γ-Fe2O3抗As2O3中毒能力的分子模拟

采用密度泛函理论研究了γ-Fe₂O₃表面As₂O₃的吸附以及掺杂改性提高抗As₂O₃中毒性能的作用机理.计算了As₂O₃在完整以及O缺陷γ-Fe₂O₃（001）表面的吸附性能,包括吸附位点、吸附结构、吸附能、PDOS等.同时建立了Mo、Ti、Mg掺杂的γ-Fe₂O₃模型,探讨了助剂掺杂对抗砷中毒能力的作用机制,并考虑了掺杂量的影响.结果表明：As₂O₃倾向于以O端化学吸附在γ-Fe₂O₃（001）表面Fe_oct位,吸附过程发生强烈的相互作用和电荷转移.当表面存在O缺陷时,As₂O₃的吸附能得到提高.Mo、Ti、Mg倾向于掺杂在Fe_oct位,增强了对As₂O₃的吸附能力,并且增大Mo的掺杂量可以强化As₂O₃的吸附.As₂O₃倾向于与活性较强的Mo、Ti、Mg发生反应,从而保护活性Fe位不受砷中毒,Ti和Mg的掺杂还抑制了相邻Fe位对As₂O₃的吸附.Mo、Ti、Mg的掺杂还促进了催化剂表面对NH₃的吸附,增强了表面酸性强度,有利于SCR反应.Mo、Ti、Mg原子的掺杂有利于提高γ-Fe₂O₃催化剂的抗砷中毒性能.     

深圳市大气颗粒物分粒径有效密度及影响因素

为探究深圳市大气颗粒物分粒径有效密度变化特征及其影响因素,本文将离心颗粒物质量分析仪(CPMA)与差分电迁移粒径分析仪(DMA)联用,通过粒径筛分测定了2020年9月~2021年2月粒径范围为50~500nm的深圳市大气颗粒物分粒径有效密度.结果表明:深圳市大气颗粒物的中值有效密度范围在1.29~1.53g/cm³,颗粒物有效密度均随颗粒物粒径增加而增大,秋季有效密度略低于冬季.清洁时期,有效密度较低且观察到双峰分布,低密度颗粒物中值有效密度在0.70~0.80g/cm³范围内,表明存在新鲜排放的黑碳颗粒物,高密度颗粒物中值有效密度在1.3~1.5g/cm³范围内,介于二次无机颗粒物和有机物的材料密度之间,推测为二者混合状态.污染时期,不同粒径有效密度值增加且呈现单峰分布,表明颗粒物呈现内混态.在新粒子生成事件中,气态硝酸凝结可能是大气颗粒物后续粒径增长和有效密度增加的主要原因.     

Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H

Fluorine-containing halogenated fluorophenol may have efect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans(PFDDs/Fs). The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K/6-31+G(d,p) level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB1K/6-311+G(3df,2p) level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600–1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive efect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O–H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.     

Radiation induced decomposition of a refractory cefathiamidine intermediate

Diisopropylthiourea（DPT）, an intermediate of a widely used cephalosporin, has been found to be one of the most refractory components in cephalosporin synthesis wastewater.This compound cannot be completely removed by conventional biological processes due to its antimicrobial property. Ionizing radiation has been applied in the decomposition of refractory pollutants in recent years and has proved effective. Therefore, the decomposition of DPT by γ-irradiation was studied. The compound was irradiated at the dose of 150–2000 Gy before a change of concentration and UV absorption of the solutions was detected.Furthermore, the decomposition kinetics and radiation yield（G-value） of DPT was investigated. The results of radiation experiments on DPT-containing aqueous showed that the DPT can be effectively degraded by γ-radiation. DPT concentration decreased with increasing absorbed doses. G-values of radiolytic decomposition for DPT（20 mg/L） were 1.04 and 0.47 for absorbed doses of 150 and 2000 Gy, respectively. The initial concentration and p H of the solutions affected the degradation. As the concentration of substrate increased,the decomposition was reduced. The decrease of removal rate and radiation efficacy under alkaline condition suggested that lower p H values benefit the γ-induced degradation. UV absorption from 190 to 250 nm decreased after radiation while that from 250 to 300 nm increased, indicating the formation of by-products.     

Theoretical study on the degradation reaction of octachlorinated dibenzo-p-dioxin with atomic oxygen O(3P) in dielectric barrier discharge reactor

Dielectric barrier discharges （DBD） have been used in the degradation of dioxins due to the large number of excimers and free radicals produced in discharge process. In this article, the density functional theory （DFT） is used to study the degradation mechanism of octachlorinated dibenzo-p-dioxin （OCDD） with the atomic oxygen O（3P） in DBD reactor. The reactants, intermediates, transition states and products are optimized at the MPWB1K/6- 31 ＋ G（d,p） level. The vibrational frequencies have been calculated at the same level. The reaction pathways and mechanisms are analyzed in detail. The effect of removing the chlorine atom on environment also has been discussed.     

压实膨润土非饱和渗透系数的一种预测分析方法

用新疆柯尔碱膨润土制备不同干密度土样进行土水特征曲线实验和渗透实验,得到不同干密度土样的土水特征曲线,通过van Genuchten模型预测出相应的非饱和渗透系数,进而得到不同干密度土样非饱和渗透系数与含水率的关系。结果显示:非饱和渗透系数随着含水率的减小非线性的减小,随干密度的增大而减小。当含水率较高时,非饱和渗透系数随含水率的变化比较小;当含水率较小时,渗透系数随含水率的变化比较大。而干密度对渗透系数的影响伴随整个实验过程,当干密度较小时,随着干密度的增大,渗透系数受干密度影响较大。当干密度较大时,此时干密度的进一步增大对渗透系数的影响不大。     

如何推进排污权交易试点？

全国范围内开展排污权交易试点工作取得了初步成效,截至2013年底,有偿使用和交易金额累计达到40亿元左右。环保部要求各地细化完善初始排污权核定,公平合理确定排污权。试点地区要于2015年底前保质保量完成现有排污单位排污权的初次核定,环境保护部争取结合“十三五”减排规划的编制,制定电力、钢铁、水泥、平板玻璃、造纸、印染等重点行业排污权初始核定技术指南。     

危险废物填埋场渗滤液初始浓度表征模拟研究

渗滤液初始浓度(C0L)是计算填埋场渗漏污染物源强的重要参数之一,由于填埋场构造复杂,其在运行过程中很难获取,因此在计算填埋场环境风险数学的模型常用浸出浓度(CL)代替C0L。本研究以典型危险废物固化飞灰为代表,开展了优势污染物Cr在不同模拟高度(h)土柱和不同浸取剂pH条件下土柱溶出模拟试验研究,通过对比不同时间段内不同体积浸出液中的总Cr浓度(CCr0),定义了表征C0L对应的采样体积数,探讨C0L的影响因素中其与h、pH的相关关系。研究结果表明浸取液的pH在3~7范围内时C0L没有明显规律性,C0L随h增大而增大,并且根据实验数据初步建立了C0L和h、pH之间的简单数学关系模型。     

贵州排污权交易初始价格定价策略探讨

排污权交易初始价格的合理性是启动排污权交易市场、刺激交易行为发生的关键因素。初始价格的确定,应遵循刺激性、适度性原则,并充分考虑贵州省现状。本研究从定价原则、定价方式、定价使用期限等方面对贵州省排污权交易价格的定价策略进行了探讨。     

区域排污权初始分配模型应用研究——以湖北省为例

针对目前湖北省水污染物排污权初始分配呈真空的现状,综合考虑环境现状、经济发展、社会公平和科技水平等众多影响因素,并细化成累计授权专利数、地区生产总值、人口总数和水资源量等指标,通过信息熵法确定各指标权重,以湖北省各市州为分配对象构建了区域排污权初始分配模型.并以2009年湖北省各市州公布的公报数据为基准进行了分配模型的应用.分配结果显示了分配模型具备较为全面的特点,且通过指标权重区分了各因素差异程度,为政府决策提供了参考.