超声催化二氧化钛深度处理染料废水

超声技术作为一种新型的氧化方法,能提高难降解有机物的降解率和增强水处理中的生物活性,在废水处理中已经发挥了一定的作用.光催化氧化降解水体中有机污染物也是近年来兴起的一项新型水处理技术,能有效地降解废水中的难降解有机物,但因其对光源要求较高等因素限制了它的使用.介绍了用超声代替紫外光源降解印染业污水的方法,探讨了降解机理,综述了其在废水处理中的研究进展,并指出今后须解决的问题和发展方向.     

秋季黄渤海C2~C5非甲烷烃海-气通量与大气反应活性

分别运用吹扫捕集和三级低温预浓缩系统与气-质联用的方法,测定了2014年11月黄渤海表层海水和大气中主要的C₂~C₅非甲烷烃（NMHCs）的浓度,研究其分布特征及海-气通量,并评价了它们的大气化学反应活性.海水中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯、异丁烯和异戊二烯的浓度平均值分别为53.0,49.4,26.4,29.2,186,62.7,35.6,89.9,42.4pmol/L.大气中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯、异丁烯和异戊二烯的体积分数平均值分别为0.043,21,0.36,6.7,7.5,0.71,0.12,0.16,0.085×10^-9.大气中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯和异丁烯具有较好的相关性,均与异戊二烯没有相关性.海-气通量的计算结果表明,近岸陆架海域可能是大气中C₂~C₅NMHCs重要的源.通过计算C₂~C₅NMHCs的臭氧生成潜势和OH·消耗速率,表明乙烯、丙烯、丙烷和正丁烷是黄渤海大气C₂~C₅NMHCs的关键活性组分.     

SO2-NO2-NH3-H2O四元反应体系中气溶胶的生成特性

通过烟雾箱实验,研究了SO₂-NO₂-NH₃-H₂O四元反应体系在气-粒转化过程中新形成颗粒物数浓度与粒径分布的变化.研究发现,SO₂-NO₂-NH₃-H₂O四元反应体系具有显著的成核能力,且其成核强度大,持续时间短.当SO₂、NO₂浓度为200mg/m³,NH₃浓度为12x10^-6时,反应体系的气溶胶总个数浓度在2min时达到峰值2.5x10⁶cm^-3.缺少任一种气体均会使气溶胶成核强度下降.SO₂、NO₂及NH₃浓度分别为0的工况下气溶胶总个数浓度峰值分别下降了41.0%、83.6%及98.5%.在电厂污染气体排放浓度区间内,NO₂对气溶胶生成影响大于SO₂.燃煤电厂控制NO_x排放浓度对改善烟囱出口气溶胶数浓度更有效.在实验基础上,对颗粒物成核特性进行拟合,反应体系在气-粒转化过程中产生的新颗粒物总个数浓度及中值粒径与气态前体物浓度线性相关;采用布朗团聚模型对气溶胶成核后的团聚过程总个数浓度及粒径变化进行模拟计算,根据给定的燃煤电厂SO₂、NO₂、NH₃排放浓度,给出预测气溶胶颗粒成核速率、粒径分布及总个数浓度变化的方法.     

·OH自由基介导2,4-二氯酚光降解机理及产物毒性变化特征的理论研究

由于2,4-二氯酚(2,4-dichlorophenol,简称2,4-DCP)具有"三致"作用及潜在的生态风险,其光化学降解机理及产物的生态毒理效应目前成为人们关注的焦点。本研究采用理论化学计算手段,系统阐明了2,4-DCP在水环境中·OH介导的间接光化学转化机理、动力学和转化产物的生态毒性变化特征。结果表明2,4-DCP很容易被·OH氧化降解,其降解主要通过·OH-加成和H-迁移路径进行。在低温条件下·OH-加成路径将占主导,主要形成4,6-二氯苯-1,3-二酚;而当温度超过313 K时,·OH提取酚羟基上的氢原子为主要降解途径,主要形成2-氯苯-对苯醌。尤其在活性物种浓度较低的高温环境中,H-迁移路径有可能生成二噁英。计算毒理学结果表明:H-迁移产物的水生毒性超过·OH-加成产物,甚至超出母体2,4-DCP一个毒性等级。因此,我们建议在以后的环境监测以及风险评估过程中,关注2,4-DCP及其转化产物特别是H-迁移路径的转化产物的生态毒理学问题。     

Nitro polycyclic aromatic hydrocarbons in atmospheric particulate matter of Athens,Greece

Polycyclic aromatic hydrocarbons (PAHs) and nitro polycyclic aromatic hydrocarbons (N-PAHs) are chemical species of proven mutant and carcinogenic activity. In this study, the concentrations of seven different N-PAHs [2-nitronaphthalene (2N-NAP), 2-nitroflourene (2N-FLU), 2-nitroflouranthene (2N-FLA), 3-nitroflouranthene (3N-FLA), 1-nitropyrene (1N-PYR) and 2-nitropyrene (2N-PYR)] were determined in two fractions of atmospheric particulate matter from the atmosphere of Athens: coarse (2.4 μm?10 μm ) and fine (<2.4 μm ). 3N-FLA was not detected, whereas 1N-PYR, mostly originating from emissions from burning fuel, showed the maximum observed concentrations for both fractions and for the whole experimental period (especially during winter). In addition, 2N-FLA, a secondary nitro-PAH produced by photochemical reactions, showed relatively high values. Analysis of statistical data for N-PAH concentrations, using clustering technique, showed that: (1) 1N-NAP, 2N-FLU and 1N-PYR are mainly produced by direct burning; and (2) photochemical reactions are the dominant sources of 2N-NAP, 2N-PYR and 2N-FLA.     

Behavior of aqueous stable colloidal nano-C60 aggregates exposed to TX100 micelles under different environmental conditions

C₆₀, as one of carbon nanomaterials widely used in various fields, could be released into the water environment thus exerting some potential health risks to human beings. This work examined the behavior of aqueous stable colloidal nano-C₆₀ (nC₆₀) aggregates under different environmental conditions including Polyethylene glycol octylphenol ether (TX100) micelles concentration, pH, and reaction time when exposed to TX100 micelles. Results show that the nC₆₀ aggregates became more dispersive and restored the capability of generating the singlet oxygen when exposed to TX100 micelles. With the increase of TX100 concentration, smaller average size of nC₆₀ aggregates was observed in dynamic light scattering (DLS) analysis, the fluorescence intensity of TX100 was more quenched by nC₆₀ aggregates, and the kinetic rate constant of generating the singlet oxygen for nC₆₀ aggregates was improved. The mean size of nC₆₀ aggregates in the presence of TX100 had no obvious variations when the pH ranged from 4 to 8. The longer reaction time between nC₆₀ aggregates and TX100 led to a higher kinetic rate constant of generating the singlet oxygen. Collective data suggest that variations in physicochemical properties of nC₆₀ aggregates are strongly dependent on the surrounding media under different environmental conditions and directly govern nC₆₀’s transport behavior and potential toxicity.     

成都郊区(新津)夏季甲醛污染特征分析

甲醛（HCHO）是大气光化学重要污染物之一,为研究西南地区郊区大气夏季甲醛污染特征选取了四川省成都市新津区进行大气甲醛观测,结合NO_x、O₃、PAN、J-value、温湿度、风速风向、天气数据进行分析.观测期间成都市新津区夏季甲醛浓度为0.76×10^-9~12.50×10^-9（V/V）,均值为3.47×10^-9±2.05×10^-9（V/V）,呈现明显的日变化规律.结合数据分析可知,一次人为排放源在成都郊区夏季日间甲醛贡献中占比较低.观测期间甲醛受光照的影响较大,与O₃、PAN、J-value普遍呈现一致的变化规律,因此成都市夏季日间甲醛主要来源为甲醛前体物的二次光化学反应.     

西南典型区域夏季大气含氧挥发性有机化合物来源解析

含氧挥发性有机物（OVOCs）是大气光化学过程中的重要中间产物,是臭氧的重要来源之一.利用质子转移反应飞行时间质谱仪（PTR-TOF-MS）在成都平原对OVOCs进行观测,探讨其日变化特征、光化学反应活性、臭氧生成潜势和来源.结果表明,10个VOCs［乙醛、丙酮、异戊二烯、甲基乙基酮（methyl ethyl ketone,MEK）、甲基乙烯基甲酮（methyl vinyl ketone,MVK）、甲基丙烯醛（methacrolein,MACR）、苯、甲苯、苯乙烯、C8芳香烃和C9芳香烃］总浓度（体积分数）为（10.97±4.69）×10^-9,OVOCs为（8.54±3.44）×10^-9,芳香烃为（1.53±0.93）×10^-9,生物源VOCs为（0.90±0.32）×10^-9;光化学活性和臭氧生成潜势均排名前三的物种为：异戊二烯、乙醛和C8芳香烃;3个OVOCs物种（乙醛、丙酮和MEK）主要来源于本地生物源和人为二次源,且丙酮有较强的区域背景值,说明该地区的污染受到较为显著的区域传输的影响.本研究可加深对西南地区臭氧的区域形成机制的认识,为科学管控臭氧污染提供依据.     

Eperimental study of photooxidation products of ethylbenzene

Smog chamber experiments were performed to investigate the composition of products formed from photooxidation of aromatic hydrocarbon ethylbenzene.Vacuum ultraviolet photoionization mass spectrometer and aerosol time-of-flight mass spectrometer were used to measure the products in the gas and particle phases in real-time.Experimental results demonstrated that ethylphenol,methylglyoxal,phenol,benzaldehyde,and 2-ethylfurane were the predominant photooxidation products in both the gas and particle phases.However,there were some differences between detected gas phase products and those of particle phase,for example,2-ethylfurane,ethylglyoxylie acid,nitroethylbenzene,3,4-dioxopentanal and ethyl-nitrophenol were only existing in the particle-phase.The possible reaction mechanisms leading to these products were also discussed and proposed.     

基于碳同位素组成的大气NMHCs光化学寿命研究

利用热解析-气相色谱-同位素质谱联用仪测定了兰州市冬季和夏季昼夜大气非甲烷烃(NMHCs)的稳定碳同位素组成.结果表明,兰州市冬季大气NMHCs的δ13C值为-30.5‰～-24.3‰,夏季为-31.9‰～-24.2%,受燃煤烟气排放的影响,冬季大气NMHCs的δ13C值明显大于夏季;冬季大气NMHCs的δ13C值夜晚大于白天,夏季不同时间点C4、C5化合物的同位素值相差不大,正己烷和正庚烷的δ13C值白天比夜晚要高.利用"碳氢化合物同位素时钟"计算出正己烷和1-丁烯在兰州市夏季大气中的平均光化学寿命分别约为6d和25min.