酸性紫色水稻土颗粒有机质对镉的吸附特性

采集典型的酸性紫色水稻土（APPS）,从中分离出颗粒有机质（POM）,通过批量试验研究POM及其来源土壤Cd²⁺的吸附动力学、等温吸附和热力学特征,通过扫描电镜-能谱仪、傅里叶红外光谱仪等手段及吸附前后镉的形态变化的测定,研究了POM对Cd²⁺的吸附机制.结果表明：POM对Cd²⁺的亲和力远高于其来源土壤.POM及土壤对Cd²⁺的吸附动力学最优模型均为准二级动力学.Langmuir、Freundlich方程均能较好地描述其等温吸附特征,其中对POM,以Freundlich方程更优,表明POM对Cd²⁺的吸附属于多分子层的非均质吸附.吸附热力学参数△G^θ均小于0、△H^θ和△S^θ均大于0,表明吸附属于自发吸热过程.根据△H^θ值及解吸试验判定POM对Cd²⁺的吸附以化学吸附为主,土壤对Cd²⁺的吸附过程以物理吸附为主.吸附平衡后,土壤中可交换态镉比例提高,而POM中交换态和络合态镉比例增加.综上及吸附前后POM的表征结果说明,POM对Cd²⁺的吸附机制包括含氧官能团的络合、离子交换、阳离子-π键、沉淀作用和静电吸附.     

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.     

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.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

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.      

Reviews of emission of biogenic volatile organic compounds (BVOCs) in Asia

Biogenic volatile organic compounds (BVOCs) in the atmosphere play important roles in the formation of ground-level ozone and secondary organic aerosol (SOA) in global scale and also in regional scale under some condition due to their large amount and relatively higher reactivity. In places with high plant cover in the tropics and in China where air pollution is serious, the effect of BVOCs on ozone and secondary organic aerosols is strong. The present research aims to provide a comprehensive review about the emission rate, emission inventory, research methods, the influencing factors of BVOCs emissions, as well as their impacts on atmospheric environment quality and human health in recent years in Asia based on the summary and analysis of literatures. It is suggested to use field direct measurement method to obtain the emission rate and model method to calculate the emission amount. Several recommendations are given for future investigation and policy development on BVOCs emission.     

餐厨垃圾生物有机肥对贫瘠黄褐土改良的研究

为了阐明餐厨垃圾生物有机肥改良贫瘠土壤的作用机制,以贫瘠黄褐土为研究对象,通过不施肥、长期（>5 a）施用化肥、中长期（5 a）施用少量餐厨垃圾生物有机肥和短期（1 a）施用大量餐厨垃圾生物有机肥4种施肥方式,分别记为CK组、CF组、LOF-5组和MOF-1组,对比分析不同施肥方式对土壤OM（有机质）、活性有机碳、营养元素和团聚体等的影响.结果表明:①施用餐厨垃圾生物有机肥可显著提高土壤OM、活性有机碳含量,其中,MOF-1组提高效果最显著,与CK组相比,w（OM）可提高173.29%,w（ROC）（ROC为易氧化有机碳）增加了39.17%,w（POC）（POC为颗粒有机碳）和w（DOC）（DOC为可溶性有机碳）分别是CK组的13.85和10.32倍.②中长期（5 a）施用少量餐厨垃圾生物有机肥可增加土壤中较大粒径团聚体的占比,且更有利于提高土壤团粒结构的稳定性,LOF-5组>2 mm粒级的团聚体占比是CK组的4.68倍;与CK组相比,LOF-5组MWD（平均重量直径）增加了100.00%,GMD（几何平均直径）增加了82.98%,>0.25 mm水稳定性团聚体质量占比（DR_0.25）增加了27.20%.③中长期（5 a）施用少量餐厨垃圾生物有机肥可增加土壤中w（TN）（TN为全氮）和w（AN）（AN为速效氮）,与CK组相比,LOF-5组w（TN）和w（AN）分别增加了77.42%和20.82%.施用餐厨垃圾有机肥也可同时增加土壤中w（AP）（AP为速效磷）和w（AK）（AK为速效钾）,MOF-1组增加效果较佳,w（AP）和w（AK）分别是CK组的9.43和3.39倍.研究显示,中长期（5 a）施用少量餐厨垃圾生物有机肥可提升土壤固碳能力,提高土壤养分利用的有效性,从而提升耕地土壤质量,减少化肥施用量,是我国贫瘠黄褐土改良的有效施肥模式.      

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.