Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

Algal toxicity induced by effluents from textile-dyeing wastewater treatment plants

This research aimed to evaluate the alga Scenedesmus obliquus toxicity induced by textiledyeing effluents(TDE).The toxicity indicator of TDE in alga at the physiological(algal growyth),biochemical(chlorophyll-a(Chl-a) synthesis and superoxide dismutase(SOD) activity) and structural(cell membrane integrity) level were investigated.Then we further study the relationship among toxicity indicators at physiological and biochemical level,and supplemented by research on algal biomacromolecules.According to the analysis of various endpoints of the alga,the general sensitivity sequence of toxicity endpoints of Scenedesmus obliquus was:SOD activity Chl-a synthesis algal growth.The stimulation rate of SOD activity increased from day 3(57.25%～83.02%) to day 6(57.25%～103.81%),and then decreased on day 15(-4.23%～-32.96%),which indicated that the antioxidant balance system of the algal cells was destroyed.The rate of Chl-a synthesis inhibition increased gradually,reaching19.70%～79.39% on day 15,while the rate of growth inhibition increased from day 3(-12.90%～10.16%) to day 15(-21.27%～72.46%).Moreover,the algal growth inhibition rate was positively correlated with the inhibition rate of SOD activity or Chl-a synthesis,with the correlation coefficients were 0.6713 and 0.5217,respectively.Algal cells would be stimulating to produce excessive reactive oxygen species,which would cause peroxidation in the cells,thereby destroying chloroplasts,inhibiting chlorophyll synthesis and reducing photosynthesis.With increasing exposure time,irreversible damage to algae can lead to death.This study is expected to enhance our understanding of the ecological risks through algal tests caused by TDE.     

Effect of struvite and organic acids on immobilization of copper and zinc in contaminated bio-retention filter media

Few studies have been carried out to connect nutrient recovery as struvite from wastewater and sustainable utilization of the recovered struvite for copper and zinc immobilization in contaminated soil. This study revealed the effect of struvite on Cu and Zn immobilization in contaminated bio-retention soil in the presence of commonly exuded plant organic acids. The research hypothesis was that the presence of both struvite and organic acids may influence the immobilization of Cu and Zn in soil. The outcome of this research confirmed that more than 99% of Cu and Zn was immobilized in bio-retention filter media by struvite application. Water-soluble Cu and Zn concentrations of struvite treated soil were less than 1.83 and 0.86 mg/kg respectively, and these concentrations were significantly lower compared to the total Cu and Zn content of 747.05 mg/kg in the contaminated soil. Application of struvite to Cu- and Zn-contaminated soil resulted in formation of compounds similar to zinc phosphate tetrahydrate (Zn₃(PO₄)₂?4H₂O) and amorphous Cu and Zn phases. Struvite was effective in heavy metal remediation in acidic soil regardless of the presence of Ca impurities in struvite and the presence of plant organic acids in soil. Overall, this study revealed that struvite recovered from wastewater treatment plants has potential for use as an amendment for heavy metal remediation in contaminated bio-retention soil.     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.     

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.      

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

某垃圾焚烧厂投产前后周边土壤二英类化合物的分布

为研究垃圾焚烧厂运行对周边土壤二英类化合物（PCDD/Fs）含量的影响,采集了珠三角地区某垃圾焚烧厂投产前和投产后周边土壤样品,分析研究了该垃圾焚烧厂运行对周边土壤中PCDD/Fs含量和组分的变化.结果表明:①2012年（投产前）珠三角地区某垃圾焚烧厂周边土壤PCDD/Fs含量较低,范围为163~591 ng/kg（毒性当量范围为0.198~0.863 ng I-TEQ/kg,I-TEQ为国际毒性当量因子折算的毒性当量值）;2017—2019年（投产后）周边土壤PCDD/Fs含量范围为151~1.75×103 ng/kg（毒性当量范围为0.812~3.88 ng I-TEQ/kg）,与其他研究相比处于较低的水平.②投产后,距该垃圾焚烧厂较近（1.5 km）的采样点（S1）土壤PCDD/Fs含量逐年增长,在较远（5.2 km）但人口较密集的采样点（S3）土壤PCDD/Fs含量整体较高,但呈逐年下降趋势.③投产后,土壤中的17种PCDD/Fs单体组分中,毒性当量贡献率最高的单体为八氯二苯并二英（OCDD）和2,3,4,7,8-五氯二苯并呋喃（2,3,4,7,8-PeCDF）,二者毒性当量贡献率范围为15.7%~45.4%.④在同一采样点土壤PCDD/Fs单体组分年间差异不明显,但同一年份不同采样点差异明显.研究显示,目前该垃圾焚烧厂周边土壤PCDD/Fs含量较低,但仍需要长期监测其可能带来的风险.      

达里诺尔湖水体DOM荧光特征及其来源解析

达里诺尔湖（简称“达里湖”）是内蒙古自治区高原地区重要的生态屏障,探究达里湖水质状况及污染来源,对加强流域水环境治理、改善水环境质量具有十分重要的意义.于2018年9月及2019年6月对湖水进行采样,并通过三维荧光光谱结合PARAFAC（平行因子分析）模型,探究达里湖水体DOM（溶解性有机质）来源及其与水质的关系.结果表明:①达里湖水体中pH较高,ρ（DOC）（DOC为溶解性有机碳）、ρ（NH₄+-N）、ρ（TP）相对较高,均超过GB 3838—2002《地表水环境质量标准》Ⅴ类水质标准限值.②水体中DOM含4种荧光组分.夏季水体DOM主要分布于河流入湖口附近,其中,类腐殖质荧光组分（紫外区类富里酸和可见区类富里酸）占总组分的62.93%,类蛋白类荧光组分（类色氨酸和类酪氨酸）占总组分的36.07%;秋季水体DOM主要分布于东南侧,其中,类腐殖质荧光组分占总组分的40.52%,类蛋白类荧光组分占总组分的59.48%.③达里湖采样点荧光参数表明,达里湖DOM自生源特征较强,腐殖化程度较低.类腐殖质荧光组分与ρ（DOC）、ρ（Chla）均呈正相关,类色氨酸荧光组分与pH呈正相关,类络氨酸与ρ（DTN）、ρ（NH4+-N）、ρ（DTP）均呈正相关.研究显示,达里湖DOM具有陆源与生物源双重特性,DOM的形成与微生物、细菌、浮游生物的生命活动密切相关.      

加入SOA示踪的深圳大气PM2.5受体模型源解析

为厘清包括二次有机气溶胶（SOA）在内的深圳市区PM_2.5各种一次和二次来源贡献,本文于2017年9月2日~2018年8月29日在深圳市大学城点位开展PM_2.5样品采集,并进行化学组分和水溶性有机物（WSOM）质谱测量,共获得162组有效数据.观测期间深圳市大气PM_2.5平均质量浓度为26μg/m³,在传统PMF源解析的基础上加入羧基离子碎片（CO₂⁺）作为SOA的示踪物,加入水溶性有机氧（WSOO）用于计算各因子O/C,验证有机物解析效果.结果表明,SOA可以被独立解析出,其O/C明显高于其他一次污染源中有机物;机动车、二次硫酸盐、二次硝酸盐、SOA为最主要的4个源,对PM_2.5质量浓度的贡献分别为25%、23%、17%和10%,船舶、地面扬尘、老化海盐、建筑尘、生物质燃烧、燃煤和工业贡献均在5%以内.各个源的变化特征表明,机动车、二次硫酸盐、二次硝酸盐、SOA等源贡献呈现冬高夏低的季节特征,与冬季季风条件下源自内陆的污染传输密切相关.污染天气时,二次硝酸盐和SOA的贡献增加相对最显著,因此NOx和挥发性有机物是减排的关键.     

珠江口夏季海陆源有机碳的模拟研究——分布特征、贡献比重及其迁移转化过程

基于经过验证的三维水动力-水质模型,对珠江口夏季有机碳进行海陆源区分,并对海陆源有机碳的分布特征、贡献比重及其通量过程进行研究.结果表明,水平方向上,珠江口夏季陆源（海源）有机碳浓度从口门到外海逐渐降低（升高）,在表、底层海水中平均浓度分别为1.45和0.87mg/L（0.97和1.05mg/L）;垂直方向上,在层化水域陆源（海源）有机碳浓度从上到下逐渐递减（升高）,在非层化水域海陆源有机碳浓度垂向分布较为均匀.珠江口夏季海源有机碳贡献率表层海水低于底层海水,平均贡献率为48.26%,沿向海方向海源有机碳贡献率逐渐增加--从内伶仃洋水域的4.43%逐渐提升到外伶仃洋东侧水域的81.20%.珠江口水动力条件复杂,在径流、潮汐、季风等因素的作用下陆源有机碳向海输送且向海输送量逐渐递减;海源有机碳在不同水域动力输送特征不同,西南水域向海输送,向海输送量逐渐递增;东北水域向岸输送,向岸输送量逐渐递减.陆源有机碳生化反应活性较弱,只有小部分被生化过程消耗,其迁移转化主要由沉降过程控制,而海源有机碳的迁移转化,则由口门的动力输送过程主控向外海的生化耗碳过程主控过渡.此外,海源有机碳沉降作用明显低于陆源有机碳,生化作用明显高于陆源有机碳.