有机锡化合物对水生无脊椎动物的毒性研究

通过不同层次水生无脊椎动物的毒理学研究，能更好地反映有机化合物的生态效应，以氯化三丁基锡（ＴＢＴＣｌ）为例，结果表明，ＴＢＴＣｌ对原生动物等５种水生无脊椎动物的半致死浓度（ＬＣ５０）为２５．６５－３５５．６３ｐｐｂ，有明显的种特异性，ＴＢＴＣｌ对河口轮虫种群净生殖率ＥＣ５０为１０ｐｐｂ，影响平均寿命ＥＣ５０为２２ｐｐｂ，根据浓度Ｃ及原生动物平衡种类数Ｓｅｑ进行回归，得方程Ｓｅｑ＝１１．８７－１．８     

用贻贝、牡蛎作为生物指示物监测渤海近岸水体中的丁基锡污染物

用贻贝和牡蛎作为生物指示物研究渤海近岸水体中丁基锡的污染现状.结果表明,丁基锡检出率达100%.总丁基锡浓度在23.4ng Sn·g-1至 162.4ng Sn·g-1 范围内,平均浓度为64.8ng Sn·g-1.在丁基锡化合物中三丁基锡为主要的污染物,表明我国继续使用含有三丁基锡的船舶防污涂料.贻贝和牡蛎对丁基锡化合物具有相似的富集能力.海产品中丁基锡的污染对人们的健康存在潜在的影响.     

苯酚、苯胺及其衍生物对斜生栅列藻的急性毒性及QSAR研究

本文应用ＯＥＣＤ标准方法测定了１８种酚类胺类化合物对斜生栅列藻的４８ｈ－ＥＣ６０值，选择参数ＥＬＵＭＯ和ｌｇＫｏｗ进行了ＱＳＡＲ分析，得到下列回归方程：－１ｇＥＣ５０＝２．５４１－０．６４９ＥＬＵＭＯ＋０．２９９ＬｇＫｏｗ，ｎ＝１８，ｒ＝０．９０３，ＳＥ＝０．３１４应用所得方程计算了化合物的毒性，探讨了毒机理。     

部分取代苯类在江水中的生物降解与结构相关性研究

测定了２７种取代苯类化合物在松花江江水中的生物降解性．采用量子化学ＭＯＰＡＣ６．０－ＡＭ１法计算了化合物的分子量(ＭＷ)、生成热(Ｈｆ)、分子总表面积(ＴＳＡ)及最高占有轨道能(ＥＨＯＭＯ),结合辛醇/水分配系数ｌｇｐ及酸解离常数ｐＫａ对其中２２种化合物的ＢＯＤ值进行多元线性回归分析,得到如下模型:ＢＯＤ＝１０５．７３－０．４３９ＭＷ－０．０７６Ｈｆ－６．６６０ｌｇＰｎ＝２２,Ｒ２＝０．８２１,ＳＥ＝８．２５０,Ｆ＝２７．５６,Ｐ＝０．０００应用所得模型对其余５个化合物的生物降解性进行了预测．只有一个化合物的相对预测误差大于２０%,为２０．８%．平均预测误差为１２．４%．     

催化动力学光度法测定水中痕量亚硝酸根

基于亚硝酸根对溴酸钾氧化甲基紫的反应具有催化作用，建立了测定亚硝酸根的催化动力学光度法，研究了最佳测试条件，用于测定水样和标准样品中的亚硝酸根，获得满意结果，方法检出限为０．１６μｇ．５０ｍｌ＾－１，线性范围为０．２５－１２．０μｇ．６０ｍＬ＾－１，回收率在９０％－１０８％之间。     

酸化—吹气—吸收法测定水及废水中的硫化物

本文设计了硫化物测定的酸化－吹气－吸收装置，验证了装置对硫化的回收效果，对硫化物标准溶液的配制及其稳定性进行了研究，对分析条件进行了最佳选择，建立了亚甲基监光度法测定硫化物的分析方法，并对实际样品进行了测定。本方法的检出限为０．００５ｍｇＳ＾２－／ｌ，线性范围为０．００５－０．７００ｍｇＳ＾２－／ｌ，可应用于水和废水样品中微量硫化物的测定。     

多聚磷酸盐的离子色谱法分析研究

本文以美国ＤＩＯＮＥＸ公司Ｏｍｎｉ Ｐａｃ ＰＡＸ－１００为分离柱，氢氧化钠为淋洗液，甲醇为有机改进剂，梯度淋洗分离多聚磷酸盐（正磷酸盐ＰＯ＾３－４，焦磷酸盐Ｐ２Ｏ＾４－７，三聚磷酸盐Ｐ３Ｏ＾５－１０）。研究了分离机理和流动相的选择、色谱条件的最佳化、降低基线噪音的方法和多聚磷酸盐的稳定性。建立了同时测定ｐｐｂ级（μｇ／ｌ）多聚磷酸盐的离子色谱新方法。对样品的测定结果回收率均在９７．４９％—１０６     

甲基纤维素在重量法测土壤硅中的应用研究

在重量法测定土壤全硅中，用甲基纤维素作凝聚剂，试验结果表明，用该凝聚剂与动物胶作凝聚剂测定土壤全硅的结果基本一致。甲基纤维素法的回收率为９３．８％—１０８．３％，标准差为０．３０％，变异系数最大为０．８８％；动物胶法的回收率为９２．３％—１０５．３％．用两种方法测定同一样品，两者间的绝对相差最大只有０．５％；ｔ检验表明，ｔ＝０．３６１＜ｔ（０．０５）＝２．２０，差异极不显著．因此，甲基纤维素可作为重量法测土壤硅的凝聚剂．     

原子吸收分光光度法测定植株中钙、镁的几种样品前处理方法的比较

本文比较了原子吸收分光光度法测定植株中钙、镁的三种样品前处理方法：干友化法、１ｍｏｌ／ＬＨＣｌ振荡提取法（振荡法）和１ｍｏｌ／ＬＨＣｌ静止浸泡提取法（浸泡法）．结果表明，振荡法和浸泡法对钙的测定结果平均分别为干灰化法的１０１％和９２．０％，对镁的测定结果平均分别为１０３％和９７．６％．振荡法和浸泡法与干灰化法之间不存在显著性差异（α＝０．０５），它们之间有极显著的正相关性（相关系数在０．９９以上）．因此，在大批量样品的常规分析中，１ｍｏｌ／ＬＨＣｌ提取法可代替干灰化法．     

阻抑动力学测定痕量砷（Ⅲ）的研究

在硫酸介质中，痕量Ａｓ（Ⅲ）能阻抑溴酸钾、镍化钾和锆试剂之间的褪色反应，研究了阻抑褪色反应的最佳佳实验条件，建立了测定初量Ａｓ（Ⅲ）的方法，本方法的最低检测限为３．６×１０＾－５μｇ·ｍｌ＾－１，测定范围为０．０－１．０μｇ·２５ｍｌ＾－１，用于测定工业废水中的Ａｓ（Ⅲ），获得了满意的结果。     

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.     

Transport of butyltins at the water‐air interface and the adsorptive behavior of tributyltin in the surface microlayer

The transfer dynamics and enrichment phenomena of monobutyltin chloride(MBT), dibutyltin chloride(DBT) and tributyltin chloride(TBT) at the water‐surface microlayer (SM) interface were studied. The transport processes of the three compounds at the interface are very fast in the estuarine environment. The mass transfer coefficients are 1.54 m/h for MBT, 2.16 m/h for DBT, 1.56 m/h for TBT. The effect of various factors, including pH, salinity, suspended particulate and temperature, on the adsorptive behavior of TBT in the water's surface microlayer was also studied.     

Population-related toxicity responses to two butyltin compounds by zoeae of the mud crab Rhithropanopeus harrisii

We exposed zoeae of the mud crab Rhithropanopeus harrisii to either bis(tri-n-butyltin) oxide (TBT) or di-n-butyltin dichloride (DBT). Experiments were repeated with zoeae from females collected from the Petaluma River, California in June–August 1983 and 1984 or from Sykes Creek, Florida (USA) in February 1985. Using probit analysis, we calculated LC₅₀ values for exposure lasting the duration of zoeal development. Tributyltin was 54 to 65 times more toxic than dibutyltin, the lower value characterizing the response of Florida zoeae. Increases in duration of zoeal development and reduction of dry weights of megalops, both sublethal responses, were dose-dependent for the two populations. However, zoeae from Florida consistently had shorter duration of zoeal development and higher megalopal weights at metamorphosis, indicating less sensitivity to an identical exposure to either organotin compound. The results of these experiments show that dibutyltin, a putative degradation product of tributyltin, is less toxic than the parent compound. In addition, early life-history stages of two populations may have significantly different responses to xenobiotic stress which, in the case of brachyuran larvae, is evident in a differential reduction of survival and growth and an increase in duration of zoeal development.     

Untersuchungen zur Nachhaltigkeit der Sanierung von Tributylzinnkontaminiertem Hafensediment durch Landablagerung

To allow ships to pass, most harbours have to be liberated from sedimented material. These sediments often contain high concentrations of tributyltin (TBT), which is used as a biocide in antifouling paints. Thus, the problem of a disposal which is acceptable with respect to a minimum risk for humans and the environment arises. The aim of our project was to assess land deposition as an alternative in dealing with TBT-contaminated harbour sediments. Therefore, we followed the biological degradation of TBT under aerobic and anaerobic conditions at different temperatures using defined laboratory experiments, and got important information about the land deposition, performing field measurements including biomonitoring. The biological degradation of TBT is faster under aerobic conditions and with increasing temperature. The half-lives found show the dependency of the degradation rates on the temperature between 5–55°C. The degradation rate determined for water under the same conditions (just biological degradation, without photolysis) is almost 4 times higher than in sediment. The field studies showed degradation rates of a maximum of 10–15% per year in untreated sediment and 30% per year in restacked sediments. We did not observe any interference of released TBT with ground water or surrounding areas. The TBT uptake in plants was low. Based on our results a multidimensional risk evaluation was performed, concerning the TBT and its degradation products dibutyltin (DBT) and monobutylin (MBT) released from the deposition areas. The land deposition appears to be a sustainable solution for dealing with TBT-contaminated harbour sediments.     

Accumulation and depuration of mercury in the American oyster Crassostrea virginica

To study the kinetics of mercury uptake in oysters, adult Crassostrea virginica (Gmelin) were held in seawater containing 10 g mercury/l (ppb) or 100 g mercury/l (ppb), added in the form of mercuric acetate, for 60 days. Mercury concentration in tissues was determined by analysis of individually homogenized oyster meats, using wet digestion and flameless absorption spectrophotometry. After 45 days, average mercury tissue concentration was 140,000 g mercury/kg tissue (ppb) and 28,000 g mercury/kg tissue (ppb) in the 100 ppb and 10 ppb experimental groups, respectively. After this time, concentrations dropped sharply, probably due to spawning. Clearance of mercury from tissue was studied by exposing treated adults to estuarine water (with no additions) for 30 days (100 ppb group) and 160 days (10 ppb group). Tissue concentrations in the 100 ppb mercury environment group declined from 115,000 to 65,000 ppb, and those of the 10 ppb group declined from 18,000 to 15,000 ppb, in 18 days; there-after, no further decline occurred in either group. Oysters accumulated mercury 1,400 times and 2,800 times above the environmental concentrations of 100 and 10 ppb mercury, respectively. Total self-purification was not achieved over a 6 month cleansing period.     

Acute toxicity and sublethal behavioral effects of copper on barnacle nauplii (Balanus improvisus)

This study documents the effects of short-term (24h) sublethal copper exposures on undirected swimming activity and photobehavior of Balanus improvisus stage II nauplii. All Cu treatments were static, with temperature and salinity conditions at 20°C and 15 or 30. The 24h LC 50 estimate for Cu is 88 ppb at 15 and >200 ppb at 30. Sub-lethal Cu concentrations cause reductions in swimming speed, which decrease progressively with increasing Cu dose. At 50 ppb Cu, this was significant primarily at light intensities below the phototactic threshold. At higher Cu concentrations, significant reductions in mean linear velocity occurred at most light intensities tested. At 30, 50 and 100 ppb Cu also reduce the positive phototactic response and 150 ppb Cu causes reversal of phototaxis at optimal intensities. Photokinesis is reduced at 100 ppb Cu and disappears at 150 ppb Cu. At 15, the behavioral effects of 50 ppb Cu resemble those occurring with 150 ppb Cu at 30. Swimming speed and photobehavior show promise as sensitive behavioral indicators of copper toxicity. Additional research is required to determine if these responses apply to a broad range of pollutants and to other planktonic organisms. There is also a need to further evaluate the significance of these behavioral effects ecologically.Contribution No. 181 from the EPA Environmental Research Laboratory, Narragansett, RI 02882, USA     

Factors affecting the accumulation and removal of mercury from tissues of the American oyster Crassostrea virginica

Adult oysters, Crassostrea virginica (Gmelin) were held in seawater containing 10 or 100 ppb mercury in the form of mercuric acetate for 45 days. Mercury concentration in tissues was determined by analysis of individually homogenized oyster meats using wet digestion and flameless absorption spectrophotometry. After 45 days, average mercury tissue concentration was 91,600 and 12,100 ppb in the 100 and 10 ppb mercury groups, respectively. A slight decline in mercury residues in the 100 ppb group during the accumulation period was attributed to spawning. Clearance of mercury from tissues was studied in a constant temperature regime (25°C±2C^o) for 25 days and in a declining temperature regime (25° to 5°C) for 80 days by exposing treated adults to estuarine water with no mercury added. The biological half-life of mercuric acetate was 16.8 and 9.3 days in the 25°C temperature regime, and 35.4 and 19.9 days in the declining temperature regime, for the 10 and 100 ppb groups, respectively. Smaller oysters (0 to 7 g) consistently accumulated more mercury per gram wet weight than larger oysters (7 to 20 g) in populations exposed to 10 and 100 ppb mercury.     

Carbon nanotubes and cyclodextrin polymers for removing organic pollutants from water

Some organic compounds are major water pollutants. They can be toxic or carcinogenic even at low concentrations. Current technologies, however, fail to remove these contaminants to parts per billion (ppb) levels. Here we report on the removal of organic pollutants from water using cross-linked nanoporous polymers that have been copolymerized with previously functionalized carbon nanotubes. These novel polymers can remove model organic species such as p-nitrophenol by as much as 99% from a 10 mg/L spiked water sample compared to granular activated carbon and native cyclodextrin polymer that removed only 47 and 58%, respectively. These polymers have also demonstrated the ability to remove trichloroethylene (10 mg/L spiked sample) to non-detectable levels (detection limit <0.01 ppb) compared to 55 and 70% for activated carbon and native cyclodextrin polymers, respectively.