焦化废水处理试验系统出水的生物毒性变化

焦化废水是一种典型的难降解工业废水,组分复杂,生物毒性高,大多采用生物处理联合物化深度处理的工艺,以满足炼焦化学工业的污染排放标准,但其排水安全性仍然令人担忧。为研究工艺排水安全性,选择发光细菌青海弧菌Q67、稀有鮈鲫(Gobiocypris rasus)血红细胞、活性污泥微生物群落为测试生物,研究了焦化废水及各处理阶段出水的急性毒性和遗传毒性变化,进而识别影响生物毒性的水质因子。焦化废水经过序批式生物膜反应器处理后,出水急性毒性比进水下降71%,遗传毒性下降为90%以上的轻度以下损伤,显示生物强化处理对焦化废水生物毒性有良好的去除作用。生物处理出水再经过深度处理后,则表现出不同的毒性变化:活性炭吸附法对生物急性毒性的消除最佳,但遗传毒性较生物处理出水有所升高;臭氧氧化法不仅水质改善效率差,且最终出水的生物急性毒性与遗传毒性均升高;臭氧催化氧化法对水中残留有机物去除效率较高,但也造成出水急性毒性与遗传毒性的升高。各水样对青海弧菌Q67的急性毒性与有机物、氮等水质指标表现出较强相关性,而遗传毒性与水质指标之间的相关性不显著。研究结果可为评价和改进处理工艺、保障水体生态安全提供参考。     

广州市某A2/O工艺城镇污水处理厂出水对大型溞的生殖毒性作用

城镇污水处理厂废水中存在大量生物毒性物质,但该废水对动物的生殖能力影响研究还十分缺乏。利用大型溞暴露实验,检测广州市某采用A~2/O工艺的城镇污水处理厂出水的急性毒性和生殖毒性。48 h急性毒性实验表明,所有水样均未表现出急性毒性效应。慢性生殖毒性(14 d)测试结果表明:(1)从进水到缺氧池出水均能显著提高第一胎产溞数量;(2)进水和沉砂池出水显著增加受试期总产溞数量;(3)从厌氧池到出水工艺段受试溞的第一胎产溞时间均推后;(4)好氧池出水的毒性显著降低,但仍然对大型溞具有生殖毒性。研究表明,好氧池(A~2/O)工艺能够显著去除具有大型溞生殖毒性的物质,但污水处理厂废水的生殖毒性仍需要引起关注。     

基于umu遗传毒性效应的饮用水致癌风险评价的尝试

化学物质暴露是导致癌症发生的重要诱因,通过饮用水暴露导致的人类致癌风险在饮用水处理技术中日益引起重视.由于水中化学物质种类繁多、组成复杂,准确地检测每个致癌物质的浓度和毒性非常困难.为了控制饮用水的安全,根据DNA损伤诱导SOS反应而表达umuC基因这一基本原理建立的SOS/umu测试法,已经广泛应用于饮用水遗传毒性的检测.论文建立了基于umu遗传毒性效应的饮用水致癌风险评价方法,并对北方某水厂饮用水的遗传毒性进行了umu测试,计算了该地区饮用水的致癌风险,提出了可能的饮用水遗传毒性基准值.结果表明,该水厂常规工艺出水的致癌风险均值为1.55×10-6,存在一定的安全隐患;而深度处理工艺能有效地削减出水致癌风险均值至5.3×10-7,达到目前先进国家水质管理的要求,保障了饮用水的安全.样品中4-硝基喹啉-1-氧化物(4-NQO)的等当量浓度(TEQ4-NQO)0.0948μg·L-1可作为饮用水遗传毒性基准值。     

基于物种敏感性分布的保护海水水生生物的石油烃急性毒性基准研究

溢油污染对水生生物的危害以及分散剂使用对原油毒性的影响一直是溢油应急响应及危害评估时关注的焦点。本研究收集筛选了基于标准测试方法的90组急性毒性数据(LC50/EC50),其中37组毒性数据来自15种油品的水容纳组分(water accommodated fraction,WAF),53组来自11种化学分散剂与15种油品的分散液(chemically dispersed water accommodated fraction,CEWAF),应用物种敏感性分布(species sensitivity distribution,SSD)方法推导了基于水生生物保护的石油烃总量(total petroleum hydrocarbon,TPH)的急性毒性基准值,同时还分析了分散剂和不同暴露方式对原油毒性的影响。结果显示,以名义浓度(nominal concentrations)所表示的毒性结果可能高估分散剂对原油毒性的影响,基于CEWAF和WAF的LC50/EC50所推导的有害浓度(HC5s)差异较小,计算出的保护水生生物TPH急性毒性基准值为0.38 mg·L-1(TPH);鱼类对原油污染的响应明显敏感于甲壳类;同时证明了SSD方法在溢油毒性评估及风险阈值推导中具有可行性和合理性。     

Comparative genotoxicity of water processed by three drinking water treatment plants with different water treatment procedures

• Genotoxicity of substances is unknown in the water after treatment processes. • Genotoxicity decreased by activated carbon treatment but increased by chlorination. • Halogenated hydrocarbons and aromatic compounds contribute to genotoxicity. • Genotoxicity was assessed by umu test; acute and chronic toxicity by ECOSAR. • Inconsistent results confirmed that genotoxicity cannot be assessed by ECOSAR. Advanced water treatment is commonly used to remove micropollutants such as pesticides, endocrine disrupting chemicals, and disinfection byproducts in modern drinking water treatment plants. However, little attention has been paid to the changes in the genotoxicity of substances remaining in the water following the different water treatment processes. In this study, samples were collected from three drinking water treatment plants with different treatment processes. The treated water from each process was analyzed and compared for genotoxicity and the formation of organic compounds. The genotoxicity was evaluated by an umu test, and the acute and chronic toxicity was analyzed through Ecological Structure- Activity Relationship (ECOSAR). The results of the umu test indicated that biological activated carbon reduced the genotoxicity by 38%, 77%, and 46% in the three drinking water treatment plants, respectively, while chlorination increased the genotoxicity. Gas chromatograph-mass spectrometry analysis revealed that halogenated hydrocarbons and aromatic compounds were major contributors to genotoxicity. The results of ECOSAR were not consistent with those of the umu test. Therefore, we conclude that genotoxicity cannot be determined using ECOSAR .     

某石化废水的综合毒性评价及其处理工艺对毒性的削减规律研究

利用生物毒性测试对环境中的污染物进行生态风险评价,是目前风险评价中的研究热点。本研究以明亮发光杆菌(Photobacterium phosphoreum)、斜生栅藻(Scenedesmus obliquus)和大型溞(Daphina magna)为受试生物,对某石化厂废水的处理流程中5个主要单元出水的急性毒性进行了测试,分析了其急性毒性与理化指标间的相关性;同时,为了解不同处理单元毒性去除效果及主要毒性来源,结合毒性鉴别评价(toxicity identification evaluation,TIE)技术对各阶段出水的毒性削减及其主要致毒物质类别进行了分析。毒性测试结果表明,该废水处理厂对石化废水的毒性去除效果比较显著,其中进水对明亮发光杆菌、斜生栅藻和大型溞分别表现为中毒、高毒和剧毒,最终处理后出水的毒性分别为无急性毒、中毒和微毒,对毒性的去除效率分别为96.4%、74.3%和99.5%。TIE结果表明,石化废水中的主要致毒物质是非极性有机物和可滤型物质。本研究结果为石化废水的综合生物毒性评价提供了研究基础,为探讨废水生物毒性的去除提供了实例参考。     

Effects of polyaluminium chloride on the freshwater invertebrate Daphnia magna

In a number of countries across the world, aluminium in the form of polyaluminium chloride has been used in the treatment of freshwaters for the direct removal of cyanobacteria, or phosphorus removal, but knowledge about its effect on zooplankton species is poor. In our study, polyaluminium chloride toxicity was tested on both artificial and natural freshwaters for a better understanding and prediction of effects in real ecosystems. Our results indicate that prediction of effects in a real ecosystem based on standard ISO methods is insufficient, and tests with nontarget species (including invertebrates) should be done before each treatment using the water samples from the treated location. Effective concentrations of polyaluminium chloride can differ markedly according to the type of water composition used in the assay. Our experiments proved that EC₅₀ values can fluctuate between 9.89 and 54.29 mg·L^?1 of Al³⁺, and the toxicity is dominantly dependent on the treated water conductivity. This parameter seems to be the dominant source of different effects on zooplankton species after treatment and thus should be properly tested before each use of polyaluminium chloride as a treatment compound.     

利用重组大肠杆菌SOS法评价污水厂出水的遗传毒性以及工艺去除效果

SOS/umu测试法被广泛应用于化合物和复杂混合物遗传毒性的评价,由于该技术所用菌种为致病菌且操作步骤繁琐等原因,制约了技术的推广应用。研究建立了基于重组大肠杆菌SOS效应的水质遗传毒性检测方法(专利号:ZL201110022476.1),应用该方法评价了某市4座污水厂出水的直接遗传毒性效应,同时以污水处理一厂为例考察了直接遗传毒性效应的季节变化规律以及不同的工艺对水中直接遗传毒性物质的去除情况。结果显示:各污水厂出水均表现出一定的直接遗传毒性,对应的4-NQO毒性当量浓度范围为0.018~0.514 mg·L-1;一年四季中夏季进出水直接遗传毒性效应最高,现有工艺中生化处理工艺段对直接遗传毒性去除效果最佳,去除率为33.33%。该方法操作便利、检测敏感性较高、操作危险性较低,可用于水中直接遗传毒性效应的测试。     

Preliminary toxicity evaluation of water from rice fields using cost‐effective microbiotests

A study was performed in a Protected Area (Natural Reserve of Sado Estuary) in 1996, to evaluate the acute toxicity for aquatic life of surface water from rice fields treated with pesticides, particularly with molinate and quinclorac. As a preliminary assessment, the following rapid toxicity tests were used: “Rotoxkit F”;, “Thamnotoxkit F”; and the recently introduced “Daphtoxkit F magna”; and “Algaltoxkit F”;. Water samples were collected from: a water source for irrigating the rice fields, two rice plots, a drainage channel and from Sado river in which the water is discharged. The results showed that samples from the rice plot treated with molinate were more toxic than those obtained from rice plot treated with quinclorac. Water samples from the river were the most toxic, causing 100% of immobility in all organisms and a substantial inhibition in the algal growth. Water collected from the drainage channel in late July, was also found to be quite toxic. The results obtained until now indicate that some characteristics of these microbiotests, like their rapidity, simplicity and relatively low cost, make them a practical tool to evaluate acute effects of pesticides in freshwater ecosystems. They may also contribute to suggest some changes in pesticides use to promote agricultural practices with lower impact to aquatic life.     

基于斑马鱼和发光细菌评估制革废水毒性及其削减效率

随着制革工业在我国的迅速发展,其导致的环境污染问题也逐渐受到人们的广泛关注。为评价制革废水的生物毒性以及处理工艺对毒性的削减效率,选择费氏弧菌、明亮发光杆菌、斑马鱼幼鱼及其胚胎作为受试生物,分析了制革废水的急性毒性和发育毒性,比较了不同受试生物对制革废水毒性的敏感性,并结合理化指标对废水的毒性削减进行了评估。结果表明:不同受试生物的敏感性大小为斑马鱼胚胎明亮发光杆菌斑马鱼幼鱼费氏弧菌明亮发光杆菌斑马鱼胚胎斑马鱼幼鱼费氏弧菌;发光菌及斑马鱼幼鱼急性毒性实验结果表明,制革废水经过整个工艺处理后,废水的急性毒性已降至检测线以下,即0TUa;斑马鱼胚胎毒性实验结果表明,经过处理的制革废水仍存在急性毒性,基础毒性当量为0.5 TUa,同时还对胚胎的发育存在一定影响,对胚胎孵化及畸形的毒性当量分别为0.7 TUa和0.13 TUa。综上可知,处理后的制革废水对环境的影响已得到初步的有效控制,但仍需进一步处理以达到更大程度削减毒性的目的。     

Utility of the QSAR modeling system for predicting the toxicity of substances on the European inventory of existing commercial chemicals∗

Many chemicals are in common commercial use for which no information on the environmental fate or toxicity exists. Recent legislation requires that many substances be assessed for their toxicity to aquatic organisms within a very short time and determine which of these chemicals need to be studied in greater detail. It would be impossible to measure the acute and chronic effects of all of these compounds on a single organism, let alone a battery of different types of organisms, communities or ecosystems. Initially, the chemicals on the European Inventory of Existing Commercial Chemical Substances (EINECS) need to be screened and relative hazard to the environment determined. In response to OECD directives, there has been a great deal of activity by government and industry scientists. At the International Workshop on Advances in Environmental Hazard and Risk Assessment it was concluded that quantitative structure activity relationships (QSAR) could and should be used in the hazard assessment process. Papers published in that volume outline the advantages, disadvantages, limitations, advances and research requirements.

The QSAR, structure‐activity based chemical modeling and information system, which was developed by the US‐Environmental Protection Agency was used to predict the acute toxicity of 113 substances from the “Old Substances”; list of the German government to the four commonly used aquatic toxicity test organisms: Daphnia magna (DM), fathead minnow (FHM), rainbow trout (RBT), and blue‐gill sunfish (BG).

Of these compounds the QSAR system predicted the acute toxicity of 87 substances towards fathead minnow. For the other three species examined the QSAR system could be used to predict toxicity for 78 compounds.

The predicted toxicities were compared to observed toxicities of compounds which have been evaluated and stored in the “Aquire”; data base. Observed toxicity values were available for at least one species for 38 compounds. The toxicities of some compounds are well predicted while those of other compounds were not well predicted. Overall, the QSAR system accurately classified the acute toxicity ranges of 50%, 64%, 56% and 56% of the compounds investigated for DM, FHM, RBT and BG, respectively. Of the compounds studied 10 were very poorly predicted, of these the QSAR system overpredicted the toxicity of three, while underpredicting the toxicity of seven. Of these seven compounds, five contained amino groups.     

淮河流域安徽段水体成组生物毒性评价

在淮河流域安徽段某区域采集了3个地表水样和12个地下水样,通过大型溞急性毒性(活动抑制)、微核及SOS/umu试验,分析了这些水样的急性毒性及遗传毒性。结果表明,急性毒性测试中,该区域地表水及大部分地下水的急性毒性均未超过US EPA废水排放毒性的控制要求(0.3 TU),有2个位点的地下水样毒性当量为0.31 TU,超过限值;经t-test分析,地表水的急性毒性显著高于地下水。SOS/umu检测中,2个地表水样和7个地下水样的结果呈阳性,表现出DNA损伤效应,其诱导率IR在(2.20±0.063)~(3.36±0.067)之间,对应的致癌风险P基本处在10-6~10-7水平。微核检测结果表明,3个地表水样具有较严重的染色体损伤效应,9个地下水样表现为阴性。总之,该区域地表水急性毒性及遗传毒性相对较高;部分浅层地下水也存在一定程度的急性毒性和遗传毒性,致癌风险处在可接受范围,但仍可能对周围居民的健康产生潜在威胁;而深层地下水没有检测到任何毒性效应。研究为周边居民饮水安全和人体健康提供了基础信息。     

Effect of biosolid hydrochar on toxicity to earthworms and brine shrimp

The hydrothermal carbonization of sewage sludge has been studied as an alternative technique for the conversion of sewage sludge into value-added products, such as soil amendments. We tested the toxicity of biosolid hydrochar (Sewchar) to earthworms. Additionally, the toxicity of Sewchar process water filtrate with and without pH adjustment was assessed, using brine shrimps as a model organism. For a Sewchar application of 40 Mg ha^?1, the earthworms significantly preferred the side of the vessel with the reference soil (control) over side of the vessel with the Sewchar treatments. There was no acute toxicity of Sewchar to earthworms within the studied concentration range (up to 80 Mg ha^?1). Regarding the Sewchar process water filtrate, the median lethal concentration (LC50) to the shrimps was 8.1% for the treatments in which the pH was not adjusted and 54.8% for the treatments in which the pH was adjusted to 8.5. The lethality to the shrimps significantly increased as the amount of Sewchar process water filtrate increased. In the future, specific toxic substances in Sewchar and its process water filtrate, as well as their interactions with soil properties and their impacts on organisms, should be elucidated. Additionally, it should be identified whether the amount of the toxic compounds satisfies the corresponding legal requirements for the safe application of Sewchar and its process water filtrate.     

基于本土物种的3种典型化合物急性生态效应阈值研究

预测无效应浓度(PNEC)是进行风险污染物水生态安全管理的重要依据。本研究进行了3种典型化合物五氯酚、硝基苯和氯化镉对10种我国不同营养级水生生物的24 h、48 h和96 h的急性毒性测试,根据实验结果计算了相应的急性PNEC,同时与根据美国环境保护局毒性数据库里的毒性数据计算获得的急性PNEC值,以及综合本实验结果与毒性数据库里的数据计算得到的急性PNEC值进行对比,发现通过3种数据来源获得的急性PNEC值中,硝基苯的PNEC值差异较大,由本次实验结果获得的急性PNEC值最小;其他2种化合物差异较小。这可能是由于本次实验所选的本土生物中华田螺和麦穗鱼对硝基苯比较敏感,并且数据库中硝基苯的急性致死数据较少、毒性值较大且变化范围较窄,而其他2种化合物数据量较为丰富,变化范围较宽,包括了较敏感物种的毒性数据。这表明为给我国水生生物提供一个安全可靠的保护,对于数据量较为丰富并且毒性值变化较宽的化合物(如五氯酚和氯化镉)可以直接根据数据库里的毒性数据进行PNEC值的计算;而对于毒性数据量较少、毒性值偏大且变化较窄的化合物(如硝基苯)需要进行本土敏感物种的毒性测试。     

成组生物毒性测试法综合评价典型工业废水毒性

为了更加准确地评估典型工业废水的综合生物毒性以及处理工艺对废水毒性的削减情况,采用发光细菌急性毒性实验、大型溞急性毒性实验和单细胞凝胶电泳实验,结合潜在生态毒性效应探测(potential ecotoxic effects probe,PEEP)指数对常州市7种典型工业废水的综合生物毒性进行了评价。结果表明,7种工业原水都表现出了急性毒性或遗传毒性,综合生物毒性强度的排序为电子厂>电镀厂>综合污水处理厂>印染厂>化工厂>食品厂>制药厂。而7种工业废水的处理后出水综合生物毒性强度的排序为印染厂>化工厂>电子厂>综合污水处理厂>食品厂>制药厂>电镀厂。其中,印染和化工厂出水综合生物毒性高于原水,分别增加了43.3%和38.7%,PEEP评价结果显示分别属于剧毒和高毒,而电镀、电子、综合污水处理和食品厂出水的综合生物毒性削减明显,分别比原水削减了76.9%、53.1%、48.3%和26.6%,PEEP结果表明基本无毒。建立在成组生物毒性实验基础上的PEEP评价方法可全面反映工业废水的综合生物毒性,进而更客观地评价废水对水生态系统乃至人类健康的潜在影响。     

Acute/chronic ratios to estimate chronic toxicity from acute data

Acute toxicity of 25 narcotic compounds to D. magna was determined in this paper. Acute/ Chronic Ratios (ACRs), which are often used to estimate chronic toxicity from acute toxicity data, are discussed based on Quantitative Structure‐Activity Relationships (QSARs) of the compounds between both acute and chronic toxicity data and n‐octanol/water partition coefficients, and an improved equation is derived to estimate chronic toxicity data from acute toxicity data. Application of the improved equation and ACRs is illustrated for D. magna and fathead minnow to estimate chronic toxicity from acute toxicity.     

An integrated assessment method of urban drainage system: A case study in Shenzhen City, China

In recent years, the urban drainage system in China is facing the dual pressure of renovation and construction. This requires that the integrated assessment for the planning and operation of the urban drainage system is obligatory. To evaluate the urban drainage system, an integrated assessment methodology based on the analytic hierarchy process (AHP), integrated simulation, and fuzzy assessment is established. This method is a multi-criteria decision adding app roach to the assessment of the urban drainage system comprehensively. Through the integration of the Storm Water Management Model (SWMM), a simple wastewater treatment plant model, and a surface water quality model, an integrated modelling system for the urban drainage system is developed and applied as a key tool for assessment. Using the established method, a case study in Shenzhen City has been implemented to evaluate and compare two urban drainage system reno vation plans, the distributed plan and the centralized plan. Because of the particularity of this case study, the established method is not applied entirely. Considering the water environ mental impact, ecological impact, technological feasibility, and economic cost, the integrated performance of the distri buted plan is better. As shown in this case study, the proposed method is found to be both effective and practical.     

斑马鱼幼鱼运动行为测试评价饮用水安全

饮用水安全直接关乎人类的健康与安全,当前迫切需要全新的毒性测试方法对饮用水的潜在人类健康风险进行全面、准确和灵敏的评估和预警。本研究以反渗透技术(RO)取代常用的固相萃取,分别浓缩饮用水厂的进厂水、出厂水和管网水进行毒性试验水样的前处理。反渗透技术前处理方法可以避免传统固相萃取方法中使用的有机溶剂对行为学测试体系的干扰。RO浓缩后的饮用水对斑马鱼胚胎进行持续暴露,采用Viewpoint行为测试软件量化分析出生后第6天(6 dpf)斑马鱼幼鱼的运动行为,选择运动距离和转向行为作为测试终点,分析进厂水、出厂水及管网水的潜在毒性及可能变化。结果表明,暴露在进厂水的幼鱼出现了明显的行为变化,尤其在较高浓度(20倍浓缩)暴露时,运动距离相比对照组显著减少,同时伴有剧烈的转向等异常行为;管网水对斑马鱼幼鱼行为存在一定程度的影响,而出厂水对幼鱼的运动行为没有显著影响。研究结果反映出当前饮用水厂深度处理工艺可以有效降低进厂水的潜在毒性和健康风险,但是经供水管网输送后,其水质可能发生了改变,导致管网水可能存在潜在的毒性。本研究所采用的反渗透技术前处理技术及斑马鱼幼鱼的运动行为学测试方法,可用于未来建立评估饮用水水质安全的早期预警系统。     

载钯树脂对偶氮类染料的吸附降解及其产物对发光菌的毒性暴露试验

合成了表面负载金属钯的聚丙烯醛异烟酰腙树脂后,通过Q67发光菌的毒性暴露实验研究了该树脂材料对直接大红、直接天蓝和桃红等3种水溶性偶氮染料的催化降解效果及其在降解过程中对发光菌的生物毒性变化情况,并对降解结果进行了气相色谱-质谱(GC-MS)分析.实验结果表明:载钯树脂对直接大红、直接天蓝和桃红等偶氮染料具有良好的吸附...     

多拷贝表达转鲑鱼降钙素基因酵母的急性、亚急性毒性

口服转鲑鱼降钙素基因酵母为鲑鱼降钙素的应用开辟了一条新的途径.为评价转鲑鱼降钙素基因酵母的安全性,将转基因酵母分别灌胃昆明种小鼠和Wistar大鼠进行急性毒性实验(7 d)、亚急性毒性实验(8周).急性毒性实验结果表明灌喂转基因酵母对小鼠无致死效应(LD50>10 000 mg/kg);亚急性毒性实验中高(2.0 g/kg)、低(0.5 g/kg)剂量组动物的一般状况、体重、主要脏器系数、血液学指标及血液生化指标与各对照组比较,均未见明显差异(P>0.05),组织病理切片检查未发现病理性变化.实验结果说明转鲑鱼降钙素基因酵母不会对实验动物造成不良影响,是安全无毒的.图3表3参16