等浓度配比法研究苯酚、硝基苯和问硝基苯胺对发光菌的联合毒性作用

分别测定了苯酚、硝基苯和间硝基苯胺对发光菌的单一毒性，以及等浓度配比和等毒性配比的二元及三元混合体系的联合毒性，采用相加指数法对其联合效应进行了评价。结果表明，等浓度比和等毒性比混合体系的联合作用结果一致：苯酚＋间硝基苯胺二元体系为协同作用，其他各体系为相加作用。为简化联合毒性实验方法，建议在研究相关系列化合物的联合毒性作用机制中，可采用等浓度配比方法。     

等毒性配比法研究甲醛与重金属的联合毒性效应

正分别测定甲醛与4种重金属的急性毒性EC50,并对等毒性配比条件下甲醛与4种重金属的二元混合体系的联合毒性进行研究,采用毒性单位法和相加指数法对其联合作用进行评价。结果表明,5种物质的急性毒性为Pb(Ⅱ)Zn(Ⅱ)Cu(Ⅱ)甲醛Cd(Ⅱ)。联合毒性结果显示,4种二元混合体系的联合作用方式类似,其中毒性单位法的评价结果均为部分相加作用,相加指数法均为拮抗作用,这主要是由于2种评价方法的评价标准等级划分范围不同造成的。     

固定毒性配比法研究重金属与土霉素的联合毒性

为了研究重金属与药物二元混合体系的联合毒性,选择3种重金属盐CdCl2、K2Cr2O7、CuSO4与土霉素（OTC）为混合物组分,以固定毒性配比法构建3组二元混合物体系：CdCl2-OTC、K2Cr2O7-OTC和CuSO4-OTC。固定的毒性配比分别为4：1、3：2、1：1、2：3和1：4。应用微板毒性分析法,测定单一物质及二元混合物对费氏弧菌（Vibrio.fishceri）的联合毒性,通过比较实验数据与浓度加和模型预测值,分析混合物的毒性作用方式。结果表明：依据单一物质EC50值,它们的毒性从大到小依次为：CuSO4 > CdCl2 > K2Cr2O7 > OTC;重金属与OTC二元混合体系均表现出拮抗作用;在选取的毒性配比范围内,CdCl2-OTC和K2Cr2O7-OTC混合物的拮抗作用强弱在一定范围内浮动,并不随毒性配比的变化而变化。然而,CuSO4-OTC混合物中,联合毒性随着OTC比例的增大,作用方式由显著拮抗向加和趋近。这说明混合物中各组分的浓度组成影响CuSO4-OTC混合物对V.fishceri的联合作用方式,但是CdCl2-OTC和K2Cr2O7-OTC并不受影响。     

竹炭吸附对硝基苯胺的过程与机理研究

研究了竹炭吸附对硝基苯胺的过程影响因子以及吸附过程的动力学、等温线和热力学。结果表明,粒径80~100目的竹炭即可实现对对硝基苯胺的高效吸附,吸附效率为95.65%。竹炭对硝基苯胺的吸附效率随溶液pH值的升高而逐渐下降,当溶液pH值超过7.0以后,下降趋势明显加快,实验条件下,溶液pH=2.0可以获得最佳吸附效果,吸附效率为95.85%,静电作用力和氢键作用力在不同溶液pH值下变化的联合作用是造成吸附效率变化的主要原因。吸附动力学研究结果表明：准二级吸附动力学模型可以很好的拟合3种不同温度下的吸附速率数据;吸附等温线研究结果表明,Redlich-Peterson吸附等温线模型可以很好的拟合3种不同温度下的吸附等温线数据,说明吸附过程兼有单分子层吸附和吸附表面异质性的特点;吸附热力学计算结果表明,吉布斯自由能ΔG0小于零,说明竹炭吸附对硝基苯胺的过程可以自发进行,吸附焓变ΔH0小于零,说明吸附反应为放热过程,并且吸附焓变数值大于单纯由范德华力引起的吸附放热范围,说明吸附过程中存在多种作用力;吸附熵变ΔS0大于零,说明吸附过程中体系的混乱度显著增大。     

载锆活性炭吸附水中对硝基苯酚和磷的研究

为了研究能有效同步去除水中有机、无机污染物的吸附剂,通过前驱体原位沉积法在活性炭表面负载锆氧化物制备得到复合吸附剂载锆活性炭,并对其去除水中对硝基苯酚(PNP)和磷的性能进行评价。结果表明:载锆活性炭对PNP和磷的吸附效果优于未改性活性炭;Langmuir吸附等温模型均能很好地描述载锆活性炭对两种污染物的吸附过程;载锆活性炭对PNP和磷的吸附过程分别符合准二级动力学模型和准一级动力学模型;离子强度对载锆活性炭的吸附磷能力影响不大,说明载锆活性炭对磷具有较好的吸附选择性。PNP和磷共存时,载锆活性炭依然有较好的吸附性能,表明该复合吸附剂可用于同步去除水中的有机、无机污染物。使用5%(质量分数)氯化钠溶液和5%(质量分数)氢氧化钠溶液可对吸附饱和的载锆活性炭进行再生,通过多次循环实验后脱附率较高且稳定,说明载锆活性炭具有良好的再生潜能。     

一株对硝基苯酚降解菌的筛选鉴定及其降解特性

从受甲基对硫磷污染的土壤中分离筛选得到一株能够以对硝基苯酚(PNP)作为唯一碳源、氮源生长的菌株,命名为TM.经16S rDNA序列分析初步鉴定该菌株为节杆菌(Arthrobacter).考察了该菌株在PNP浓度、盐度(NaCl)、pH、外加碳源(葡萄糖)、外加氮源等因素下对PNP降解特性的影响.结果表明:该菌株对PNP的最大耐受质量浓度为300 mg/L,并在降解的过程中生成NO2-该菌株的耐盐能力可达0.30％(质量分数),其最佳pH为8.在此pH下,200 mg/L的PNP在16h时即可被完全降解,添加0.30％(质量分数)的葡萄糖可使生物量和降解速率达到最大,牛肉膏作为外加氮源最有利于该菌株对PNP的降解.     

化学物质对发光菌的联合毒性评价方法

毒性单位法(TU)的理论基础来源于剂量加和模型(DA),目前仅在二元联合毒性评价中广泛应用。为了确定TU模型适合评价的混合物类型,实验选取5种剂量效应曲线类型不同的物质,采用微板光度计测试了一元、二元混合物对发光菌青海弧菌-Q67(Vibrio-qinghaiensis sp.-Q67)的急性毒性。根据物质的剂量效应曲线形状将物质分为A、B、C 3类,利用毒性单位法(TU)和联合作用定义法分别对AA类、AB类、AC类、BC类混合物进行分析。结果表明,TU法仅适合于由剂量效应曲线接近直线的物质组成的混合物进行联合毒性的评价。以效应为基准、TU模型为框架建立了TU’模型,该模型可以满足对任何类型已知成分的混合物或者未知成分的实际水样之间的多元联合作用的评价。     

铜、镉对水螅的急性和联合毒性作用

试验研究重金属铜(Cu2 )、镉(Cd2 )对水螅的急性毒性和联合毒性作用,探索水螅(Hydra sp.)对Cu2 、Cd2 以及两者混合的毒性效应,为水产动物病害的防治中合理使用消毒、杀虫剂以及水体污染评价提供一些参考信息.结果表明,Cu2 对水螅的24 h半致死浓度(LC50)、48 hLC50、72 hLC50、96 hLC50分别为0.072、0.054、0.042、0.037 mg/L;Cd2 对水螅的24 hLC50、48hLC50、72 hLC50、96 hLC50分别为0.001 70、0.000 63、0.000 36、0.000 36 mg/L;Cu2 、Cd2 对水螅的安全浓度分别为3.7×10-4、3.6×10-6mg/L.水螅对两种重金属的毒性反应既快速又敏感,其中Cu2 对水螅的毒性较Cd2 快,但Cd2 的毒性比Cu2 的强.等毒性配比的两种重金属混合液对水螅的毒性大于单一毒性,为协同作用.两种重金属对水螅的LC50随试验时间的延长而减小,它们对水螅的安全浓度远低于渔业水质标准.     

磁强化次氯酸钠氧化法处理邻硝基苯酚废水的实验研究

利用磁强化次氯酸钠氧化法对邻硝基苯酚废水进行了处理实验研究。结果表明,对于质量浓度为250mg／L、CODCr为2000mg／L、色度为150倍的100mL邻硝基苯酚废水,当次氯酸钠（2．5％）用量8mL、颗粒活性炭用量200mg、溶液pH为6．0、反应时间5min时,邻硝基苯酚的去除率达94．4％,CODCr的去除率达94．2％,色度的去除率达100％。采用外加磁场,当磁场强度为60mT时,邻硝基苯酚和CODCr达到相同的去除率,反应时间缩短了3min,显著提高了反应效率。同时对磁强化氧化法的机理进行了理论上的分析。     

超声波/零价铁降解对硝基苯胺的试验研究

对在超声波、零价铁和超声波/零价铁(U/Fe0)等体系中对硝基苯胺的降解规律进行了研究。研究结果表明,对硝基苯胺在超声波作用下,降解规律符合一级反应动力学模型,但超声波对高浓度的对硝基苯胺降解效果较差。在U/Fe0体系中,超声波和零价铁对降解对硝基苯胺具有协同作用,对硝基苯胺降解速率显著提高。降解机理显示,对硝基苯胺在零价铁表面上发生原电池反应,被还原为对苯二胺,在超声波作用下进一步降解。在U/Fe0体系中添加Cu2+,形成Fe/Cu原电池,可进一步促进对硝基苯胺的降解速率,降解效率优于铸铁屑形成的Fe/C原电池。     

The joint effects of sulfonamides and their potentiator on Photobacterium phosphoreum: differences between the acute and chronic mixture toxicity mechanisms

Organisms are typically exposed to mixtures of chemicals over long periods of time; thus, chronic mixture toxicity analysis is the best way to perform risk assessment in regards to organisms. However, most studies focus on the acute mixture toxicity. To investigate the difference between chronic mixture toxicity and acute mixture toxicity, Photobacterium phosphoreum were exposed to chronic (24 h exposure) and acute (15 min exposure) toxicity of single sulfonamide (SA) and their potentiator (trimethoprim, TMP), both individually and mixtures (SA with TMP). A comparison of chronic vs. acute mixture toxicity revealed the presence of an interesting phenomenon, that is, that the joint effects vary with the duration of exposure; the acute mixture toxicity was antagonistic, whereas the chronic mixture toxicity was synergistic. Based on the approach of Quantitative Structure Activity Relationships (QSARs) and molecular docking, this phenomenon was proved to be caused by the presence of two points of dissimilarity between the acute and chronic mixture toxicity mechanism: (1) the receptor protein of SAs in acute toxicity was Luc, while in chronic toxicity it was Dhps, and (2) there is a difference between actual concentration of binding-Luc in acute toxicity and individual binding-Dhps in chronic toxicity. This deep insight into the difference between chronic and acute mixture toxicity will benefit environmental science, medical science, and other disciplines. The existence of these differences poses a challenge for the assessment of routine combinations in medicine, risk assessment, and mixture pollutant control, in which, previously, only a synergistic effect has been observed between SA and their potentiator.     

混合重金属对硝化颗粒污泥毒性作用的析因实验研究

分别测定了Cu2 、Zn2 和Cd2 对硝化颗粒污泥的单一毒性,采用析因实验研究了二元和三元重金属混合体系对硝化颗粒污泥的联合毒性.结果表明,Cu2 、Zn2 和Cd2 的2 h半抑制浓度EC50分别为95.23、62.11和12.48 mg/L,由析因实验所得的响应曲面模型具有较好的优度(其R2＞0.95),能够对混合体系的联合毒性很好地进行预测,析因实验可以用于环境领域混合体系联合毒性的研究.     

Temperature and salinity effects on the toxicity of common pesticides to the grass shrimp,Palaemonetes pugio

This study investigated the effects of increased temperature and salinity, two potential impacts of global climate change, on the toxicity of two common pesticides to the estuarine grass shrimp, Palaemonetes pugio. Larval and adult grass shrimp were exposed to the fungicide chlorothalonil and the insecticide Scourge® under standard toxicity test conditions, a 10°C increase in temperature, a 10 ppt increase in salinity, and a combined increased temperature and salinity exposure. Toxicity of the fungicide chlorothalonil increased with temperature and salinity. Toxicity of the insecticide Scourge® also increased with temperature; while increased salinity reduced Scourge® toxicity, but only in adult shrimp. These findings suggest that changes in temperature and salinity may alter the toxicity of certain pesticides, and that the nature of the effect will depend on both the organism's life stage and the chemical contaminant. Standard toxicity bioassays may not be predictive of actual pesticide toxicity under variable environmental conditions, and testing under a wider range of exposure conditions could improve the accuracy of chemical risk assessments.     

The SeKT joint research project: definition of reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests

- In current biotest approaches, intact organisms or in vitro systems are exposed to sediments using different exposure scenarios. The most important issue in sediment toxicity testing protocols is the question which test phase (solid or liquid) should be used. Whole-sediment exposure protocols represent the most realistic scenario to simulate in situ exposure conditions in the laboratory. However, until now there is no agreement in how to acquire and to evaluate the data of the various available sediment contact assays. The SeKT joint research project was initiated with the aim to compare recently developed sediment contact assays by addressing reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests.     

A comparison of mixture toxicity assessment: examining the chronic toxicity of atrazine, permethrin and chlorothalonil in mixtures to Ceriodaphnia cf. dubia

Pesticides predominantly occur in aquatic ecosystems as mixtures of varying complexity, yet relatively few studies have examined the toxicity of pesticide mixtures. Atrazine, chlorothalonil and permethrin are widely used pesticides that have different modes of action. This study examined the chronic toxicities (7-d reproductive impairment) of these pesticides in binary and ternary mixtures to the freshwater cladoceran Ceriodaphnia cf. dubia. The toxicity of the mixtures was compared to that predicted by the independent action (IA) model for mixtures, as this is the most appropriate model for chemicals with different modes of action. Following this they were compared to the toxicity predicted by the concentration addition (CA) model for mixtures. According to the IA model, the toxicity of the chlorothalonil plus atrazine mixture conformed to antagonism, while that of chlorothalonil and permethrin conformed to synergism. The toxicity of the atrazine and permethrin mixture as well as the ternary mixture conformed to IA implying there was either no interaction between the components of these mixtures and/or in the case of the ternary mixture the interactions cancelled each other out to result in IA. The synergistic and antagonistic mixtures deviated from IA by factors greater than 3 and less than 2.5, respectively. When the toxicity of the mixtures was compared to the predictions of the CA model, the binary mixture of chlorothalonil plus atrazine, permethrin plus atrazine and the ternary mixture all conformed to antagonism, while the binary mixture of chlorothalonil plus permethrin conformed to CA. Using the CA model provided estimates of mixture toxicity that did not markedly underestimate the measured toxicity, unlike the IA model, and therefore the CA model is the most suitable to use in ecological risk assessments of these pesticides.     

Challenges in assessing the toxic effects of polycyclic aromatic hydrocarbons to marine organisms: a case study on the acute toxicity of pyrene to the European seabass (Dicentrarchus labrax L.)

The acute toxicity (96 h) of pyrene (PY) to European seabass (Dicentrachus labrax) juveniles assessed in a semi-static bioassay (SSB) with medium renewal at each 12 h, and in a static bioassay (SB) without medium renewal was compared in laboratorial conditions (water PY concentrations: 0.07-10 mg L⁻¹). Main findings in the SSB that assessed mainly the toxicity of PY and its metabolites were: increased levels of bile PY metabolites in good agreement with the profile of lipid peroxidation levels (LPO) in exposed fish relating PY exposure and oxidative damage; increased levels of PY-type compounds in the brain indicating their ability to cross the blood-brain barrier; increased levels of these substances in liver and muscle which are edible tissues for humans thus raising concern on potential adverse effects on consumers of fish from PY contaminated areas; a significant inhibition of glutathione S-transferase activity suggesting its involvement in PY detoxication as toxicant scavenger; finally, an almost complete impairment of the swimming velocity at all the PY concentrations linking sub-individual to higher population level effects. In the SB, where the overall toxicity of PY, its metabolites and environmental degradation products was evaluated, 19% and 79% of PY decay in test media was found at 12 and 96 h, respectively. In general, the effects were similar to those of SSB but with significant effects being induced at higher PY concentrations indicating that the parental compound is more toxic than its environmental degradation products. The other main differences relatively to the SSB were: increased levels of PY-type substances in the liver suggesting more accumulation in this organ. Therefore, these findings highlight the need of carefully considering experimental design options when assessing the toxicity of readily degradable substances to marine fish, and stress the importance of taking into consideration the toxicity of environmental degradation products in addition to toxic effects of the parental substance and its metabolites for marine ecological risk assessment.     

A comparative study of the toxicity of 1,1,2-trichloroethane,dieldrin, pentachlorophenol and 3,4 dichloroaniline for marine and fresh water organisms

The aquatic toxicity of 1,1,2-trichloroethane, dieldrin, pentachlorophenol and 3,4-dichloroaniline was determined for about 15 marine and fresh water animals and several unicellular algae. Acute, subchronic and chronic tests including reproduction studies, were carried out. The results are summarized in five tables.     

Evaluation on the toxicity of ionic liquid mixture with antagonism and synergism to Vibrio qinghaiensis sp.-Q67

Ionic liquids (ILs) are a fascinating group of new chemicals with the potential to replace the classical volatile organic solvents, stimulating many applications in chemical industry. In case ILs are released to the environment, possible combined toxicity should be taken into account and it is, however, often neglected up to now. In this paper, therefore, the concentration-response curves (CRCs) of four groups of IL mixtures with various mixture ratios to Vibrio qinghaiensis sp.-Q67 were determined using the microplate toxicity analysis and were compared to the CRCs predicted by an additive reference model, the concentration addition (CA) or independent action (IA), to identify the toxicity interaction. It is showed that most of the IL mixture rays displayed the classical addition while the remaining rays exhibited antagonism or synergism. Moreover, it is found that the pEC₅₀ values of the mixture rays exhibiting antagonism or synergism are well correlated with the mixture ratio of a certain IL therein.     

Embryo toxicity of pesticides and heavy metals to the ramshorn snail, Marisa cornuarietis (Prosobranchia)

An invertebrate embryo toxicity test with the ampullariid snail, Marisa cornuarietis, to assess the toxicity of pesticides and heavy metals recently was established. Snail embryos were treated with atrazine (100, 1000, 10 000, and 30 000 μg/L), imidacloprid (10 000, 25 000, and 50 000 μg/L), Ni²⁺ (0.1, 1, 10, and 100 μg/L) or Zn²⁺ (100, 200, 500, 1000, 2000, and 5000 μg/L). The effect of these substances was examined by monitoring the following endpoints: mortality, formation of tentacles and eyes, heart rate, hatching, and weight after hatching. Effects in term of a significant delay on the formation of both tentacles and eyes were found after treatment with 100 μg/L Ni²⁺ or 200 μg/L Zn²⁺. The heart rate was shown to significantly decrease at 25 000 μg/L imidacloprid or 1000 μg/L Zn²⁺. At 100 μg/L atrazine, 10 μg/L Ni²⁺, or 1000 μg/L Zn²⁺ a significant delay in hatching became visible. No significant mortality was observed for the tested concentrations of atrazine, imidacloprid, or Ni²⁺, while 5000 μg/L Zn²⁺ resulted in 100% mortality after 10 d. The weight of freshly hatched individuals remained unaffected in all treatments. On the basis of the lowest observed effect concentrations (LOECs) recorded, we could show the M. cornuarietis embryo toxicity test (MariETT) to react up to three orders of magnitude more sensitive (for metals) and at least one order of magnitude more sensitive (for the tested organics) than the established Danio rerio embryo test.