城市大气中挥发性有机化合物监测技术进展

挥发性有机物(VOCs)是臭氧及二次有机颗粒物(SOA)的主要前体物。近年来,我国逐步将VOCs纳入大气污染物控制体系。准确可靠的监测技术是大气VOCs研究及控制的重要前提保障。按照采样方法、分析方法 2个方面介绍并讨论了城市大气中VOCs的现有监测方法,较为详细地介绍了几类广泛采用的离线及在线监测技术,简要讨论了目前VOCs监测中存在的一些问题,展望了今后的发展趋势。     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

郑州市春季大气污染过程VOCs特征、臭氧生成潜势及源解析

利用GC5000在线气相色谱仪于2018年4月15日～5月15日对郑州市城区环境大气挥发性有机物(VOCs)进行监测,开展其污染特征、臭氧生成潜势(OFP)和来源解析研究.结果表明,监测期间,郑州市春季VOCs平均体积分数为40.26×10~(-9),非污染日和污染日VOCs平均体积分数分别为35.82×10~(-9)和44.12×10~(-9),污染日相较非污染日增长23%;VOCs物种对OFP的贡献表现为烯烃芳香烃烷烃炔烃;源解析结果显示监测期间郑州市VOCs主要来源是LPG源(66.05%)、机动车源(47.39%)、工业溶剂源(37.51%)、燃烧源(37.80%)和植物排放源(11.25%),且污染日的LPG源和植物排放源的贡献率较非污染日增长22.92%和68.50%.     

中国集成电路制造行业VOCs排放特征及控制对策

中国电子信息产业发展迅速,集成电路等电子器件产量不断增加.在集成电路制造的过程中,大量有机溶剂的使用导致VOCs的产生和排放,从而对大气环境造成影响.为掌握集成电路制造行业VOCs的排放特征,系统分析了其工艺流程和产排污环节,分析了行业废气收集和治理现状,通过对典型企业VOCs的排放监测,获得VOCs排放水平;采用排放因子法核算行业VOCs历史排放量,并基于行业排放特征及减排潜力分析,提出了相应的污染防治对策.结果表明：在集成电路制造中,VOCs排放环节主要集中在光刻、清洗、去胶等过程,1 m²集成电路产量约使用87 g有机溶剂,VOCs产生量较大;通过采取高效的VOCs治理技术,集成电路制造行业有组织排放水平较低,平均浓度为2.1 mg·m^-3,但厂界无组织排放浓度相对较高,平均浓度为0.78 mg·m^-3,接近国家标准的排放限值.根据排放量核算结果,2011—2016年中国集成电路制造行业VOCs排放量呈逐年上升的趋势,主要受产量增加而相应污染控制技术水平提升有限的影响,无组织排放量比重大,占排放总量的38.1%~45.1%.     

基于稳定氢同位素的太原市大气单环芳烃来源

采集太原市城北和城南区域环境空气和5类污染源挥发性有机物样品,测定样品中典型单环芳烃稳定氢同位素（δD）组成,基于同位素质量平衡原理计算单环芳烃从源到环境空气受体的δD初始混合值,探讨单环芳烃来源.结果表明,柴油挥发源、溶剂挥发源、汽油挥发源（97^#）、汽油挥发源（95^#）、机动车尾气（97^#）、机动车尾气（95^#）和民用燃煤源中单环芳烃δD范围依次为：（-138.7‰~-115.5‰）、（-147.0‰~-121.0‰）、（-150.8‰~-117.6‰）、（-131.8‰~-113.8‰）、（-171.2‰~-120.0‰）、（-138.9‰~-102.7‰）和（-168.3‰~-142.3‰）,民用燃煤源中单环芳烃δD显著贫重氢同位素（D）组成,机动车尾气源与汽油挥发源中苯的δD相比显著贫D,可用于探索污染物转化过程;城北和城南环境空气中δD范围为（-131.7‰~-115.1‰）和（-131.9‰~-74.9‰）,δD初始混合值为-138.4‰和-173.9‰,体现了其来源差异.     

金属表面涂装行业VOCs排放特征及排放系数

对比了浙江省2014和2018年金属表面涂装企业的有机废气排放及治理情况,分析了该行业涂料及稀释剂的使用、主要污染因子,测算了溶剂型、水性涂料的挥发性有机物（VOCs）产生系数和排放系数.结果表明：2018年VOCs治理水平明显高于2014年,水性涂料使用企业比例由18%上升至36%,纯溶剂型企业由82%下降至64%;金属表面涂装行业的主要排放污染物为二甲苯、丁醇、乙酸乙酯、乙酸丁酯、甲苯、丙二醇、乙苯、苯乙烯等8种有机物.溶剂型和水性涂料的VOCs产生系数分别为0.72和0.31kg/kg;溶剂型和水性涂料2014年VOCs排放系数为0.64和0.29kg/kg,2018年为0.48和0.21kg/kg.     

离子液体吸收废印刷线路板热拆解过程中挥发性有机物——基于COSMO-RS模型

模拟废印刷线路板（WPCB）的热拆解过程,分析热拆解过程中的挥发性有机物（VOCs）组分;利用真实溶剂似导体屏蔽（COSMO-RS）模型对浓度较高的污染物进行量子力学模拟,研究离子液体（ILs）组成单元对目标污染物溶解度的影响差异,分析溶解过程中主导分子间作用力类型,确定优选吸收剂;测定不同溶剂进行溶解性,验证模型适用性.结果表明：①乙酸乙酯和环戊酮是浓度较高的VOCs组分,在240和250℃时浓度分别为43.1,153mg/m³和105,252mg/m³,质量百分比总和分别为76.3%和67.3%.②高表面屏蔽电荷密度分布峰、长烷基链阴阳离子和亲电基团的存在可提高乙酸乙酯和环戊酮在ILs中的溶解度.双三氟甲磺酰基亚胺盐（NTf₂^-）类ILs是一类优良吸收剂.静电力和范德华力对溶解过程起主导作用.③COSMO-RS模型可定性和半定量用于预测乙酸乙酯和环戊酮的溶解度.     

Preparation of hydrophobic hierarchical pore carbon–silica composite and its adsorption performance toward volatile organic compounds

Carbon–silica materials with hierarchical pores consisting of micropores and mesopores were prepared by introducing nanocarbon microspheres derived from biomass sugar into silica gel channels in a hydrothermal environment.The physicochemical properties of the materials were characterized by nitrogen physical adsorption(BET),scanning electron microscopy(SEM),and thermogravimetric(TG),and the adsorption properties of various organic waste gases were investigated.The results showed that microporous carbon materials were introduced successfully into the silica gel channels,thus showing the high adsorption capacity of activated carbon in high humidity organic waste gas,and the high stability and mechanical strength of the silica gel.The dynamic adsorption behavior confirmed that the carbon–silica material had excellent adsorption capacity for different volatile organic compounds(VOCs).Furthermore,the carbon–silica material exhibited excellent desorption characteristics:adsorbed toluene was completely desorbed at 150℃,thereby showing superior regeneration characteristics.Both features were attributed to the formation of hierarchical pores.     

Removal and desorption of chromium in synthetic effluent by a mixed culture in a bioreactor with a magnetic field

Two chromium removal experiments were performed in bioreactors with and without a magnetic field under the same conditions.The release of the chromium present in the biomass was tested in two experiments one with the initial pH of the medium and one with pH 4.0.The objective was to remove Cr(Ⅵ) and total Cr from the effluent,this was carried out by placing biological treatments of synthetic effluent contaminated with 100 mg/L of Cr(Ⅵ) in a bioreactor with neodymium magnets that applied a magnetic field(intensity85.4 mT) to the mixed culture.The removal of Cr(Ⅵ) was approximately 100.0% for the bioreactor with a magnetic field and 93,3% for the bioreactor without a magnetic field for9 hr of recirculation of the synthetic effluent by the bioreactor.The removal of total Cr was61.6% and 48.4%,with and without a magnetic field,respectively;for 24 hr.The desorption of Cr(VI) in the synthetic effluent was 0.05 mg/L,which is below the limit established by Brazilian legislation(0.1 mg/L) for the discharge of effluent containing Cr(Ⅵ) into bodies of water.The results obtained for the removal of chromium in synthetic effluent suggested that there was no significant influence on the viable cell count of the mixed culture.The desorption of Cr(Ⅵ) in synthetic effluent after bioadsorption of chromium by the mixed culture in the process of removal of chromium in bioreactors with and without a magnetic field was not significant in either of the experiments with different initial pHs.     

杭州湾北岸36种挥发性有机物污染特征及来源解析

为研究杭州湾北岸VOCs（挥发性有机物）的浓度水平、组成特征、反应活性和潜在来源,采用GC-FID在线监测系统对杭州湾北岸环境大气中的36种VOCs开展了为期1 a（2017年12月-2018年11月）的连续观测,采用LOH（VOCs的·OH消耗速率）和OFP（O₃生成潜势）2种方法估算了大气VOCs的反应活性,并利用PMF（正定矩阵因子分解）和CPF（条件概率函数）模型分析其来源.结果表明:①φ（VOCs）小时平均值在冬季（26.47×10-9）最高,夏季（9.76×10-9）最低;全年φ（VOCs）小时平均值为21.24×10-9,其中烷烃、烯烃+炔烃、芳香烃、卤代烃的贡献率分别为33.24%、34.13%、15.63%、17.00%;φ（烷烃）、φ（芳香烃）和φ（卤代烃）呈较明显的昼夜变化特征,φ（烯烃）和φ（炔烃）无明显昼夜变化趋势.②大气VOCs的总LOH和OFP分别为9.39 s-1和220.57 μg/m3,KOH（·OH反应速率常数）和MIR（最大增量反应活性）系数的平均值分别为17.34×10-12 cm3/（molecule·s）和3.31;KOH和MIR系数的平均值分别与间/对-二甲苯的KOH和乙苯的MIR系数接近,表明大气VOCs的化学反应活性较强;VOCs关键活性物种为异戊二烯、乙烯、丙烯、甲苯、二甲苯和顺-2-丁烯.③特征物种相关性分析表明,杭州湾北岸大气存在老化现象,异戊烷和正戊烷受煤燃烧源影响较大,二甲苯和乙苯受溶剂排放源影响较大,甲苯和苯除受机动车尾气影响外,还受其他排放源影响.④PMF和CPF模型来源分析表明,大气VOCs主要来自石化工业源、燃料挥发源、生物质燃烧和煤燃烧源、机动车排放源和溶剂使用源,其中,机动车排放源主要来自西北方向,其他源主要来自西北、西和西南方向.研究显示,杭州湾北岸大气VOCs来源复杂,受周边工业区的影响较大.