化学沉淀法去除垃圾渗滤液中的氨氮

为了有效地去除垃圾渗滤液中高浓度的ＮＨ＾＋４－Ｎ而避免传统吹脱法造成吹脱塔内碳酸盐结垢问题,探讨了采用化学药剂诸加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ或ＭｇＯ和Ｈ３ＰＯ４使ＮＨ＾＋４－Ｎ生成磷酸铵镁的化学沉淀去除法。小试研究结果表明,当垃圾渗滤液中投加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ而使Ｍｇ＾２＋：ＮＨ＾＋４：ＰＯ＾３－４的比例为１：１：１时,在最佳ｐＨ为８．５～９．０     

气相过氧化氢的生成及大气中浓度的测定

研究了ＨＣ－ＮＯ２－空气体系中Ｈ２Ｏ２和有机氢过氧化物的生成。模拟实验结果表明：Ｈ２Ｏ２生成浓度的最大值与碳氢化合物的初始浓度成正比;生成规律与Ｏ３生成规律类似,比值［Ｏ３］ｍａｘ／［Ｈ２Ｏ２］ｍａｘ随［ＨＣ］０增大而减小。在乙烯、戊烷体系中,Ｈ２Ｏ２在总过氧氢化物的比例为０．６左右;而丙烯体系中,随光照时间的延长,有较多的有机氢过氧化物产生。大气监测结果显示：Ｈ２Ｏ２的生成受污染物排放、日照及温度的影响,早晚浓度低,午后形成峰值,日变化规律与Ｏ３浓度变化相似,监测到的最大浓度值在春季为１．３×１０－９,在秋节为０．６４×１０－９。     

溴代烷烃光氧化的研究

本文模拟大气条件,研究了ＣＨ３Ｂｒ＋Ｈ２Ｏ２＋Ｏ２,ＣＨ３Ｂｒ＋Ｏ２,ＣＨＢｒ３＋Ｈ２Ｏ２＋Ｏ２,和ＣＨＢｒ３＋Ｏ２４个体系的光化学反应。这些体系在２５３．７ｎｍ的紫外光照射下Ｈ２Ｏ２产生了ＯＨ自由基,ＯＨ自由基与ＣＨ３Ｂｒ和ＣＨＢｒ３反应,在２０ｍ的长光程气体池中ＦＴＩＲ测量这些反应产物,发现在ＣＨ３Ｂｒ＋Ｈ２Ｏ２＋Ｏ２和ＣＨ３Ｂｒ＋Ｏ２体系其光化Ｏ２其光化学反应产物为ＣＯ和ＣＯ２,并从这些产物     

不同离子在CCl4引发自由基反应中的作用及其环境生物学意义

报道了一种简便的ＣＣ１４体外引发自由基反应的模型，以小鼠肝匀浆脂质过氧化产物丙二醛（ＭＤＡ）的ＯＤ５３２ｍｍ值（ＭＤＡ－ＯＤ５３２ｍｍ）作为测定自由基反应的间接指标，研究了Ｈｇ＾２＋、Ｍｎ＾２＋、Ｎｉ＾２＋、Ｃｒ＾３＋、ＳｅＯ３＾２－等离子和Ｓs２Ｏ３水溶液在ＣＣ１４引发自由基反应体系中的作用。结果表明：Ｍn＾２＋能显著抑制自由基的生成，Ｃr＾３＋有一定的抑制作用，而ＨgＴ＾２＋对自由基产生有明显促进     

沿海地区海盐和大气污染物反应的致酸作用

着重研究全球沿海地区海盐和在气污染物ＳＯ２,ＮＯｘ反应的致酸作用,通过资料分析发现：海盐和大气污染物反应的致酸存在临界浓度,在氏气溶胶浓度的大气中,海盐和大气污染物反应致酸的ＳＯ２的临界浓度为０．００４３ｍｇ／ｍ＾３。海盐和大气污染物反应的致酸存在３种类型：火山排放ＳＯ２和海盐反应致酸,降水中过量氯与Ｈ＾＋浓度呈正相关,过量氮对Ｈ＾＋浓度最大贡献可达５０％;外来输送ＳＯ２、ＮＯｘ和海盐反应的致酸,     

长光路FTIR研究HFC152a光化学反应

用长光路ＦＴＩＲ技术研究氟里昂替代物ＨＦＣ１５２ａ（ＣＨ３ＣＨＦ２）在对流层中的化学反应，氯离子作反应的引发剂，用相对速度方法测定了ＨＦＣ１５２ａ与Ｃｌ原子反应速率常数为（２．３±０．５）×１０＾－１３ｃｍ＾３·ｍｏｌ＾－１·ｓ＾－１（２９８±Ｋ）。ＨＦＣ１５２ａ在对流层中的主要含氟光解产物为ＣＯＦ２，产率为８８％。有关反应机理进行了讨论。     

阿魏酸芥子酸清除亚硝基自由基的动力学研究

利用脉冲辐解方法，研究了阿魏酸、芥子酸（ＨＣＡ）快速清除ＮＯ２的机理，测得ＮＯ２从ＨＣＡ抽氢反应的动力学常数为（７．２－７．４）×１０＾８ｄｍ＾３．ｍｏｌ＾－１．ｓ＾－１量级，并发现在弱酸性条件下ＨＣＡ也能有效清除ＨＮＯ２。     

几种类Fenton试剂的氧化特性及在工业废水处理中的应用

根据文献资料，概述了羟基自由基（·ＯＨ）的性质，系统地介绍了Ｆｅｎｔｏｎ试剂及其几种类Ｆｅｎｔｏｎ试剂Ｈ２Ｏ２＋ｕｖ（ｕｌｔｒａｖｉｏｌｅｔ）、Ｈ２Ｏ２＋Ｆｅ＾２＋＋ｕｖ、Ｈ２Ｏ２＋Ｆｅ＾２＋＋Ｏ２、Ｈ２Ｏ２＋ｕｖ＋Ｏ２和Ｈ２Ｏ２＋Ｆｅ＾２＋＋ｕｖ＋Ｏ２的氧化特性，并对该领域国内外研究动态及在工业废水处理中的应用状况进行了较为详细的阐述。     

碳酸铅作为铅酸蓄电池电极材料的研究

采用粉末微电极技术和循环伏安法研究了ＰｂＣＯ３转化为铅酸电池电极活性物质的途径以及几种因素对ＰｂＣＯ３转化的ＰｂＳＯ４／ＰＢ电极性能的影响。ＰｂＣＯ３粉末在Ｈ２ＳＯ４溶液中化学转化－电化学活化后,正、负极的伏这行为与文献报道的类似。结果表明,较高扫速活化的ＰｂＳＯ４／Ｐｂ电极性能稳定且活性较高;转化ＰｂＣＯ３的Ｈ２ＳＯ４浓度０．５￣１．０ｍｏｌ·Ｌ＾－１优于２．５￣５．０ｍｏｌ·Ｌ＾－１,３０℃附     

在H2O2存在下CH3Br和CHBr3光解特性

模拟大气条件,研究了ＣＨ３Ｂｒ＋Ｈ２Ｏ,ＣＨＢｒ３＋Ｈ２Ｏ２两个体系的光解特性,这些体系在２５３．３７ｎｍ的紫外光照射下Ｈ２Ｏ２产生了ＯＨ基,ＯＨ自由基与ＣＨ３Ｂｒ反应,在２０ｍ的长光程气体池中用ＦＴＩＲ测量这些反应产物。     

Organic peroxy radicals: Kinetics,spectroscopy and tropospheric chemistry

The present state of knowledge of organic, or carbon-based, peroxy radicals (RO₂) is reviewed. Data on the chemical and physical properties of peroxy radicals in the gas-phase is considered, as well as the role of peroxy radicals in tropospheric chemistry and measurements of their concentrations in the atmosphere. Where appropriate, peroxy radicals are grouped together by type (alkyl, acyl, oxygen-substituted, halogen-substituted and aromatic radicals) to facilitate comparison. Data on the hydroperoxy radical (HO₂) is included where it is directly relevant to measurements on organic peroxy radicals, eg. absorption cross-sections used in measurements of RO₂ + HO₂ rate constants. The literature data is critically reviewed and recommendations for absorption cross-sections, rate constants and branching ratios are made where considered appropriate.The laboratory experimental techniques which have been used for the generation and detection of peroxy radicals and the products of their reactions are discussed. The structure, spectroscopy and thermochemistry of the radicals are examined. Although the majority of spectroscopic data concerns the u.v. spectra much used for kinetic studies, near-infrared, infrared and electron spin resonance spectra are also considered. In many cases, peroxy radical u.v. spectra are well-fitted by a Gaussian distribution function, enabling the cross-sections to be easily calculated at any wavelength.For the purpose of this review, the chemical reactions of peroxy radicals are divided into reactions with organic peroxy radicals with HO₂, with NO and NO₂, and finally with other species. Peroxy radical abstraction and addition reactions with closed-shell species are sufficiently slow to be of negligible importance at temperatures pertinent to the atmosphere and are consequently not covered. Data on both the kinetics and mechanisms of peroxy radical reactions are considered.The role of peroxy radicals as intermediates in the atmospheric degradation of volatile organic compounds and in the production of ozone in the troposphere under both low and high [NO_x] conditions is discussed. The involvement of peroxy radicals in night-time oxidation chemistry and the oxidation of halocarbons is also indicated. The techniques used for the difficult measurement of peroxy radical concentrations in the atmosphere are described, together with the results to date.Finally, some tentative suggestions as to further avenues of research are made, based on the data reviewed here and with particular reference to the solution of outstanding problems in atmospheric chemistry. Although a great deal of progress has been made in recent years, it is clear that additional work is needed in most areas covered by this review. New, sensitive and selective laboratory techniques are required for studies of peroxy radical kinetics and high level ab initio calculations would help design laser-based detection techniques. Further product studies of photooxidation systems are needed, particularly as a function of temperature. Recent work has shown that the rate constants for RO₂ + HO₂ reactions used in modelling studies may be too low; if so, these reactions will be correspondingly more important than previously believed in tropospheric oxidation. Recent kinetic studies of the potentially important reactions of methylperoxy radicals with ClO and NO₃ need to be confirmed and mechanistic work is necessary. Although substantial progress has been made towards the monitoring of peroxy radical concentrations in the atmosphere, more work is needed, both on measurements and the development of new techniques.     

基于总过氧自由基观测研究合肥市西郊夏季O3生成特征

2020年8月利用化学放大法对合肥市西郊大气总过氧自由基RO^*₂·(RO₂·+HO₂·)体积分数进行监测,并结合O₃和其前体物,分析了过氧自由基体积分数、O₃生成速率和O₃生成对前体物的敏感性.结果表明,观测期间总过氧自由基体积分数的日均值呈典型的单峰型变化,12:00左右出现最高值,日间峰值体积分数为43.8×10^-12,日间RO^*₂·与太阳辐射强度、温度和O₃呈明显的相关性.利用实测RO^*₂·和NO,获得合肥市西郊夏季O₃生成速率,日间峰值为10.6×10^-9h^-1,O₃生成速率对NO变化更为敏感.基于大气自由基和NO_x(NO+NO₂)反应去除速率占比(Ln/Q),对合肥...     

广州城市大气HOx化学过程初步研究

根据广州城市大气中OH自由基和其它污染物同步测量结果,计算了城市大气HO_x(OH+HO₂)化学过程中主要反应的转化速率,分析了城市大气化学过程的主要特征,并与清洁大气中的化学过程进行了对比.研究结果表明:广州城市大气中OH和HO₂总的生成速率分别约为4.5×10⁸分子/(cm³·s)和3.8×10⁸分子/(cm³·s),比清洁大气中要快得多;城市大气中的OH净生成主要来自气相HNO₂的光解,而OH的去除主要与VOCs、HCHO、NO₂和CO反应,有别于清洁大气.     

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO₂) and superoxide (O₂⁻) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO₂/O₂⁻. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO₂/O₂⁻, and cycled between the Cu(II) and Cu(I) forms. Cu⁺ reacted with FeOH²⁺ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10⁷ M⁻¹s⁻¹. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO₂/O₂⁻. Only at high oxalate concentrations was the Fe(II)C₂O₄ complex also formed, and it reacted relatively rapidly with hydrogen peroxide (k = (3.1 ± 0.6) × 10⁴ M⁻¹s⁻¹). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH²⁺ with Cu(I) and HO₂/O₂⁻, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO₂ present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO₂/O₂⁻, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO₂/O₂⁻.     

Multiple transformation pathways of p-arsanilic acid to inorganic arsenic species in water during UV disinfection

p-Arsanilic acid(p-ASA) is widely used in China as livestock and poultry feed additive for promoting animal growth.The use of organoarsenics poses a potential threat to the environment because it is mostly excreted by animals in its original form and can be transformed by UV–Vis light excitation.This work examined the initial rate and efficiency of p-ASA phototransformation under UV-C disinfection lamp.Several factors influencing p-ASA phototransformation,namely,p H,initial concentration,temperature,as well as the presence of Na Cl,NH4+,and humic acid,were investigated.Quenching experiments and LC–MS were performed to investigate the mechanism of p-ASA phototransformation.Results show that p-ASA was decomposed to inorganic arsenic(including As(Ⅲ) and As(V))and aromatic products by UV-C light through direct photolysis and indirect oxidation.The oxidation efficency of p-ASA by direct photosis was about 32%,and those by HOU and1O2 were 19% and 49%,respectively.Cleavage of the arsenic–benzene bond through direct photolysis,HOU oxidation or1O2 oxidation results in simultaneous formation of inorganic As(Ⅲ),As(IV),and As(V).Inorganic As(Ⅲ) is oxidized to As(IV) and then to As(V) by1O2 or HOU.As(IV) can undergo dismutation or simply react with oxygen to produce As(V) as well.Reactions of the organic moieties of p-ASA produce aniline,aminophenol and azobenzene derivatives as main products.The photoconvertible property of p-ASA implies that UV disinfection of wastewaters from poultry and swine farms containing p-ASA poses a potential threat to the ecosystem,especially agricultural environments.     

172nm真空紫外辐射降解水相有机染料的机理研究

研究了氙准分子灯的172nm真空紫外辐射对水相有机染料枣红的分解机理.氙准分子灯为平面状结构,反应溶液作为灯的一端电极直接与灯表面接触.分别在枣红溶液中通入氧气和氮气以及加入KCl,以具体确定172nm辐射对枣红分子的降解是通过直接光分解还是自由基起作用.研究结果表明,在枣红的降解过程中,直接光分解起主要作用,光降解过程符合准一级动力学反应,光量子产率为6 8×10 - 3mol·eistein- 1 .在HO·、HO2 ·和O2 ·- 自由基作用下,枣红的降解在10min后偏离了准一级反应.枣红降解效率达到约80 %后,COD去除率开始增大.GC MS分析表明,在光分解和热氧化作用下,枣红分子在降解过程中形成了许多小分子碎片.     

Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.     

吸收协同高级氧化工艺处理低浓度含氰废气实验研究

以乙腈作为含氰废气的典型组分,考察吸收协同不同高级氧化体系下低浓度乙腈的去除效率以及产物分配情况.研究结果表明：UV/PS和VUV/PS体系均能有效吸收并降解乙腈,在60 min内其脱除效率近100%,且矿化率近80%或以上.主要原因是吸收液中的过硫酸盐（PS）可以在紫外光的激发下产生大量的HO^·和SO₄^·-,这些自由基可以促进乙腈和中间产物的氧化.同时实验还观察到乙腈中的氮元素主要被转化为NO₃^-和NH₄⁺,这说明乙腈的直接氧化和水解反应同时进行.NO₃^-的累积会竞争消耗反应体系中的自由基,这是其稳定性实验中乙腈矿化率下降的主要原因.此外,干扰离子Cl^-也会由于自由基的捕获作用抑制乙腈的降解.最后,根据产物的分析结果,提出了包含氧化与水解路径的乙腈总体降解反应途径.     

南京夏季大气臭氧光化学特征与敏感性分析

对流层臭氧（O₃）主要由氮氧化物（NO_x）和挥发性有机物（VOCs）经过一系列光化学反应生成,反应过程呈现复杂的非线性关系.为深入了解O₃的光化学特征及生成机制,利用2018年夏季大气O₃与VOCs的观测数据,结合大气零维框架模拟模型F0AM-MCM,研究O₃超标日和非O₃超标日的O₃光化学特征之间的差异性.观测结果表明,O₃超标日期间φ（O₃）和φ（TVOCs）的平均值分别为47.8×10^-9和49.0×10^-9,为非O₃超标日期间O₃（26×10^-9）和TVOCs（30×10^-9）体积分数的1.8倍和1.6倍.使用F0AM模型,借助EKMA曲线和RIR分析等识别O₃敏感性,发现南京市O₃超标日和非O₃超标日O₃的形成均主要受VOCs和NO_x的协同控制.F0AM-MCM模拟结果表明,在O₃超标日,·OH和HO₂的日平均混合比分别是非O₃超标日的1.3倍和1.8倍,表明O₃超标日期间具有更强的大气氧化能力,且·OH和HO₂的形成和损失速率也有明显的增加,表明自由基循环的增强.此外,O₃超标日的O₃生成速率明显高于非O₃超标日,从而导致了O₃超标日的O₃净生成速率明显高于非O₃超标日.以上发现提高了对南京夏季O₃超标日大气O₃光化学特征的认识.     

Cu-Al2O3中骨架铜类芬顿催化去除水中有机污染物

为解决传统铁基芬顿催化剂在水体通常酸碱(pH6)条件下活性低的问题,采用简单共沉淀法制备了Cu掺杂的Al_2O_3类芬顿催化剂.通过X射线衍射(XRD)、X射线光电子能谱(XPS)和紫外可见(UV-vis)吸收光谱分析表明,Cu-Al_2O_3中铜掺杂的质量分数低于4.77%时,催化剂中铜主要以Cu~(2+)和Cu~+的形式共存于Al_2O_3的骨架结构中,形成Al—O—Cu键;过量的铜掺杂会导致外骨架铜物种如铜氧化物团簇的存在.以难降解有机污染物2-氯苯酚(2-chlorophenol,2-CP)和染料罗丹明B(Rhodamine B,Rh B)为目标污染物,对Cu-Al_2O_3的类芬顿催化性能进行了详细地研究.结果表明,骨架铜物种在中性温和条件下对2-CP和Rh B显示出很高的催化去除效率和稳定性,反应2 h,Cu-Al_2O_3(Cu质量分数4.77%)对2-CP的去除率达到54%,相应的TOC去除率达到49%,而铜离子溶出浓度仅为0.025 5 mg·L-1,而Cu-Al_2O_3(Cu质量分数7.58%)由于外骨架铜的存在导致催化活性增加缓慢和稳定性下降.ESR测试结果表明,·OH和HO_2~-/O_2~-·是反应中主要的活性物种.