电场与MnxCey催化剂在苯氧化反应中的协同效应及机理探究

挥发性有机物（VOCs）大量排放已成为日益严重的环境问题,为了实现VOCs的高效去除,本文采用自蔓延燃烧合成法制备了一系列锰铈复合氧化物催化剂,将稳恒直流电场引入典型VOCs气体苯的催化氧化过程,并基于不同电场条件下催化剂的理化性质表征结果进行机理分析.实验结果表明,Mn_xCe_y催化剂对含苯废气的去除有良好的效果,稳恒直流电场显著促进了催化剂的活性,其中Mn₁Ce₃的催化性能最佳,电流为5 mA时,Mn₁Ce₃催化剂在155℃可达到50%的苯转化率,在202.4℃可达到90%的苯转化率,对应的转化温度T₅₀和T₉₀比传统方法分别降低了62.4℃和48.3℃,且电场中的反应活化能由52.32 kJ·mol^-1降低至32.31 kJ·mol^-1.根据实验现象及表征结果,发现协同效应与活性位点的快速持续再生及活性氧物种的转化有关,由此提出苯在Mn_xCe_y催化剂上的氧化机理及电场协同催化的反应模型.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(III) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Three model systems consisting of different iron porphyrins were compared, and the results showed that the peroxynitrite/T(p-Cl)PPFeCl system was the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

北京温榆河流域微生物污染调查研究

随着工业化和城市化进程的加快,我国河流普遍受到了不同程度的水质污染,而微生物指标对于水质评价具有重要作用.本研究选取细菌总数、总大肠菌群、粪大肠菌群以及SC噬菌体、F噬菌体作为指示微生物对北京市温榆河开展了历时一年多的调查研究,结果表明,除了有机污染和富营养化问题外,温榆河流域的微生物污染非常突出.温榆河上游已经受到了一定程度的微生物污染,微生物浓度(以粪大肠菌群为例)波动较大(5.01×10²~5.37×10⁶个·L^-1);下游受清河、坝河等排水河道的影响,微生物污染普遍严重(均值达6.3×10⁶个·L^-1以上),与地表水Ⅴ类水质标准(GB 3838—2002)相比FC浓度平均超出两个数量级.统计分析显示,温榆河微生物污染受季节的影响并不显著(p>0.05),表明人为因素很可能是其主要影响因素.温榆河处于微生物高污染水平,可能威胁地下水水质和农作物质量安全,应从源头加强微生物风险控制.     

Removal kinetics of phosphorus from synthetic wastewater using basic oxygen furnace slag

Removal kinetics of phosphorus through use of basic oxygen furnace slag (BOF-slag) was investigated through batch experiments. Effects of several parameters such as initial phosphorus concentration, temperature, BOF-slag size, initial pH, and BOF-slag dosage on phosphorus removal kinetics were measured in detail. It was demonstrated that the removal process of phosphorus through BOF-slag followed pseudo-first-order reaction kinetics. The apparent rate constant (k_obs) significantly decreased with increasing initial phosphorus concentration, BOF-slag size, and initial pH, whereas it exhibited an opposite trend with increasing reaction temperature and BOF-slag dosage. A linear dependence of k_obs on total removed phosphorus (TRP) was established with k_obs = (3.51 ± 0.11) × 10^− 4 × TRP. Finally, it was suggested that the Langmuir–Rideal (L–R) or Langmuir–Hinshelwood (L–H) mechanism may be used to describe the removal process of phosphorus using BOF-slag.     

利用DGT高分辨率研究沉积物孔隙水中重金属的浓度和释放通量

2006年5月采集了大辽河河段3个柱状沉积物,测定了沉积物的理化性质和重金属元素的含量,并利用常规离心方法和DGT方法测定了柱状沉积物孔隙水中重金属元素的含量.研究发现沉积物中Cd、Co、Cr和Cu元素含量高低的顺序依次是Cr>Cu>Co>Cd.用DGT方法测定的孔隙水中Cd、Co、Cr和Cu的浓度比用离心方法测定的浓度要低.DGT测定的孔隙水中Cd、Co、Cr和Cu的浓度c_DGT与离心方法测定的孔隙水浓度c的平均比值R分别为0.389、0.328、0.863和0.403,这说明沉积物中这几种金属从固相到液相的再补给速率大小遵循如下规律：Cr>Cu>Cd>Co.沉积物中Cd、Co、Cr和Cu元素的释放通量分别为1.12×１０^{-7～3.28×10-7　nmol/(cm2·s)、2.48×１０-7～10.40×10-7　nmol/(cm2·s)、8.80×１０-6～12.65×10-6 nmol/(cm2·s)和6.14×１０-6～13.93×10-6　nmol/(cm2·s).相关分析结果表明,Cd和Cu元素的迁移转化主要受有机质影响;而Cr元素的迁移转化除了受有机质影响外,还受铁锰氧化物影响比较显著;而Co元素可能受氧化还原电位影响较大.}     

电化学微传感器检测水中痕量铜离子

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点,提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征,所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点,因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后,对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4,电导率为36.1S/m,富集时间为360s,富集电位为-1.2V的最佳条件下,铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外,微传感器的可重复性、长期稳定性以及选择性也得到了验证.     

大伙房水库上游矿产企业的潜在风险研究

对大伙房水库上游矿产企业尾矿库进行样品采集,分析其矿渣及渗滤液特征污染因子含量,并与库区沉积物中重金属含量进行比对,结果表明:金矿、铜矿的尾矿库对水库水质安全潜在威胁较大,铁矿次之,分析其污染成因,提出防范措施。     

渤海湾大型底栖生物群落结构变化及原因探讨

根据近6年来的渤海湾大型底栖生物群落的资料,以及2011年的现场调查数据,从渤海湾底栖生物群落结构的变化特征出发,分析了其变化的过程和规律.同时结合渤海湾水域近几年来的水动力条件以及营养盐、溶解氧等水质特征变化,探讨底栖生物群落变化的原因.结果表明,渤海湾大型底栖生物的物种数、生物量、丰度、丰富度指数、多样性指数的高值区皆集中分布在海河口北侧离岸较远的海域,而低值区则基本集中分布近岸海域,且呈现由近岸向外海逐渐增加的趋势.渤海湾大型底栖生物群落变化可大体分为3个明显的时间节点:第一个时间节点为2005年和2008年,底栖生物群落无论总物种数、生物量和丰度都较高;第二个时间节点为2009年和2010年,底栖生物群落的上述指标值最低,表明这两年渤海湾受自然变化和人为因素干扰的程度加剧;2011年,由于渤海湾水域的各项强有力的环保措施的实施,底栖生物群落的上述指标值最高,说明其得到一定程度的恢复.渤海湾水域底栖生物群落变化受到该区域的物理因素、化学因素和生物因素的共同影响,变化特征也与各环境因素的变化基本吻合.     

Emissions of SO2, NO and N2O in a circulating fluidized bed combustor during co-firing coal and biomass

This paper presents the experimental investigations of the emissions of SO2, NO and N2O in a bench scale circulating fluidized bed combustor for coal combustion and co-firing coal and biomass. The thermal capacity of the combustor is 30 kW. The setup is electrically heated during startup. The influence of the excess air, the degree of the air staging, the biomass share and the feeding position of the fuels on the emissions of SO2, NO and N2O were studied. The results showed that an increase in the biomass shares resulted in an increase of the CO concentration in the flue gas, probably due to the high volatile content of the biomass. In co-firing, the emission of SO2 increased with increasing biomass share slightly, however, non-linear increase relationship between SO2 emission and fuel sulfur content was observed. Air staging significantly decreased the NO emission without raising the SO2 level. Although the change of the fuel feeding position from riser to downer resulted in a decrease in the NO emission level, no obvious change was observed for the SO2 level. Taking the coal feeding position R as a reference, the relative NO emission could significantly decrease during co-firing coal and biomass when feeding fuel at position D and keeping the first stage stoichiometry greater than 0.95. The possible mechanisms of the sulfur and nitrogen chemistry at these conditions were discussed and the ways of simultaneous reduction of SO2, NO and N2O were proposed.     

应用WRF/Chem模拟河南冬季大气颗粒物的区域输送特征

基于WRF/Chem模式,设置多组区域排放源的情景实验定量估算河南、京津冀、山东、山西、安徽和江苏、湖北6个区域人为源排放对河南省2015年12月PM_(2.5)和PM_(10)浓度贡献率,并结合气象资料研究3个代表性城市的污染输送特征.结果表明:河南省冬季PM_(2.5)和PM_(10)主要来源为本省排放,平均贡献率分别为54.83%、61.32%.区域污染输送对河南颗粒物的贡献也占有很大比例,京津冀、安徽和江苏、山东、山西以及湖北对PM_(2.5)平均贡献率分别为11.95%、11.69%、7.95%、7.40%、4.30%,对PM_(10)平均贡献率分别为10.42%、10.03%、7.00%、6.89%、3.80%.PM_(2.5)外来输送率比PM_(10)要高,表明细颗粒物比粗颗粒物更易跨区域长距离输送.冬季长持续时间的污染过程大多受静风或小风控制,省内污染贡献最大,过程结束时伴随着大风,周边区域的污染贡献有所增加.不同城市的颗粒物来源与其地理位置、风速、风向等气象条件密切相关.区域污染来源具有复杂性,改善河南省空气质量是需要整个区域共同面对和解决的问题.