模拟日光照射下土霉素的复合光化学转化动力学及环境归趋

环境水体中存在众多可解离的有机污染物,而不同的解离形态表现出相异的环境行为,如光化学反应活性和归趋.本文以土霉素(OTC)为例,研究了水中可解离化合物的表观光降解、光氧化等复合光化学转化动力学,并揭示了其相应的环境光化学归趋和贡献.模拟日光(λ290nm)照射下,OTC的光降解遵循准一级反应动力学,光解速率常数(k)对pH表现出明显的依赖性.这是由于随pH值升高,解离形态(i)从OTCH_2~0、OTCH~-到OTC~(2-)渐变,相应的k_i和量子产率(Φ_i)显著增大.竞争动力学实验进一步表明,·OH和~1O_2均可以氧化降解OTC,且降解速率随着pH的增大而加快.这与3种解离形态不同的去质子化程度和氧化反应活性有关.去质子化增加化合物的电子密度,利于活性氧物种的亲电攻击,从而促进光氧化反应.基于以上OTC解离形态的不同光化学转化活性,评估了环境表层水体(pH=6~9)中的复合光化学转化半减期(t_(1/2,E)).t_(1/2,E)值依赖于基质pH和季节,北纬45°晴天正午,t_(1/2,E)在0.131 h(仲夏,pH=9)到3.63 h(仲冬,pH=6)之间.多数情况下,OTC的表观光解是其最主要的光化学转化途径,~1O_2氧化次之,而·OH氧化的贡献非常小.以上结果证明了OTC不同解离形态具有不同的光化学转化动力学.因此,为了准确评价水环境中抗生素等可解离有机污染物的光化学归趋和风险,有必要综合考虑所有解离形态的复合光化学行为.     

Photochemical production of carbonyl sulfide, carbon disulfide and dimethyl sulfide in a lake water

Photochemical production of carbonyl sulfide(COS),carbon disulfide(CS_2) and dimethyl sulfide(DMS) was intensively studied in the water from the Aohai Lake of Beijing city.The lake water was found to be highly supersaturated with COS,CS_2 and DMS,with their initial concentrations of 0.91 ± 0.073 nmol/L,0.55 ± 0.071 nmol/L and 0.37 ± 0.062 nmol/L,respectively.The evident photochemical production of COS and CS_2 in the lake water under irradiation of 365 nm and 302 nm indicated that photochemical production of them might be the reason for their supersaturation.The similar dependence of wavelength and oxygen for photochemical production of COS,CS_2 and DMS implied that they might be from the same precursors.The water cage effect was found to favor COS production but inhibit CS_2and DMS formation,indicating that COS photochemical production was mainly from direct degradation of the precursors and the formation of CS_2 and DMS needed intermediates via combination of carbon-centered radicals and sulfur-centered radicals.The above assumptions were further confirmed by simulation experiments with addition of carbonyls and amino acids(cysteine and methionine),and the photochemical formation mechanisms for COS,CS_2 and DMS in water were derived from the investigations.     

Pollution characteristics, sources and lung cancer risk of atmospheric polycyclic aromatic hydrocarbons in a new urban district of Nanjing, China

This paper focused on the pollution characteristics,sources and lung cancer risk of atmospheric polycyclic aromatic hydrocarbons(PAHs) in a new urban district of Nanjing,China.Gaseous and aerosol PM_(2.5)(particulate matter with aerodynamic diameter smaller than2.5 urn) samples were collected in spring of 2015.Sixteen PAHs were extracted and analyzed after sampling.Firstly,arithmetic mean concentrations of PAHs and BaP_(eq)(benzo[a]pyrene equivalent) were calculated.The mean concentrations of PAHs were 29.26±14.13,18.14±5.37 and 48.47±16.03 ng/m~3 in gas phase,particle phase and both phases,respectively.The mean concentrations of BaP_(eq) were 0.87±0.51,2.71±2.17 and 4.06±2.31 ng/m~3 in gas phase,particle phase and both phases,respectively.Secondly,diagnostic ratios and principal component analysis were adopted to identify the sources of PAHs and the outcomes were the same:traffic exhaust was the predominant source followed by fuel combustion and industrial process.Finally,incremental lung cancer risk(ILCR) induced by whole year inhalation exposure to PAHs for population groups of different age and gender were estimated based on a Monte Carlo simulation.ILCR values caused by particle phase PAHs were greater than those caused by gas phase PAHs.ILCR values for adults were greater than those for other age groups.ILCR values caused by total(gas + particle) PAHs for diverse groups were all greater than the significant level(10~6),indicating high potential lung cancer risk.Sensitivity analysis results showed that cancer slope factor for BaP inhalation exposure and BaP_(eq) concentration had greater impact than body weight and inhalation rate on the ILCR.     

添加剂F127对CPVC超滤膜性能的影响研究

文章探讨了添加剂F127的质量百分含量(5%、7%、10%和13%)对CPVC超滤膜微观结构及其性能(包括水通量、截留率、机械性能、亲水性和耐污染性能)的影响.结果表明:随着F127含量的增加,铸膜液剪切粘度增加,截留率上升,亲水性和耐污染性能大幅度提高,纯水通量和机械性能有所下降.综合比较添加剂F127含量为10%时,CPVC超滤膜性能较好.     

某工矿废弃地重金属污染评价及农田复垦修复建议

以四川某废弃硫磺矿厂区域为研究区,采集78个土壤样本,测定土壤Cd、Cr、Cu、Ni含量及p H值。采用单因子污染指数、内梅罗综合污染指数评价研究区重金属污染程度,采用聚类分析解析污染来源,GIS制图呈现污染空间分布。以土壤环境质量二级标准值为参考,单因子污染指数评价结果显示,重金属样本点位超标率由高到底依次为Cd(84.6%,表层)Cu(53.9%,表层)Ni(51.3%,表层)Cr(32.3%,次表层);内梅罗综合污染指数评价结果表明研究区属于中度污染级别;聚类分析结果表明研究区重金属Cr、Cu、Ni污染来源于矿渣,Cd污染来源尚不明确;GIS制图结果表明污染程度较重的区域主要分布在研究区西南侧。本调查评价旨在为土壤污染治理方案的制定提供参考。     

绿色屋面不同基质组分对降雨径流水质和水量的影响

通过模拟降雨强度50~80 mm的降雨实验,研究了3种常用基质(商业基质、火山岩基质和田园土基质)绿色屋面的径流滞留率和径流水质的特点.结果表明:商业基质的径流滞留率最高,达到48.6%,火山岩基质和田园土基质的滞留率分别为33.6%和30.4%;随着降雨历时的延长,3种基质屋面径流中各水质参数浓度呈现出逐渐降低的趋势,但是,随着降雨强度的加大,商业基质径流中TN浓度和COD呈现出逐渐升高的趋势,而火山岩和田园土基质径流水质参数未呈现出明显变化;田园土基质屋面径流EC、TN、COD、TP和TSS的浓度均值高达3973.54、36.96、503.67、2.64和92.02 mg·L~(-1),显著高于商业基质屋面和火山岩基质屋面;商业基质屋面能够有效地中和模拟降雨的pH,且径流中EC、TP和TSS浓度与火山岩基质屋面径流无明显差异.但是,这2种基质屋面径流中TN和COD的浓度(商业基质:17.47 mg·L~(-1)和87.99 mg·L~(-1),火山岩基质:10.95 mg·L~(-1)和157.85 mg·L~(-1))均超出国家地表水环境质量V类标准;通过综合分析3种屋面基质径流滞留率和径流水质,认为商业基质是我国北方地区较为适宜的绿色屋面基质.研究结果可为绿色屋面的科学构建和城市暴雨径流管理提供科学依据,并为我国海绵城市的建设提供重要的理论依据.     

添加几种秸秆并淹水对海南土壤N2O和CH4排放的影响

利用室内培养试验研究了淹水条件下,不同种类的秸秆对退化菜地土壤修复过程中土壤N_2O和CH_4排放及其综合温室效应的影响.试验设大豆秸秆、花生秸秆、甘蔗渣、水稻秸秆和空白5个处理,试验培养条件为土壤淹水和30℃.结果表明,添加大豆秸秆、花生秸秆和水稻秸秆均能显著提高土壤的pH、有机质和速效钾含量,且能快速降低土壤氧化还原电位Eh.添加大豆秸秆、花生秸秆、甘蔗渣均能显著降低土壤N_2O的排放,其中,大豆秸秆的减排效果最佳.但添加大豆秸秆、花生秸秆、水稻秸秆会促进CH_4大量排放,从而导致综合温室效应增加.花生秸秆处理增加的综合温室效应最大,其次是水稻秸秆处理.甘蔗渣处理的综合温室效应显著低于空白,但甘蔗渣处理对土壤改良效果不佳,其不能快速创造强还原条件,未能提高pH与速效钾等.比较4种材料,添加大豆秸秆增加的综合温室效应较小,且改良土壤效果较佳,更适合作为强还原灭菌法的理想材料.     

环丙沙星在污水处理过程中的迁移转化及对污水生物处理的影响

环丙沙星(Ciprofloxacin,CIP)是一种被广泛用于人类医学和动物疾病预防的抗生素类药物,在自然环境中普遍存在,以前的研究主要集中在采用不同方式对环境介质中的CIP进行吸附降解及CIP的药物作用上,有关其在污水处理过程中的迁移转化及对污水生物处理的影响尚不得而知.基于此,本文通过CIP在活性污泥处理污水中的迁移转化实验,解析其对污水生物处理过程的影响.实验结果表明:CIP的去除途径主要为生物吸附,且对低浓度CIP(0.003、0.03和0.3 mg·L~(-1))有较好的吸附效果,但高浓度CIP(3和6 mg·L~(-1))很难被去除;CIP短期/长期暴露对污泥活性及污泥生物细胞完整性无显著影响,但长期暴露会显著提高活性污泥沉降性能,同时会降低生物脱氮除磷的效率.CIP(0.05、0.5、5 mg·L~(-1))的存在使磷的去除率从97.1%±1.2%分别下降到95.8%±0.9%、89.1%±0.6%和74.3%±0.7%,出水中氨氮的去除率从96.1%±1.1%分别下降到94.6%±0.8%、87.9%±0.4%和70.2%±0.6%.机理实验表明,CIP通过抑制好氧阶段和缺氧阶段胞内聚合物聚羟基脂肪酸酯和糖原的转化来抑制磷的吸收和反硝化过程,这是CIP影响生物脱氮除磷的重要原因.此外,亚硝酸盐还原酶和多磷酸激酶的活性也受到CIP的抑制.