铝系混凝剂优势形态分析及其混凝特性

聚合氯化铝（PACl）是常用的水处理混凝剂,在应用过程中通常表现出比传统铝盐更为优异的效果.研究表明,这种优异性能主要得益于其特殊的组成,特别是高分子聚合物Al₁₃和Al₃₀独特的物化特性.Al₁₃和Al₃₀是铝离子水解过程中的中间产物,在地球科学和环境化学等领域有着重要的研究价值.于水处理而言,二者的结构和分子特性是研究者关注的重点,大量研究基于此展开,很多重要的发现为实际应用奠定了基础.基于对PACl及其组成性质的研究,本文对PACl的混凝特性及其优势形态分子的分析进行了综合阐述.     

科技创新投入对环境全要素生产率的影响机制

使用2004~2015年的中国280个地级市的面板数据,对科技创新投入与环境全要素生产率间的非线性关系、内部影响机理和空间异质性进行分析,结果显示：科技创新投入与环境全要素生产率之间呈现倒N型关系,两个拐点的位置分别为7.722（2257.47万元）和9.610（14913.17万元）;在外部资本进入、污染治理、市场规模效应3种影响路径中,科技创新投入影响下的外部资本进入对环境全要素生产率依然存在污染避难所的负向效应,科技创新投入与外部资本间效应为0.1363,外部资本与环境全要素生产率间效应为-0.0065;科技创新投入能够增强企业的污染治理技术并提高环境全要素生产率,三者间前后效应分别为-0.0277和-0.0311;科技创新的投入与高效益增强了市场规模效应,有效促进生产结构的转型进而提高环境全要素生产率,三者间前后效应为0.0186和0.4346.空间异质性中,外部资本进入与溢出效应带来的污染避难所负效应在中部地区显著,在西部和东北部地区不显著,而污染天堂正效应在东部地区存在但不显著;污染创新治理投入的技术正溢出效应在东部和西部地区效应显著,在中部和东北部不显著;科技创新投入与市场需求规模效应在空间区域无差异且显著为正.建议依据科技创新投入的不同影响路径来实施空间差异化策略.     

Role of glycine on sulfuric acid-ammonia clusters formation: Transporter or participator

Glycine(Gly) is ubiquitous in the atmosphere and plays a vital role in new particle formation(NPF).However,the potential mechanism of its on sulfuric acid(SA)-ammonia(A)clusters formation under various atmospheric conditions is still ambiguous.Herein,a(Gly)_x·(SA)_y·(A)_z(z≤x+y≤3) multicomponent system was investigated by using density functional theory(DFT) combined with Atmospheric Cluster Dynamics Code(ACDC) at different temperatures and precursor concentrations.The results show that Gly,with one carboxyl(-COOH) and one amine(-NH_2) group,can interact strongly with SA and A in two directions through hydrogen bonds or proton transfer.Within the relevant range of atmospheric concentrations,Gly can enhance the formation rate of SA-A-based clusters,especially at low temperature,low [SA],and median [A].The enhancement(R) of Gly on NPF can be up to 340 at T=218.15 K,[SA]=10~4,[A]=10~9,and [Gly]=10~7 molecules/cm~3.In addition,the main growth paths of clusters show that Gly molecules participate into cluster formation in the initial stage and eventually leave the cluster by evaporation in subsequent cluster growth at low [Gly],it acts as an important "transporter" to connect the smaller and larger cluster.With the increase of [Gly],it acts as a "participator" directly participating in NPF.     

Dynamic nano-Ag colloids cytotoxicity to and accumulation by Escherichia coli: Effects of Fe3+, ionic strength and humic acid

Released Ag ions or/and Ag particles are believed to contribute to the cytotoxicity of Ag nanomaterials, and thus, the cytotoxicity and mechanism of Ag nanomaterials should be dynamic in water due to unfixed Ag particle:Ag⁺ ratios. Our recent research found that the cytotoxicity of PVP-Ag nanoparticles is attributable to Ag particles alone in 3 hr bioassays, and shifts to both Ag particles and released Ag⁺ in 48 hr bioassays. Herein, as a continued study, the cytotoxicity and accumulation of 50 and 100 nm Ag colloids in Escherichia coli were determined dynamically. The cytotoxicity and mechanisms of nano-Ag colloids are dynamic throughout exposure and are derived from both Ag ions and particles. Ag accumulation by E. coli is derived mainly from extracellular Ag particles during the initial 12 hr of exposure, and thereafter mainly from intracellular Ag ions. Fe³⁺ accelerates the oxidative dissolution of nano-Ag colloids, which results in decreasing amounts of Ag particles and particle-related toxicity. Na⁺ stabilizes nano-Ag colloids, thereby decreasing the bioavailability of Ag particles and particle-related toxicity. Humic acid (HA) binds Ag⁺ to form Ag⁺-HA, decreasing ion-related toxicity and binding to the E. coli surface, decreasing particle-related toxicity. HA in complex conditions showed a stronger relative contribution to toxicity and accumulation than Na⁺ or Fe³⁺. The results highlighted the cytotoxicity and mechanism of nano-Ag colloids are dynamic and affected by environmental factors, and therefore exposure duration and water chemistry should be seriously considered in environmental and health risk assessments.     

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

郑州市VOCs组分排放清单及其臭氧生成潜势

基于人为源挥发性有机物（VOCs）活动水平统计和源成分谱梳理,采用排放因子法,建立了郑州市2016年VOCs组分排放清单,评估了各类源臭氧生成潜势（OFP）.结果表明,2016年郑州市人为源VOCs排放总量为96215.3 t,排放量最高的是道路移动源（29.7%）,其次是有机溶剂使用源（28.1%）;排放量最高的组分是烷烃（29.8%）,其次是芳香烃（29.0%）.郑州市人为源VOCs的OFP为341291.0 t,贡献最高的排放源是道路移动源（30.5%）,其次是溶剂使用源（28.8%）,其中轻型汽油车、内墙涂料使用、机动车表面涂层、加油站装卸油和非金属矿物制造是OFP的主要次级排放源,也是郑州市降低臭氧污染时需重点管控的VOCs排放源.对于VOCs种类而言,贡献较高的是芳香烃（42.8%）,其次是烯烃（38.9%）,未来应加强对间/对-二甲苯、丙烯和乙烯等物种排放来源的控制.     

汶川地震重灾区泥石流灾损土地利用及生态修复模式——以北川县都坝河小流域为例

汶川地震诱发了大量泥石流灾害,灾损土地利用和生态修复是灾区产业重建面临的重要课题。以北川县都坝河小流域为研究对象,通过调查灾损土地禀赋、灾害特征、土地需求,采取多因素耦合和关键因子限制分析法,探讨灾害胁迫条件下的经济活动与生态修复之间的互馈作用,结果表明：（1）流域新增土地供给源主要为泥石流灾损土地,土地资源化利用受灾害、聚落和产业结构控制;（2）灾损土地根据成因划分为沟口堆积型、沟道冲淤型以及岸坡侵蚀型,三者的肥力、安全性及交通条件等特征具有显著差异;（3）基于“因灾分区、耕地优先、产业共建、美居造景”的原则,建立了灾损土地的利用方式和生态修复模式,并选取杨家沟进行验证,沟域灾损土地利用方式为生态林地、产业林地及优质耕地,分别占比28.5%、56.3%、15.2%,生态修复措施主要为提高土地安全度、提升植被覆盖率和增强水保功能。该研究建立的震区土地利用和生态修复模式可有力协调人地矛盾、发展绿色经济和提升人居环境。     

水动力对沉积物-水界面氧通量产生机制的影响

选取三峡库区支流御临河为研究对象,测量了5个水动力条件（平均流速为0.00,0.03,0.07,0.12,0.20m/s）下沉积物-水界面（SWI）氧通量的变化及水动力条件对SWI氧通量产生机制的影响.结果表明,随着平均流速的升高,SWI氧通量增加,由0.00m/s时的1.197mmol/（m²·h）增加为0.20m/s时的43.981mmol/（m²·h）,溶解氧穿透深度增加,氧进入沉积物更深处并被微生物和还原性物质所利用,沉积物耗氧量上升;当平均流速较低时,沉积物耗氧量以生物耗氧量为主,在0.00m/s与0.03m/s时生物耗氧量为氧通量的85.3%与57.7%;当水体平均流速较高,化学耗氧量与其他耗氧量中的化学过程耗氧量在氧通量中的比重逐步提高.     

利用HYSPLIT模型研究珠三角地区VOCs时空分布特征

于2016年在中国广东大气超级监测站,开展4个季节的VOCs长时间观测,共获得2142组有效数据,并利用HYSPLIT模型分析珠三角地区VOCs时空分布特征.结果表明,各类VOCs混合比和化学反应活性具有明显的季节变化特点.观测期间,VOCs平均浓度为（18.523±20.978）×10^-9,其中,低碳烯烃和苯系物二者混合比之和仅占46%,但贡献了85%的·OH消耗速率（L_OH）、82%的臭氧生成潜势（OFP）和97%的二次气溶胶生成潜势（SOAFP）.观测站点主要受来自北部内陆地区气团（1#）、西部内陆地区气团（2#）、台湾海峡南端气团（3#）以及南部海洋地区气团（4#）的影响.1#气团中炔烃和苯系物的混合比占比最高,分别达到10%、37%,而3#气团中低碳烷烃的浓度水平最高,达到（8.437±5.561）×10^-9.通过估算气团中VOCs的化学反应活性,可以发现,1#气团的VOCs化学反应活性最强,其对O₃和SOA的生成贡献最高.1#、2#、3#和4#气团中VOCs的化学反应活性主要由苯系物和低碳烯烃贡献.