收率在90.4%-105.0%之间,RSD在3.2%-9.3%之间.     

热解析-GC/MS方法测定大气中的羰基化合物

本文发展了五氟化苯肼(PFPH)衍生化.热解析-GC/MS方法,质谱采用SIM扫描方式,可实现对大气中23种羰基化合物的测定,并建立了方法相应的质量控制和质量保证(QA/QC)程序.采用美国环保局TO-15标准气体测量了这些羰基化合物衍生化采集测定的相对误差.方法检测限为0.01-0.25nmol,对大气样品采集测定的相对误差为-7.8%-40.2%.在2007年"好运北京"奥运测试赛的机动车限行前后和限行期间对大气中的羰基化合物进行实际观测,测得的羰基化合物的总平均浓度为31.47±11.53μg·m-3,主要组分为2,5-二甲苯苯甲醛、乙二醛、乙醛、正癸醛和苯甲醛.结果表明,2007年车辆限行期间,大气中羰基化合物浓度水平较2005年观测有显著降低.     

有机锡致海洋腹足类性畸变分子机制的研究进展

有机锡作为防污损生物附着添加剂曾被大量使用,在极低浓度下就能诱发腹足类发生性畸变现象,严重危害了海洋生态系统的平衡。虽然三丁基锡已被国际海事组织全球禁用,但目前报道的环境有机锡污染仍然非常严重,而且其致毒机制一直众说纷纭。首先,简述了腹足类性畸变及其在世界各个海域有机锡污染监测中的应用,重点综述了有机锡致海洋腹足类性畸变分子机制的3种假说:脊椎动物类型的类固醇激素假说、神经肽假说以及视黄酸X受体(retinoid X receptor,RXR)假说,另外,结合快速发展的分子生物学技术,探讨了研究腹足类性畸变分子机制的新思路和新方法。     

Bioconcentration of butyltin compounds by round crucian carp

Bioconcentration factors (BCF) by round crucian carp and partition coefficients between n‐octanol and water (Pow) were measured for dibutyltin, tributyltin and triphenyltin compounds. Pow was 0.97–3.66 for 7 organotin compounds. BCF of tributyltin and triphenyltin compounds was 1.70–2.77 for muscle, 1.70–2.66 for vertebra, 2.05–3.70 for liver and 1.49–3.50 for kidney.     

Ecotoxicity studies of some organotin compounds

The ecotoxicities of three organic compounds containing spacer groups, an intermediate organotin premonomer, four organotin monomers, their homopolymers and six copolymers of tributylin α‐chloroacrylate (TCA) are reported against two microorganisms viz., Pseudomonas aeruginosa and Sarcina lutea and a larval species Anemia salina (Nauplii II). The organic compounds containing spacer group were less toxic whereas the monomers were found to be highly toxic. The homopolymers were found to be more toxic than that of tributyltin acrylate (TBTAA), tributyltin methacrylate (TBTMA) and tributyltin α‐Chloroacrylate (TCA). The toxicity of TCA copolymers increased with the increase in tributyltin (TBT) content in the polymer. From this study it was not possible to establish any relationship between the chemical nature of the comonomer with its toxicity.     

Comparative effects of two antifouling paints on the oyster Crassostrea gigas

The effects of two antifouling paints, one containing organotin compounds, the other copper oxide, were studied from September 1983 to October 1984 on Crassostrea gigas (Thunberg) grown under natural field conditions in the Bay of Arcachon, France. The organotin paint reduced growth rate expressed as weight, length and width, but did not affect shell height; it drastically decreased the dry condition factor and shell density, but did not affect the viability of embryos and larvae from exposed oysters. However, some decrease in larval growth rate was observed. The copper paint had no effect on oyster growth, but lowered the condition factor compared to controls. Neither viability of embryos or larvae nor larval growth were affected by this paint.     

QSAR计算中的分子连接性指数法

本文介绍了分子连接性指数法和原理及各阶指数的计算方法，以及在ＱＳＡＲ计算中的应用实例，并对特殊连接性指数的用法作了分析。     

Imposex in marine gastropods may be caused by binding of organotins to retinoid X receptor

Organotin compounds have been widely used as antifouling paints for ships and fishing nets since the 1960s and have thus been released into marine environments. Aquatic invertebrates, particularly marine gastropods, are extremely sensitive to organotin compounds such as tributyltin (TBT) and triphenyltin (TPT) and undergo changes in sexual identity in response to exposure. This worldwide phenomenon is one of the worst consequences of pollution by man-made chemicals and has led to the ban of such compounds in antifouling paints in a number of countries, although organotin compounds still exist in the environment. So far, very low-concentrations of TBT or TPT have been shown to induce imposex (superimposition of male genitalia on female) in marine gastropods. Although the imposex induction mechanism has been controversial for many years, it was recently reported that TBT and TPT are potent and efficacious activators of retinoid X receptor (RXR), a member of the nuclear receptor superfamily. In this review, I discuss the involvement of RXR in the development of gastropod imposex. Physical and Chemical Impacts on Marine Organisms, a Bilateral Seminar Italy–Japan held in November 2004     

Speciation of organotin compounds in sediments of semi-closed areas along the Mediterranean coast of Alexandria

Organotin compounds were measured in sediments of four different semi-closed areas of the Mediterranean coast of Alexandria: the Eastern Harbour, Western Harbour, El-Max Bay, and Abu-Qir Bay. Due to the commercial trade activity inside the Western Harbour, in addition to the effect of wastes discharged from El Noubaria canal, it shows the highest concentrations of total tin (6.34 μg g^-1 dry weight), dibutyl tin (1.63 μg g^-1 wet weight), tributyl tin (0.33 μg g^-1 wet weight) and diphenyl tin (1.06 μg g^-1 wet weight) compared with other locations. The concentrations of TBT species showed the highest contents compared with DBT and DPhT compounds in all sampling areas. This trend might be due to the worldwide use of TBT not only as biocides in antifouling paints but also as preserving agents for wood, fungicides in agricultural activities, and heat and UV stabilizers of PVC, which results in a direct release of TBT into the water body, accumulation in aquatic fauna. There is also precipitation into sediments and a decrease in degradation rate into its derivatives. Variations, types, concentrations, and distribution of different organotin compounds are discussed in the areas under investigation. The study reveals a new record of organotin compounds along the Alexandria coast and makes comparisons with other surrounding areas of interest.     

有机化合物水中溶解度的测定与估算

本文介绍用摇瓶法、产生柱法和动态联柱高效液相色谱法等方法测定有机化合物在水中溶解度的研究方法,同时给出了某些农药、硝基多环芳烃和氯苯类化合物的水中溶解度的实验数值.     

Retrospektives Monitoring von Organozinnverbindungen in biologischen Proben aus Nord- und Ostsee – sind die Anwendungsbeschränkungen erfolgreich?

Background, aim, and scope Organotin compounds are used as biocides, plastic additives and catalysts. With respect to environmental effects, tributyltin (TBT) and triphenyltin (TPT) compounds are the most relevant, because of their high aquatic toxicity and endocrine effects on mussels and snails. TBT was mainly used as antifouling agents in coatings of ships and boats. In 1989, Germany banned the application to ships <?25?m length. Finally, in 2003, the use of organotin-based antifoulants within the European Union was completely banned. To verify the effectiveness of the restrictions a retrospective monitoring study was initiated. Material and methods A set of appropriate archived samples was retrieved from the German environmental specimen bank (ESB) comprising standardized pooled samples of eelpout (Zoarces viviparus) muscle tissue and of soft bodies of common mussels (Mytilus edulis) sampled at two locations in the North Sea and one in the Baltic Sea. Analysis of organotin compounds included n-hexane extraction, derivatisation with sodium tetraethyl borate, capillary gas-chromatographic separation and atomic emission detection. Results and Discussion Altogether, time series cover the period 1985 to 2006, including data of an earlier study (Rüdel et al. 2003). Until the late 1990s, TBT remained more or less constant in all samples (e.?g. 17?±?3?ng/g wet weight, ww, in mussels from Jadebay/North Sea). The German ban of TBT-based antifoulings for small ships had no effects on environmental concentrations because large ships dominate in the investigated North Sea regions. After the EU-wide ban of TBT in 2003, however, significant decreases in mussel and fish contamination could be observed. In mussels from Jadebay, TBT concentrations were 14 and 6?ng/g ww in 2004 and 2005, respectively. TBT contamination in eelpout of the same region decreased to about 30 percent of the initial concentrations in 2006. Corresponding decreases were detected for TPT. Declining trends were also found in fish and mussels sampled from a Baltic Sea offshore site. Conclusions The results demonstrate the effectiveness of the legal measures undertaken to control organotin inputs into the aquatic environment. Nevertheless, organotin compounds are still relevant pollutants. Water concentrations calculated from the measured tissue concentrations by using the respective bioconcentration factors are still above the Environmental Quality Standards derived in the context of the Water Framework Directive (0.2?ng/l) and the OSPAR mussel EAC (Environmental Assessment Criteria; 2.4?ng/g ww). Thus adverse effects to marine organisms cannot be excluded. Recommendations and perspectives Further studies should be performed to verify the declining trends. More sensitive analytical methods, e.?g. species-specific isotope dilution analysis, are recommended in order to detect lower environmental concentrations.