宇宙环境中的某些化学问题

本文讨论了宇宙环境中的化学概况,特别是宇航环境化学和宇航适应问题。     

水体中羟基自由基介导的三氯卡班氧化机制的量子化学研究

因羟基自由基引发的初始反应对于研究高级氧化过程中有机污染物的转化至关重要.本研究采用量子化学计算探究羟基自由基与三氯卡班加成与抽氢反应的机理,并利用ECOSAR软件预测并评价产物的生态毒性.结果表明,除C₁₄位点加成反应外,其它反应过程均为放热 反应;反应活化自由能为6.55~23.5 kcal·mol^-1,其中,最小值和最大值分别为C₂₀和C₁₄位点的加成反应;同时,C₁、C₃、C₂₅和C₁₄位点的加成反应与三氯卡班的脱氯或C—N的断裂存在协同.进一步动力学研究结果显示,加成与抽氢反应的总速率为2.27×10⁸ L·mol^-1·s^-1,其中,速率最大和最小的反应分别为C₂₀（1.11×10⁸ L·mol^-1·s^-1）和C₁₄（1.30×10^-5 L·mol^-1·s^-1）位点的加成,并且加成反应占主要通道（74.8%）,尤以C₂₀位点的加成产物最为突出（49.0%）,以上研究与平均局部离子化能计算结果相一致.生态毒性评价结果虽然表明加成反应可有效脱毒,但大部分产物对 水生生物仍具有一定威胁.     

太湖流域污水排放对湖水天然水化学的影响

为揭示太湖流域污水排放对湖水天然水化学(主要离子)的影响,对太湖上游19个污水处理厂的进水、出水及雨水、入湖河水和湖水中主要离子进行了分析,同时收集历史数据对比了太湖1950s年代和目前的天然水化学特征.结果表明,太湖水体天然水化学类型主要受流域碳酸盐岩风化作用控制,而受雨水影响较小;流域排放的污水主要离子特征类似于干旱地区的河水,部分工业污水甚至具有海水水化学特征,说明人为活动对当地淡水水质的重要影响.同时,太湖水化学已从60年前的重碳酸盐钙型水转变为目前的氯化物钠型水.进一步通过修正的完全混合断面污染物浓度模型的计算结果显示,生活污水排放可以解释对太湖多数主要离子的影响,生活和工业污水的排放可以更好地解释Cl#的变化;但太湖Ca2+和Mg2+浓度(硬度)的增长受污水影响较小,而是受流域酸沉降的影响控制.分析显示,60年来受流域不断增长的污水排放影响,太湖水体的优势阴阳离子组分均已发生了显著变化,目前湖水(Ca2++Mg2+)-HCO-3和(Na++K+)-Cl-均分布在1∶1线上侧,而(Ca2++Mg2+)/(Na++K+)比值则下降了约1半,同时湖水的Cl#/Na+比值显示出显著的升高趋势,说明流域人类活动已经成为影响太湖水化学的主要原因.本研究可为湖泊水化学演化研究及强烈人为干预条件下的水环境管理提供新的基础.     

南京冬季云凝结核活化特征及闭合研究

2017年12月~2018年1月在南京地区对气溶胶的云凝结核（CCN）活化特征进行外场观测,并利用4种常用的闭合方法实现对CCN数浓度的预测.结果表明本次观测期间南京地区的气溶胶具有较高的CCN活性,吸湿性参数（κ）的平均值为0.36.对清洁到不同程度雾-霾天气溶胶污染的CCN活化特征进行对比分析,发现随着污染程度的加深,气溶胶的吸湿性逐渐减弱;在同一能见度（VIS）范围内,环境相对湿度（RH）更高的天气类型中气溶胶的吸湿性和活化能力也更高,这可能由于高RH条件能促进大气中非均相及液相反应生成更多的二次无机气溶胶.4种闭合方法的结果显示,利用临界粒径、截断粒径及粒径分辨的活化谱三种方法总体上均有较好的闭合结果.其中,对于低过饱和度（S）下的预测来说,利用截断粒径方法的闭合结果最为理想.     

晴隆锑矿和煤矿矿集区岩溶地下水环境质量评估

锑是环境中广泛分布、具有慢性毒性和潜在致癌性的典型毒害重金属,是一种新兴的全球性环境污染物。过去对锑的地球化学行为研究较多,但对岩溶地下水的环境质量影响的研究较少。选择锑矿和煤矿分布广泛的贵州晴隆县境内龙摆尾地下河为研究对象,对研究区的地表水和地下水的水化学特征和污染特征进行研究,以《生活饮用水卫生标准》(GB 5749—2006)和《地表水环境质量标准》(GB 3838—2002)中的Ⅲ类标准值为评价标准对该地区水质予以评价。结果表明:在锑矿未开采情况下,第四系碧痕营组地下水中锑的浓度较高,平均值为1.55μg/L,最高为6.32μg/L;锑、砷的迁移受氧化还原条件的控制;岩溶地下水整体来说水质符合生活饮用水标准,但碧痕营组水中锑、锰超标,龙潭组中节理裂隙水存在pH、锰超标情况;而煤矿开采污染的地表水中锰、铁的污染具有普遍性,含量均超过地表水环境质量标准的限值,且超标倍数较大。因此,该研究区岩溶地下水可直接作为饮用水源,而碧痕营组和龙潭组中地下水须做处理后才可饮用。     

太原煤化工区有毒气体泄漏环境风险分析

针对太原煤化工区氯气、氨气和光气这3种泄漏风险最高的有毒气体的事故条件,采用非定常的CALPUFF大气扩散模式进行了一整年的事故扩散模拟.获得逐时次事故扩散浓度场并分析3种污染物泄漏的全年平均风险及各季变化.结果定量描述了氯气、氨气和光气的致死浓度、中毒浓度和刺激浓度的全年及各季平均风险范围,并分析了不同有毒气体风险范围的差异及四季变化的原因.     

应用铁铜双金属有机骨架活化过硫酸盐催化剂去除水中有机污染物的研究

基于MIL-101(Fe)的合成方法,首次采用合成前金属掺杂法制备了双金属有机骨架MIL-101(Fe,Cu)催化剂,并利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、扫描电镜(SEM)和X射线能谱仪(EDS)对催化剂进行表征.同时,以罗丹明B(Rh B)为目标降解物,研究此催化剂催化过硫酸盐降解Rh B的性能,并初步尝试将催化剂应用于邻苯二甲酸二丁酯(DBP)的催化降解.XRD、FTIR、SEM和EDS等分析结果表明,铜离子的掺杂导致MIL-101(Fe)的结构与形貌发生了改变,提高了对污染物的吸附和催化降解作用.相比MIL-101(Fe),在90 min时MIL-101(Fe,Cu)对Rh B的去除率达到95%,在180 min时对DBP的去除率达到68%.此外,分析了催化剂催化性能提高的原因:配位竞争导致铁离子的不饱和趋向;形貌的变化加强了对污染物的吸附作用.     

Fe (II)活化过硫酸盐处理喹啉工艺参数优化及生物毒性

以喹啉为处理目标物,采用Fe²⁺活化K₂S₂O₈（PS）的高级氧化体系在不同环境因素下降解喹啉.结果表明：与单一PS体系和Fe²⁺体系相比,Fe²⁺/PS体系可以有效降解喹啉.在初始喹啉浓度为250mg/L,喹啉/PS物质的量比为1：10,PS/Fe²⁺物质的量比为3,初始pH3,反应温度为45℃,反应时间为80min的条件下,喹啉降解率可达100%.提高PS和Fe²⁺浓度均能有效提高喹啉降解率,但超过一定限值后对喹啉去除效果不明显.Fe²⁺/PS去除喹啉的过程符合一级反应动力学.溶液初始pH值越高,喹啉去除率越低;反应温度越高,喹啉去除率越高.自由基淬灭实验证实,Fe²⁺活化PS体系中有SO₄^-·和OH·的存在,其中由SO₄^-·产生的OH·对喹啉的降解占主导地位.通过GC/MS检测到2种中间产物8-羟基喹啉和2（1H）-喹啉酮,据此推测基于硫酸根自由基强化喹啉降解的可能路径.大肠杆菌急性毒性实验结果证实,虽然Fe²⁺/PS体系去除喹啉过程中产生了毒性更强的中间产物,但酸性条件和较高的反应温度有利于体系脱毒.     

烷烃条件下CF2ClBr的紫外光解离机理研究

以气相色谱、红外光谱为主要分析手段,对气态ＣＦ２ＣｌＢｒ在ＣＲ２ＣｌＢｒ－Ｃ６Ｈ１２体系中的紫外光解离进行了研究,结果表明,在２５３．７ｎｍ紫外光照射下,该体系的主要光解产物为ＨＣＶＦ２Ｃｌ、ＨＢｒ以及Ｃ６Ｈ１２的聚合物,体系中ＣＦ２ＣｌＢｒ的解离近似精同缀反应,解离反应的速率常数为２．８７７×１０＾－６ｓ＾－１表观量子产率约０．１,基于此,对该光解反应的机理做了分析。     

The Application of Chemical Leasing Business Models in Mexico

- DOI: http://dx.doi.org/10.1065/espr2006.02.294 Background, Aim and Scope. To better address the requirements of the changing multilateral order, the United Nations Industrial Development Organization (UNIDO) Cleaner Production Programme, in 2004, developed the new Sustainable Industrial Resource Management (SIRM) approach. This approach is in accordance with the principles decided at the United Nations Conference on Environment and Development (UNCED) in Rio de Janeiro, Brazil in 1992. Unlike the traditional approaches to environmental management, the SIRM concept captures the idea of achieving sustainable industrial development through the implementation of circular material and energy flows in the entire production chain and reduction of the amount of material and energy used with greater efficiency solutions. The SIRM approach seeks to develop new models to encourage a shift from selling products to supplying services, modifying, in this manner, the supplier/user relationship and resulting in a win-win situation for the economy and the environment. Chemical Leasing represents such a new service-oriented business model and is currently being promoted by UNIDO′s Cleaner Production Programme. Main Features. One of the potential approaches to address the problems related to ineffective use and over-consumption of chemicals is the development and implementation of Chemical Leasing business models. These provide concrete solutions to the effective management of chemicals and on the ways negative releases to the environment can be reduced. The Chemical Leasing approach is a strategy that addresses the obligations of the changing international chemicals policy by focusing on a more service-oriented strategy. Mexico is one of the countries that were selected for the implementation of UNIDO's demonstration project to promote Chemical Leasing models in the country. The target sector of this project is the chemical industry, which is expected to shift their traditional business concept towards a more service and value-added approach. This is being achieved through the development of company specific business models that implement the above-indicated Chemical Leasing concept with the support from the Mexican National Cleaner Production Centre (NCPC). Results and Conclusions. The implementation of Chemical Leasing in Mexico has proven to be an efficient instrument in enhancing sustainable chemical management and significantly reducing emissions in Mexico. Several companies from the chemical industrial sector implement or agreed to implement chemical leasing business models. Based on the positive findings of the project, several Mexican companies started to negotiate contents of possible Chemical Leasing contracts with suitable business partners. The project further aimed at disseminating information on Chemical Leasing. It successfully attracted globally operating companies in the chemicals sector to explore possibilities to implement Chemical Leasing business models in Mexico. At the international level, the results of the UNIDO project were presented on 20TH September 2005 during a side event of the Strategic Approach to International Chemicals Management (SAICM) Preparation Conference in Vienna. Recommendations and Outlook. To facilitate the promotion and application of Chemical Leasing project at international level, UNIDO is currently developing a number of tools to standardize Chemical Leasing projects. These include, among others, Chemical leasing contract models; Chemical Leasing data base to find partners for chemical leasing; and guidelines to implement Chemical Leasing projects and work programmes.