Acute toxicity variation of hydroxyl benzophenone UV filters during photoinduction–chlorination disinfection processes

Benzophenones(BPs), a group of widely used UV filters, exert multiple, significant toxicity effects. The 11 BPs were selected as target compounds, and the photobacterium acute toxicity test and an index for acute toxicity formation potential(ATFP) were used to evaluate the toxicity variation of BPs before and after a photoinduction–chlorination disinfection process.Orthogonal experiments were performed at different pH values and chlorine dosages. The characteristics of ATFP values for 11 BPs after a photoinduction–chlorination process can be summarized as follows:(1) The ATFPs decreased as the hydroxyl group number increased in BPs molecules.(2) For those BPs with the same hydroxyl group number, the ATFPs were higher when the hydroxyl groups were located at the 3-or 4-position than those at the 2-position; the BPs with hydroxyl groups distributed on two benzene rings had higher ATFPs than those on one ring.(3) Introducing a methoxyl group and sulfonic acid group into BP molecules increased the ATFP values.(4) The ATFPs were p H-dependent, the values of which were lowest at the neutral condition and highest at the acid condition.(5) The ATFPs increased and then decreased as the chlorine dosage increased. The results can be used as a reference to scientifically evaluate the environmental fate and potential risk of BPs in photoinduction–chlorination disinfection processes.     

厌氧酸化在焦化废水脱氮和毒性削减中的作用

分别用厌氧酸化-缺氧-好氧(A₁-A₂-O)生物膜法和缺氧-好氧(A/O)生物膜法处理焦化废水,比较了二者对废水毒性的削减效果.试验结果表明,焦化废水的毒性大于0.19mg/L氯化汞的毒性.其毒性削减与有机氮去除有一定关系,厌氧酸化在提高废水有机氮去除率和降低废水的毒性方面起到了重要的作用.废水经A₁-A₂-O生物膜系统处理后,毒性大大降低,当HRT为37.9h时,出水对发光菌的相对发光度可达96.8%,其毒性相当于0.023mg/L氯化汞的毒性.     

Toxicity-based assessment of the treatment performance of wastewater treatment and reclamation processes

The reclamation and reuse of wastewater is one of the possible ways to relieve the serious fresh water resource crisis in China. Efficient reclamation treatment technologies ensure the safe reuse of reclaimed water. In order to screen out and evaluate technologies appropriate for reclamation treatment, a great deal of efforts have been brought to bear. In the present study, a toxicity-based method including a Photobacterium phosphoreum test for acute toxicity and SOS/umu test for genotoxicity, accompanied by the traditional physicochemical parameters DOC (dissolved organic carbon) and UV₂₅₄ (absorbance at 254 nm), was used to measure the treatment performance of different reclamation processes, including the anaerobic-anoxic-oxic biological process (A²O) and subsequent physical/chemical reclamation processes (ultrafiltration, ozonation, chlorination). It was found that for the secondary effluent after the A²O process, both the toxicity and physicochemical indices had greatly decreased compared with those of the influent. However, chemical reclamation processes such as ozonation and chlorination could possibly raise toxicity levels again. Fortunately, the toxicity elevation could be avoided by optimizing the ozone dosage and using activated carbon after ozonation. It was noted that by increasing the ozone dosage to 10 mg/L and employing activated carbon with more than 10 min hydraulic retention time, toxicity elevation was controlled. Furthermore, it was shown that pre-ozonation before activated carbon and chlorination played an important role in removing organic compounds and reducing the toxicity formation potential. The toxicity test could serve as a valuable tool to evaluate the performance of reclamation processes.     

水中萘普生的紫外光降解机制及其产物毒性研究

以120 W汞灯为紫外光光源,通过活性氧物种(ROS)的淬灭实验和溶解氧(DO)浓度实验和发光菌毒性实验,对水中萘普生(NPX)的降解机制、反应动力学及其产物毒性进行了研究.结果表明,NPX的紫外光降解过程包括了直接光解和ROS参与的自敏化光解两个过程,同时.OH、1O2、O.2-的自敏化光解贡献率分别为0.1%、80.2%、35.7%;溶解氧浓度实验表明,溶解氧对萘普生的降解具有抑制作用,而且浓度越大,抑制效果越明显;发光菌毒性实验表明,萘普生光降解生成了具有较萘普生更高风险的中间产物.本研究中萘普生的所有光解实验过程均符合准一级动力学方程.     

白洋淀地区污染状况的生物毒性评价

从1992年10月到1994年4月先后几次对白洋淀集水区,包括淀区及排污河道等十几个样点进行了水样采集和多指标生物毒性检验。选用的生物组合包括：荧光发光菌（Photobacteriumphosphorum）、斜生栅藻（Scenedesmusobliqnus）和大型（Daphiniamagna）,罗非鱼（Tilapiamossambica）鱼肝细胞毒性检验,结果表明大部分样品对光合藻有明显刺激生长的作用。污水库沿线和安新县排污渠水样对浮游动物有毒性作用。府河沿线的水样仅对鱼肝细胞有毒性作用,对发光菌无明显抑制。这些潜在的生物毒性效应是否会影响白洋淀淀区的水生生态系统,需进一步深入研究。     

Formation of THMs and HANs during bromination of Microcystis aeruginosa

Bromine-contained disinfectants and biocides are widely used in swimming pools, recreational waters and cooling towers. The objective of this study was to evaluate the formation of thrihalomethanes (THMs) and haloacetonitriles (HANs) and their cytotoxicity in algae solutions during free bromine disinfection. Disinfection by-products formation potential experiments were conducted using model solutions containing 7 mg/L (as total organic carbon) Microcystis aeruginosa cells. Effects of free bromine dosage, pH and ammonia were investigated. The results showed that brominated disinfection by-products were the major products when free bromine was applied. The total THMs formed during bromination was much as that formed during chlorination, whereas HANs were elevated by using bromination instead of chlorination. Dibromoacetonitrice (C2H2NBr2 ) and bromoform (CHBr3 ) were the only detected species during free bromine disinfection. The production of C2H2NBr2 and CHBr 3 increased with disinfectant dosage but decreased with dosing ammonia. CHBr3 increased with the pH changing from 5 to 9. However, C2H2NBr2 achieved the highest production at neutral pH, which was due to a joint effect of variation in hydrolysis rate and free bromine reactivity. The hydrolysis of C2H2NBr2 was base-catalytic and nearly unaffected by disinfectant. Finally, estimation of cytotoxicity of the disinfected algae solutions showed that HANs formation was responsible for the majority of toxicity. Considering its highest toxicity among the measured disinfection by-products, the elevated C2H2NBr2 should be considered when using bromine-related algaecide.     

二氧化氯消毒前后污水毒性的变化及消毒条件的影响

采用发光细菌试验和umu试验,分别考察了二氧化氯投加量和反应时间对污水二氧化氯消毒后急性毒性和遗传毒性变化的影响.结果表明,随着二氧化氯消毒剂投加量的增加,消毒后水样的急性毒性不断增大,但遗传毒性逐渐减小后趋于稳定.随着反应时间的延长,二氧化氯的消耗量不断增大,消毒后水样的急性毒性先增大后减小,遗传毒性逐渐减小后趋于稳定.由于消毒条件对污水急性毒性和遗传毒性有着不同的影响,说明污水中产生急性毒性和产生遗传毒性的物质不同,对于某一种污水,通过控制消毒条件可以使消毒后污水的急性毒性和遗传毒性都较低.     

Effects of silver adsorbed on fumed silica, silver phosphate glass, bentonite organomodified with silver and titanium dioxide in aquatic indicator organisms

In order to reduce the level of transmission of diseases caused by bacteria and fungi, the development of antimicrobial additives for use in personal care, hygiene products, clothing and others has increased. Many of these additives are based on metals such as silver and titanium. The disposal of these products in the environment has raised concerns pertaining to their potential harmfulness for beneficial organisms. The objective of this study was to evaluate the influence of the shape, surface chemistry, size and carrier of three additives containing silver and one with titanium dioxide (TiO₂) on microcrustacean survival. Daphnia magna was used as a bioindicator for acute exposure test in suspensions from 0.0001 to 10,000 ppm. Ceriodaphnia dubia was used for chronic test in TiO₂ suspensions from 0.001 to 100 ppm. D. magna populations presented high susceptibility to all silver based additives, with 100% mortality after 24 hr of exposure. A different result was found in the acute experiments containing TiO₂ suspensions, with mortality rates only after 48 hr of incubation. Even on acute and chronic tests, TiO₂ did not reach a linear concentration-response versus mortality, with 1 ppm being more toxic than 10,000 ppm on acute test and 0.001 more toxic than 0.01 ppm on chronic assay. Silver based material toxicity was attributed to silver itself, and had no relation to either form (nano or ion) or carrier (silica, phosphate glass or bentonite). TiO₂ demonstrated to have a low acute toxicity against D. magna.     

四氟硼酸化1-烷基—3-甲基咪唑离子液体对小鼠的急性经口毒性

采用寇式改良法研究了四氟硼酸化1-烷基—3-甲基咪唑离子液体对小鼠的急性毒性,考察了烷基侧链长度对毒性的影响,同时采用HE染色法观察了离子液体对小鼠胃、小肠、大肠、肝和肾组织的损害.结果表明,4种离子液体([Cnmim] BF4,n=10、12、14、18)对小鼠的肠、肝、肾等组织均有损伤,其LD50值在56.16 ～214.18 mg·kg-1之间,为中等毒性.四氟硼酸化1-烷基—3-甲基咪唑离子液体对小鼠的急性毒性与烷基侧链长度有关,当碳链长度为14时,毒性最强.     

镉与S-异丙甲草胺对斜生栅藻的联合毒性作用

采用毒性标准实验方法研究了Cd2+与S-异丙甲草胺单独及联合作用对斜生栅藻急性毒性、总可溶性蛋白含量、超氧化物歧化酶(SOD)活性和细胞膜通透性的影响.结果表明Cd2+与S-异丙甲草胺单独作用时EC50均随时间的延长而减小,且S-异丙甲草胺的急性毒性大于Cd2+;Cd2+、S-异丙甲草胺的EC50-24h分别为0.27 mg·L-1、0.24 mg·L-1,EC50-96h分别为0.16mg·L-1、0.13 mg·L-1.Cd2+与S-异丙甲草胺联合作用时低浓度表现为协同作用,高浓度表现为拮抗作用.暴露96 h后,Cd2+与S-异丙甲草胺单独及联合作用下,随有毒物质浓度升高,斜生栅藻总可溶性蛋白含量降低,SOD酶活性先激活后抑制,细胞膜通透性逐渐增大.     

Rac-及S-异丙甲草胺对2种微藻毒性特征影响研究

应用急性毒性试验方法,在对映体水平上研究了除草剂Rac-及S-异丙甲草胺对斜生栅藻(Scenedesmus obliquus)和普通核小球藻(Chlorella vulgaris)的急性毒性特征及腐殖酸对除草剂毒性的影响.结果表明,Rac-及S-异丙甲草胺的急性毒性与浓度及暴露时间呈正相关,Rac-及S-异丙甲草胺对微藻细胞的急性毒性存在立体选择性差异.Rac-异丙甲草胺对普通核小球藻和斜生栅藻的EC50,96 h分别是S-异丙甲草胺的2.25和1.81倍,S-异丙甲草胺对微藻细胞的生态毒性较大,而斜生栅藻对Rac-及S-异丙甲草胺的敏感性更强,且Rac-及S-异丙甲草胺对斜生栅藻和普通核小球藻的急性毒性存在一定的线性相关性.腐殖酸的加入能够改变Rac-及S-异丙甲草胺对微藻细胞生态毒性,对S-异丙甲草胺的生态毒性的影响更为明显(P<0.05).     

Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process

Benzophenones （BPs） are a class of widely used UV filters, which have been frequently detected within multiple environmental matrices. Disinfection is a necessary process in water treatment processes. The transformation behaviors and toxicity changes of 14 BP-type UV filters during chlorination disinfection treatment were investigated in this study. A new index, the acute toxicity formation potential, was proposed to evaluate the toxicity changes and potential risks of BP-type UV filters during chlorination treatment. It was found that 13 of 14 BP-type UV filters exhibited toxicity decreases in the chlorination disinfection process, more or less, while one showed a toxicity increase. The toxicity changes were dependent on substitution effects, such that 2,4-di-hydroxylated or 3-hydroxylated BPs exhibited significant toxicity decreases after chlorination treatment due to the ready cleavage of the aromatic ring. Importantly, the acute toxicity changes could be duplicated in an ambient water matrix.     

Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles (AgNPs) have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion (Ag⁺) into the aquatic environment. Our recent study revealed that ubiquitous natural organic matter (NOM) could reduce Ag⁺ to AgNP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag⁺ and AgNPs with varied Ag⁺% through the sunlight-driven reduction of Ag⁺ by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag⁺ was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution pH and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8 hr-median lethal concentration (LC₅₀) demonstrated that the reduction of Ag⁺ by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag⁺ and AgNPs, and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag⁺ from AgNPs.     

饮用水含氮与含碳消毒副产物的生成潜能及其毒性

消毒副产物生成潜能测试常用于表征水中消毒副产物的前体物含量.不同于三氯甲烷等含碳消毒副产物,二卤代乙腈（DHANs）与二卤代乙酰胺（DHAcAms）等含氮消毒副产物在氯消毒的余氯存在下易分解,并且在氯胺消毒过程中可由氯胺提供氮源生成,因此常用于含碳消毒副产物的生成潜能测试方法（如Krasner提出的测试法）可能无法有效揭示DHANs与DHAcAms的前体物水平.本研究以三氯甲烷和氯醛两种含碳消毒副产物为对比,考察DHANs与DHAcAms在饮用水氯消毒与氯胺消毒过程中不同投氯量与反应时间下的生成量,识别最大生成量对应的消毒条件,以便更好地评估水样中DHANs与DHAcAms的前体物浓度.同时,对消毒过程中生成的这些挥发性消毒副产物进行毒性评价.结果显示,两个水样氯消毒的DHANs与DHAcAms生成量分别为6.19~40.08、1.34~15.75 nmol·mg^-1（mg^-1以TOC计）;氯胺消毒的DHANs与DHAcAms生成量分别为2.63~21.46、18.43~49.99 nmol·mg^-1.Krasner测试法条件下的DHANs与DHAcAms生成量均最低.在投氯量为TOC+8×NH₃-N、反应时间为24 h的氯消毒条件下,氯胺投加量20×TOC、反应时间为3 d的氯胺消毒条件下,两个水样具有最高水平的DHANs与DHAcAms生成量,并且消毒副产物毒性也高于Krasner法测试条件下的毒性水平.因此,氯消毒采用投氯量TOC+8×NH₃-N、反应时间24 h,氯胺消毒采用投加量20×TOC、反应时间3 d的生成潜能测试条件可能更好地揭示水中DHANs和DHAcAms的前体物浓度水平.     

Evaluation of biostimulation and Tween 80 addition for the bioremediation of long-term DDT-contaminated soil

The bioremediation of a long-term contaminated soil through biostimulation and surfactant addition was evaluated. The concentrations of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) and its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE) were monitored during an 8-week remediation process. Physicochemical characterization of the treated soil was performed before and after the bioremediation process. The isolation and identification of predominant microorganisms during the remediation process were also carried out. The efficiency of detoxification was evaluated after each bioremediation protocol. Humidity and pH and the heterotrophic microorganism count were monitored weekly. The DDT concentration was reduced by 79% after 8 weeks via biostimulation with surfactant addition (B + S) and 94.3% via biostimulation alone (B). Likewise, the concentrations of the metabolites DDE and DDD were reduced to levels below the quantification limits. The microorganisms isolated during bioremediation were identified as Bacillus thuringiensis, Flavobacterium sp., Cuprivadius sp., Variovorax soli, Phenylobacterium sp. and Lysobacter sp., among others. Analysis with scanning electron microscopy (SEM) allowed visualization of the colonization patterns of soil particles. The toxicity of the soil before and after bioremediation was evaluated using Vibrio fischeri as a bioluminescent sensor. A decrease in the toxic potential of the soil was verified by the increase of the concentration/effect relationship EC₅₀ to 26.9% and 27.2% for B + S and B, respectively, compared to 0.4% obtained for the soil before treatment and 2.5% by natural attenuation after 8 weeks of treatment.     

3种氯酚对噬热四膜虫的毒性效应

以原生动物噬热四膜虫作为受试生物,研究了3种氯酚的急性毒性和遗传毒性及环境因子对污染物的生物效应,探讨了水体硬度对3种氯酚生物毒性的影响.结果表明,3种氯酚毒性大小依次为五氯酚(PCP)>2,4,6-三氯酚(2,4,6-TCP)>2,4-二氯酚(2,4-DCP),表明随着氯原子数目的增加,生物毒性增强.硬度实验结果显示随水体硬度升高,3种氯酚对四膜虫的急性毒性先降低后增加,但不同的水体硬度下2,4-DCP对四膜虫的24、48、72和96 h EC50值分别为3.69、3.54、3.02和2.34 mg·L-1;2,4,6-TCP分别为3.23、2.83、2.56和1.97 mg·L-1;PCP分别为0.63、0.45、0.34和0.28 mg·L-1,3种氯酚的EC50值分别在同一数量级上,表明对四膜虫的毒性影响不大.采用单细胞凝胶电泳技术(SCEG)研究了3种氯酚对四膜虫核DNA的损伤作用,结果显示氯酚类化合物具有细胞毒性,彗星实验可以较好地指示氯酚类化合物的遗传毒性.     

不同pH值下对发光菌的毒性及QSAR研究

测定了11种苯酚类化合物在不同pH下对发光菌的急性毒性(15minEC50。)。应用两种理化参数logP和pKa对毒性数据进行了定量构效关系(QSARs)研究,并在此基础上初步探讨了苯酚类化合物的毒性机制。结果表明,苯酚类化合物对发光菌的毒性随pH的升高而减小,这与不同pH下苯酚类化合物的电离程度有关。相同pH下,苯酚类化合物的毒性随取代基团的种类、个数及取代位置而不同。苯酚类化合物属于极性麻醉(麻醉Ⅱ型)化合物,毒性可用logP和pKa来联合描述。     

咪唑型离子液体对小鼠的急性毒性

采用寇氏改良法研究了咪唑型离子液体对小鼠的急性毒性,并考察了烷基侧链长度对其毒性的影响,同时采用HE染色法观察了其对小鼠肝脏的毒性.结果表明,4种咪唑型离子液体([C10mim]Br、[C12mim]Br、[C14mim]Br和[C18mim]Br)对小鼠肝脏均有损伤,其LD50值在98.91～220.16 mg·kg...     

铜、锌对小麦的联合毒性及其预测模型研究

利用溶液培养实验,研究了不同Ca浓度和Cu/Zn配比下,Cu、Zn对小麦的联合毒性;基于毒性单位模型(TU)和生物配体模型(BLM),建立了Cu-Zn对小麦的联合毒性预测模型TUfmix-BLM.结果表明,随着溶液中Ca浓度增加,单一Cu和Zn的毒性均明显减弱.不同Ca浓度、不同Cu/Zn浓度配比下(1∶50、1∶200、1∶800),Cu-Zn联合毒性均表现为加和作用.基于Cu、Zn单一毒性的BLM络合常数,结合TU模型,预测了CuZn对小麦的联合毒性.与单独利用TU模型相比,TUfmix-BLM预测的RMSE从13.06减小到10.01,R2从0.89增加到0.94,表明TUfmix-BLM模型可以很好地预测Cu-Zn的联合毒性.