硝基芳烃类对斜生栅列藻的毒性及中毒症状

藻类实验是水生态毒理学研究中的主要方法。通过ＯＥＣＤ标准藻类阻碍生长实验,得到２５种典型硝基芳烃化合物对斜生栅列藻的４８ｈ半数有效抑制浓度ＥＣ５０值。其毒性由高到低的顺序为：二硝基氯苯〉二硝基苯〉二硝基苯胺〉二氯硝基苯＝二硝基甲苯〉硝基溴苯＝硝基氯苯〉硝基甲苯＝硝基苯甲醚＝硝基苯酚〉硝基苯胺〉硝基苯。同时在光学显微下详细观察到斜生栅列藻的中毒症状：①似亲孢子释放受阻;②质壁分离;③细胞核和细胞器解     

疏浚物对栉孔扇贝急性致死量的实验研究

本文探讨实验室室条件下疏浚物对栉孔扇贝９６ｈ半致死浓度以及试验条件的筛选，实验结果表明，疏浚物粒径小于６３μｍ，海水中悬浮物浓度为１０％，水温（２０±１）℃，ｐＨ８．０－８．３，盐度２９－３０，充氧条件下，栉孔扇贝９６ｈ内的死亡率为６３％。     

Seven microcystins from Microcystis waterbloom in Lake Dalai,China

Seven types of microcystins,isolated from Microcystis waterbloom in Lake Dalai, were characterized.The major toxins:MCYST-LR,MCYST-RR,[D-Asp³]MCYST-LR and [Dha⁷]MCYST-LR were identified by high performance liquid chromatography(HPLC),as compared with the authentic microcystins.The minor toxins:MCYST FR,[L-Mser⁷]MCYST-LR and an unknown MCYST which was most likely to be MCYST-(H₄)YR were identified with fritfast atom bombardment liquid chromatography/mass spectrometry(Frit-FAB LC/MS)and amino acid analysis.The toxigenic diversity in blue-green algae(cyanobacteria)was discussed.     

含氯苯酚类化合物结构表征与毒性预测

将有机化合物中的不同非氢原子及非氢原子之间的关系参数化得到新的结构描述符,运用该描述符对部分含氯苯酚类化合物分子结构进行了参数化表征。采用偏最小二乘回归(PLS)方法构建了化合物结构与毒性(-lg IC50)之间的关系模型,模型的建模相关系数(R2)为0.948,"留一法"交互检验的相关系数(Q2)为0.922,标准偏差(SD)为0.184。结果表明结构描述符能较好地表征化合物分子结构特征,所建模型稳定性好、预测能力强,对于酚类化合物QSAR研究具有一定的参考价值。     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

国内典型城市降雨径流初期累积特征分析

提出以携带50%污染物负荷的径流定义初期雨水,选取累积50%污染物负荷的历时(T50)及对应累积径流深度(D50)两个参数,总结分析典型山地城市、平原城市、河网城市等6个城市17场降雨径流污染物累积特征.进一步以山地城市和平原城市为例,探讨了不同降雨强度、区域环境径流污染物累积特征及相互影响.结果表明,径流污染物累积趋势完全一致但特征不同,山地城市、河网城市、高原城市和河口城市表现为初期累积,平原城市则表现为中期累积.随着雨强增大,污染物D50骤增,T50锐减.相比平原城市,山地城市不同类型污染物D50更大、T50更小,山地城市和平原城市分别截留初期7.4mm和5.2mm径流可以控制50%污染物负荷.     

Effect of humic acids and sunlight on the cytotoxicity of engineered zinc oxide and titanium dioxide nanoparticles to a river bacterial assemblage

The effect of a terrestrial humic acid (HA) and Suwannee River HA on the cytotoxicity of engineered zinc oxide nanoparticles (ZnONPs) and titanium dioxide nanoparticles (TiO2NPs) to natural aquatic bacterial assemblages was measured with spread plate counting. The effect of HA (10 and 40 ppm) on the cytotoxicity of ZnONPs and TiO2NPs was tested factorially in the presence and absence of natural sunlight (light irradiation (LI)). The experiment was of full factorial, completely randomized design and the results were analyzed using the General Linear Model in SAS analytical software. The method of least squares means was used to separate the means or combinations of means. We determined the mechanism of toxicity via measurements of oxidative stress and metal ions. The toxicity of ZnONPs and TiO2NPs to natural aquatic bacterial assemblages appears to be concentration dependent. Moreover, the cytotoxicity of ZnONPs and TiO2NPs appeared to be affected by HA concentration, the presence of sunlight irradiation, and the dynamic multiple interactions among these factors. With respect to light versus darkness in the control group, the data indicate that bacterial viability was inhibited more in the light exposure than in the darkness exposure. The same was true in the HA treatment groups. With respect to terrestrial versus Suwanee River HA for a given nanoparticle, in light versus darkness, bacterial viability was more inhibited in the light treatment groups containing the terrestrial HA than in those containing Suwanee River HA. Differences in the extent of reactive oxygen species formation, adsorption/binding of ZnONPs/TiO2NPs by HA, and the levels of free metal ions were speculated to account for the observed cytotoxicity. TEM images indicate the attachment and binding of the tested nanoparticles to natural bacterial assemblages. Besides the individual parameter, significant effects on bacterial viability count were also observed in the following combined treatments: HA-ZnONPs, HA-LI, ZnONPs-LI, and HA-ZnONPs-LI. The main effects of all independent variables, plus interaction effects in all cases were significant with TiO2NPs.     

6种含氮杂环化合物对发光细菌的毒性研究

研究了吲哚，吡啶，喹啉，异喹啉、2-甲基喹啉和8-羟基喹啉6种含氮杂环化合物对发光细菌的急性毒性作用及上述物质两两混合对发光细菌的联合毒性作用。结果表明，上述物质对发光细菌的EC50分别为11．75、591．50、24．30、8．24、52．26和0．88mg／L，毒性由强至弱依次为8-羟基喹啉、异喹啉、吲哚、喹啉、2-甲基喹、吡啶。所有物质两两混合的联合毒性作用均表现为相加作用。     

LC-MS/MS法测定沉积物中磺胺类和四环素类抗生素

沉积物样品用乙腈-柠檬酸缓冲溶液提取后经HLB-SPE柱净化,采用LC-MS/MS法在MRM模式下测定17种磺胺类和4种四环素类抗生素,通过优化测定条件,使方法在0. 500μg/kg～100μg/kg范围内线性良好。方法检出限为0. 15μg/kg～1. 2μg/kg,2个质量比水平的加标回收率为44. 1%～125%,试验5次结果的RSD 16. 0%。将该方法用于测定厦门近岸海域沉积物中抗生素,共有6种磺胺类和4种四环素类抗生素检出,测定值为0. 3μg/kg～26. 2μg/kg。