实测/预测辽河铬(Ⅵ)水生生物基准与风险评估

该研究对辽河流域重金属铬(Ⅵ)的水生生物毒性数据进行搜集与筛选,推导辽河流域铬(Ⅵ)的水生生物基准值,并对辽河流域25个采样点位采集水样,测定铬(Ⅵ)的环境暴露浓度,最后对辽河流域水生生物铬(Ⅵ)暴露的潜在风险进行评估.此外,采用美国环境保护署(US EPA)物种种间关系估算模型(ICE)对辽河流域物种毒性值进行预测,并对基于预测毒性值的水生生物基准进行推导.结果表明,辽河流域基于实测毒性数据的水生生物急性基准值(CMC)为17.73μg·L-1,慢性基准值(CCC)为12.15μg·L-1;ICE模型预测的辽河流域生物毒性值推导的CMC值为13.97μg·L-1,实测CMC值与预测值比较接近,表明ICE模型可应用于水生生物基准值的预测.铬(Ⅵ)的水质分析结果表明25个采样点位水体铬(Ⅵ)浓度较低,均达到GB 3838-2002地表水质标准中铬(Ⅵ)的Ⅰ类或Ⅱ类标准,水质状况良好;然而,在对水生生物的潜在风险方面,通过生态风险评估得出7月辽河流域25个点位中环境暴露值超过慢性基准CCC值的有7个,12月超过慢性基准CCC值的有6个,表明辽河流域个别点位铬(Ⅵ)暴露可能会对水生生物产生不可接受的风险.     

原子荧光法分析地表水中砷的价态

由于砷的化学形态不同,在环境中的毒性、分布、生物效应亦不相同,因而砷的形态分析在环境监测治理中有着不可忽视的重要作用.陆地水中溶解态砷的含量通常在以下,常以砷(三价)、砷(五价)两种价态形式存在,其化合物均有毒性,三价化合物比五价化合物毒性强,多以砷酸盐状态存在.在环境管理中,砷是第一类污染物,环保部门地表水监测也只测总砷,而用氢化物发生原子荧光法可以测定地表水中不同价态的无机砷.在一定的酸度条件下可以选择性地将As3 用硼氢化钾溶液还原成砷化氢,从而将两种价态砷得以有效分离,用原子荧光法测定.As5 在加入还原剂后被还原成As3 ,然后用相同方法测出总砷量,差减去As3 量得到As5 量.此方法灵敏度高,精度好,适用于地表水大量水样中不同价态的砷分析.     

我国淡水生物菲水质基准研究

菲是一种国内外水体中普遍检出的优控多环芳烃,会对水生生物产生有害影响.然而,由于本土物种生态毒理学数据匮乏等问题,关于菲的基准阈值研究鲜有报道.本研究以9种本土水生生物为研究对象,进行了9种水生生物的急性生态毒理学实验及3种慢性生态毒理学实验并推导了菲的基准阈值.此外,基于物种敏感性分布法(species sensitivity distribution,SSD)对本地和非本地物种之间的差异进行了比较,以期探究美国水生生物毒性数据在我国本土基准阈值推导过程中的可行性.结果显示,采用US EPA"指南"推荐的方法对菲本土水生生物急性基准阈值(CMC)和慢性基准阈值(CCC)进行了推导,分别为0.033 mg·L~(-1)和0.012 mg·L~(-1);另外,本土与美国物种敏感性分布不存在显著性差异,这表明存在使用美国水生生物毒性数据来推导我国菲水生生物基准阈值的可能性.     

重金属砷的前期处理实验

砷是一种有毒元素,自然界较常见的砷为三价或五价,三价砷有强毒性,五价砷毒性较弱.先进行前期处理将三价砷氧化为五价,以备下一步砷的去除.为此,试验用纯氧、双氧水使用2种氧化剂,将三价砷氧化成五价并比较不同温度、酸碱环境、氧化剂浓度、是否添加催化剂铜等参数.发现碱性环境较酸性环境有利砷的氧化,双氧水氧化效果比纯氧好,可能是它的反应活化能远小于纯氧的缘故.     

应用物种敏感度分布法研究中国无机汞的水生生物水质基准

基于中国的水生生物区系特征,筛选了包括植物、无脊椎动物和脊椎动物等90个水生生物的急性毒性数据,使用物种敏感度分布法探讨了各类物种的敏感度分布特征,推导了中国无机汞的水生生物水质基准.结果表明,甲壳类生物对无机汞最为敏感,Log-Slogistic3对各组数据拟合效果最佳.基于对全部数据的拟合结果,得出无机汞的急性水质基准和慢性水质基准分别是1.743和0.467μg.L-1.该基准值与其他国家使用类似统计外推法得到的基准值在同一数量级,但也存在着差异,反映了各国水生态系统物种组成的差异.中国无机汞水生生物水质基准的建立,旨在保护中国地表水生态系统中的水生生物免受无机汞的高浓度急性暴露以及低浓度慢性暴露产生的毒害效应.比较不同水体无机汞的浓度水平发现,除嘉陵江水体溶解态汞可能会对水生生物具有潜在风险外,西南地区地表水活性汞均不会对水生生物产生危害.     

我国土霉素的淡水生物水质基准与标准及生态风险评估研究

土霉素是一种典型的抗生素类新污染物,具有使用量大、生态毒性强等特点,其环境基准标准和水生态风险受到学界广泛关注.本文基于美国毒理数据库、Web of Science、中国知网等相关数据库,收集整理了土霉素对我国淡水生物的毒性数据和水环境暴露数据,制定了保护淡水生物的水质基准,并进行了风险评估.结果表明：(1)依据《中国动物志》和《淡水生物水质基准推导技术指南》等,对毒性数据的物种和试验条件进行筛选,最终土霉素急性毒性数据涉及5门10科13种,最敏感物种为模糊网纹溞(Ceriodaphnia dubia);慢性数据涉及3门9科10种,最敏感物种为水蕴草(Egeria densa).(2)物种敏感度分布法研究表明,急性数据符合逻辑斯蒂分布模型,推导出的短期水质基准为61.2μg/L;慢性毒性数据符合正态分布模型,推导出的长期水质基准为18.7μg/L.(3)毒性百分数排序法推导的基准最大浓度为34.0μg/L,基准连续浓度为7.4μg/L.(4)共搜集近15年(2007年1月—2022年3月)我国主要水体土霉素浓度数据803条,浓度范围为0.1～97 433.8 ng/L,北方流域的土霉素...     

太湖不同富营养化水域砷的分布特征及其环境影响因素

对夏季与冬季太湖不同营养水平湖区(竺山湾、梅梁湾、贡湖湾和南太湖)上覆水的砷含量及水质参数进行调查,运用多元分析技术分析砷的空间与季节分布特征及其与水质参数之间的关系.结果表明,北部湖区(竺山湾、梅梁湾和贡湖湾)水体中总砷(TAs)、砷酸盐[As(Ⅴ)]、亚砷酸盐[As(Ⅲ)]及甲基砷(MMA+DMA)的平均含量(2.58~3.34、1.37~2.34、0.53~0.64和0.16~0.36μg·L-1)均高于南太湖(1.73、1.10、0.31和0.10μg·L-1),显示了砷在太湖北部与南部的空间分布差异.此外,夏季TAs、As(Ⅴ)、As(Ⅲ)和甲基砷的平均含量分别为3.40、2.06、0.73和0.25μg·L~(-1),均高于冬季(1.78、1.10、0.30和0.17μg·L~(-1)),呈现明显的季节分布特征.因子分析与冗余分析结果进一步表明,总磷(TP)、总铁(TFe)和叶绿素a(Chl-a)是影响太湖水体砷时空分布的关键环境因子.其中,TP、TFe与太湖水体中TAs和As(Ⅴ)的分布存在显著正相关;Chl-a含量对As(Ⅲ)和甲基砷的分布有显著影响,推测浮游植物(Chl-a)对砷还原和生物甲基化具有一定的调控作用.     

微生物-铁氧化物交互作用对黄土中砷活化迁移的影响

中国黄土高原地区普遍存在地下水砷超过饮用水标准问题,迫切需要深入认识和理解高砷地下水形成机制.在分析黄土中砷的含量、赋存状态基础上,以乳酸钠为有机碳源,开展缺氧条件下厌氧微生物-铁氧化物交互作用影响黄土中砷活化迁移的模拟实验研究.结果表明黄土中砷含量在23~30 mg·kg-1,变化范围很小.砷主要以吸附态、铁氧化物结合态、残渣态形式存在,平均值分别为10.57 mg·kg-1(占总砷37.76%)、10.12 mg·kg-1(占总砷36.15%)、7.19 mg·kg-1(占总砷25.69%);当水中存在有机物形成缺氧环境时,厌氧微生物异化铁还原菌(DIRB)和硫酸盐还原菌(SRB)直接或间接还原铁氧化物引起部分铁氧化物分解,导致吸附态和铁氧化物结合态砷部分释放到地下水中,引起地下水中砷升高,砷释放量主要与水中有机物浓度有关.研究表明,当有机物浓度达到100 mg·L-1时,固液比为1∶10,在土著微生物作用下,砷浓度可以达到15μg·L-1;接种DIRB和SRB以及两种微生物同时存在都有明显的促进黄土中砷活化迁移的作用,水中砷浓度可以达到40μg·L-1.     

大连湾53号排污口附近海域砷的迁移规律研究

砷(Arsenic)的化合物,通常因在海水中pH、Eh的不同,存在的价态不同,因而毒性的强弱也不同。砷的毒性次序是:砷化氢(AsH_3)>亚砷酸盐(AsO_3~(3-))>氧化砷(As_2O_3)>砷酸盐(AsO_4~(3-))>砷酸(H_3AsO_4)。一般认为三价砷能与硫氢基(-SH)结合形成稳定的螯合物,而五价砷对(-SH)基没有这种亲和性,因此三价砷的毒性作用是     

微生物对砷的氧化还原竞争

滤池被广泛运用于饮用水厂中,前期研究发现某水厂生物滤池处理含砷地下水时,一方面三价砷可被生物氧化锰氧化为五价砷,另一方面滤池系统中存在的微生物砷还原酶可促使五价砷还原为三价砷,而滤池表面存在的这种微生物竞争关系会影响滤池的稳定性及处理效率.为探讨其内在机制,本研究选取1株锰氧化模式菌(Pseudomonas sp.QJX-1)和1株砷还原模式菌(Brevibacterium sp.LSJ-9),考察在Mn2+、As(As3+、As5+)共存时,两菌株对空间、营养物质以及对砷氧化/还原的竞争关系.结果表明,不同的反应时间,Mn、As质量浓度/价态不同,三价及五价砷体系中,Pseudomonas sp.QJX-1生成的锰氧化物在砷的氧化还原反应中占主导地位,即能迅速氧化本身存在的As3+(三价砷体系)和砷还原菌产生的As3+(五价砷体系),最终两体系中砷都主要以As5+的形式存在.PCR及RT-PCR结果表明,反应过程中锰氧化菌功能基因(cum A)抑制了砷还原酶(ars C)的表达,锰氧化菌16S rRNA表达量始终比砷还原菌高两个数量级,即锰氧化菌在生长竞争过程中占优势.实验结果表明滤池的水力停留时间是决定出水中砷价态的一个重要因素.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.