Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (¹O₂) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of UOH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and ¹O₂. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

膨润土负载纳米铁的改性及对水中As(Ⅴ)的吸附

用十六烷基三甲基溴化铵(CTMAB)对膨润土负载纳米零价铁(Bent-n ZVI)进行表面改性,得到表面改性膨润土负载纳米铁(Bent-n ZVI)/CTMAB。通过SEM、Zeta电位和中位径d(50)分析,与膨润土(Bent)、改性膨润土(CTMAB-Bent)、Bent-n ZVI进行了对比,结果表明:相比Bent-n ZVI,(Bent-n ZVI)/CTMAB中的纳米铁颗粒更为分散且呈链状分布,d(50)仅为5.21μm,并且Zeta电位为+0.65 m V,更易静电吸引和吸附阴离子As O43-。4种材料的除砷结果亦表明其中(Bent-n ZVI)/CTMAB去除率最高,达到了93.9%。光电子能谱(XPS)分析表明(Bent-n ZVI)/CTMAB的除砷产物中只有As(Ⅴ),并不存在其还原态As(Ⅲ),说明(Bent-n ZVI)/CTMAB是通过吸附作用去除As(Ⅴ)。     

2种四环素类抗生素在凹凸棒石黏土中的吸附研究

通过静态吸附实验,探究凹凸棒石黏土对四环素和土霉素的吸附动力学;采用准一级动力学、准二级动力学和颗粒内扩散模型拟合实验数据,分析吸附过程。测定凹凸棒石黏土对四环素和土霉素的动态吸附曲线和吸附容量,研究凹凸棒石黏土对水溶液中四环素和土霉素的动态吸附性能。探讨初始质量浓度对穿透曲线的影响,采用Thomas模型对动态试验数据拟合,获得相关参数。结果表明,凹凸棒石黏土能够有效去除水中的四环素和土霉素,且四环素的吸附容量高于土霉素,在初始浓度为400mg/L时,对四环素的饱和吸附量达74.5mg/g,对土霉素的饱和吸附量达69.2mg/g。穿透曲线呈S型,且随着初始浓度的增大,穿透点向左移,穿透时间缩短,平衡吸附量增加。     

不同晶型纳米TiO_2在斑马鱼体内的富集与清除

为探讨纳米材料的慢性生物效应以及材料结构对生物富集的影响,开展了A-TiO2(锐钛型纳米TiO2)和R-TiO2(金红石型纳米TiO2)在斑马鱼(Danio rerio)体内的长期富集和清除试验.采用半静态暴露试验,试验周期为46 d(暴露阶段28 d,清除阶段18 d),每种晶型设置2个处理组(ρ分别为4.0和10.0 mg/L),测定各时间点斑马鱼体内不同晶型纳米TiO2含量(以w计);以暴露阶段的BAF(生物富集系数)以及清除阶段的排出速率常数、总量清除率为终点,比较斑马鱼对2种晶型纳米TiO2的富集、清除的异同.结果表明:在暴露阶段,A-TiO2在斑马鱼体内的富集量显著高于R-TiO2,10.0 mg/L处理组斑马鱼体内富集量均显著高于4.0 mg/L处理组;4.0和10.0 mg/L的A-TiO2处理组的BAF分别为76.7和105.4 L/kg,略高于R-TiO2(41.6和36.1 L/kg),二者在斑马鱼体内均不具有生物蓄积性.在清除阶段,斑马鱼体内的2种晶型的纳米TiO2均可被排出,清除阶段的清除率为88.0%~100%;斑马鱼体内2种晶型纳米TiO2富集量的下降均符合一阶指数衰减方程,排出速率常数在0.26~1.01 d-1之间.     

都柳江河道急流-深潭-沙(砾)滩系统水质差异研究

河流是流域生态系统的重要组成部分,河流形态结构与水质变化间关系研究可以为河流生态修复提供理论依据。河流是由急流-深潭-沙(砾)滩不断重复出现构成的系统,急流-深潭-沙(砾)滩是河流的基本结构单元,并以都柳江上、中、下游9个急流-深潭-沙(砾)滩单元为对象,测定了水质指标,分析了山区典型河道基本结构单元与水质变化之间的关系。结果表明:都柳江深潭水体中氮素浓度与pH值大于急流,其浓度分别是总氮0.97mg/L和0.87mg/L;硝酸盐氮0.60mg/L和0.56mg/L;氨氮0.22mg/L和0.20mg/L;pH8.22和8.14。而磷素、溶解氧、BOD5和COD则是深潭小于急流。其浓度分别是总磷0.0187mg/L和0.0202mg/L;正磷酸盐0.0070mg/L和0.0085mg/L;溶解氧11.93mg/L和13.50mg/L;BOD53.75mg/L和5.36mg/L;COD10.986mg/L和12.807mg/L。电导率深潭与急流相等,均为169.7μS/cm。方差分析表明,深潭与急流水体总氮和硝酸盐氮在夏季差异极显著;磷素和pH在春季差异极显著;电导率在秋季差异极显著;氨氮、溶解氧、BOD5和COD差异均不显著。研究工作显示,河流形态结构变化影响着水环境质量,急流-深潭-沙(砾)滩不断重复出现使河流水质得到改善,在河道生态修复中需要遵循河流形态结构规律以便提高河流的自净能力。     

随州市环境空气中苯系物的污染特征

2013年1月对随州市环境空气中苯系物(BTEX-苯,甲苯,乙苯和二甲苯)的质量浓度进行了监测,并分析了其变化规律及影响因素。结果表明,随州市环境空气中几种苯系物的浓度差异明显,其中苯的浓度最高,平均浓度为58.92μg/m3,甲苯、乙苯、间,对-二甲苯、邻-二甲苯的平均浓度分别为15.17、7.69、22.46、12.11μg/m3。对比发现,环境空气中苯系物的日间浓度高于夜间,工业区苯系物的浓度高于居住区和商业区。用SPSS软件对监测数据进行了分析,结果表明,溶剂的挥发和涂料喷涂行业是苯的重要来源。苯系物的浓度变化特征与交通尾气排放、化石燃料燃烧、光化学反应活动等密切相关。     

GAM的区域PM_(2.5)浓度影响因子识别及关联关系分析

区域PM_(2.5)浓度影响因子及显著程度对区域PM_(2.5)浓度模拟和污染控制具有重要意义。该研究应用广义加性模型(GAM)建立模型分析2013年京津冀区域PM_(2.5)浓度与AOD、气象因子(相对湿度、温度、降雨量、大气压、风速)和土地利用类型(水体、林地、耕地、建设用地、裸地)之间的相关关系。结果表明,温度、大气压、AOD、林地、建设用地和裸地显著的影响PM_(2.5)浓度;且温度、AOD、裸地、林地与PM_(2.5)存在复杂相关关系,大气压、建设用地与PM_(2.5)浓度存在线性相关关系。GAM模型R~2为0.952,拟合结果与实测结果的线性回归方程系数为0.959,模型交叉验证后得到R2为0.792。结果表明,利用GAM能有效的识别区域PM_(2.5)浓度的影响因子,根据影响因子进行PM_(2.5)浓度拟合并得到可靠的拟合结果。     

基于BN的模糊系统事故风险管理辅助分析

为提高模糊系统事故定量风险管理水平,将三角模糊数与贝叶斯网络相结合,提出基于BN的模糊系统事故风险管理辅助分析方法.首先通过致险机理分析确定风险事件各致险因子,在此基础上构建贝叶斯网络(BN),致险因子的先验概率用三角模糊数进行处理;然后利用BN的推理技术对风险事件进行概率预测、致因诊断和致险因子重要度分析;最后以某化工企业储油罐体火灾爆炸事故为例,应用该方法进行实证研究.结果表明:该方法能定量预测风险事件发生概率以界定风险等级,致因诊断能快速查明最可能的致因因素及其组合,重要度分析能找出系统薄弱环节以明确风险管理控制要点,从而为模糊系统事故风险管理提供辅助决策支持.