硝基苯气相氟代脱硝反应热安全性的理论研究

为研究硝基苯气相氟代脱硝反应的热安全性,采用Gaussian98软件,运用密度泛函理论(DFT)B3LYP,在6-31G(D)基组水平上,全优化计算气相条件下氟离子对硝基苯进攻的氟代脱硝反应的微观机理,得到反应路径并通过IRC验证,并对反应过程中反应物,各中间体、过渡态、产物进行分子几何构型优化,标准热力学函数计算。理论计算研究表明:该反应属于SN2亲核取代反应;反应能垒较低,反应所需能量可以从过程R→IM1和TS3→P所释放的能量(279.06 kJ/mol,143.34 kJ/mol)中获得;与席曼反应相比较,该反应速率下降3个数量级,热安全性更高,符合化工工程设计的本质安全化要求,具有广阔的应用前景。     

Numerical and experimental study of the explosions caused by residual pressure in quick actuating vessels

The explosion accident caused by residual pressure is one of the most common kinds of accidents in quick actuating pressure vessels. And it is important to provide some reliable methods, which can give reasonable analysis of the explosion. In this study, experiments of the explosion are preformed by using two quick actuating pressure vessels with residual pressure, and a new mathematical model is presented. The model is based on the combination of the Spalart-Allmaras turbulence fluid model and Newton’s second Law for the solid motion. And the model is solved with local remeshing method. By performing the simulation with the same parameters of experiments, the results of the simulation confirm the accuracy of the model. And the results shows the crucial factor of vessel structure, which the maximum ejected speed of the lid highly depends on. Based on that, the optimal design of the structure is presented, which can provide better security.     

外军皮肤防护器材化学防护性能测试与评价用标准物质研究进展

本文简迷了皮肤防护器材--化学防护服(衣)化学防护性能试验与评价用标准物质的重要性,系统地概述了外军化学防护服(衣)化学防护性能试验与评价用标准物质的研究现状,并提出了我国化学防护服(衣)防护性能试验与评价用标准物质研制过程中应注意的一些问题.     

新旧版GB6566《建筑材料放射性核素限量》比较研究

为了方便检测机构、消费者和企业理解掌握新版GB6566-2010标准内容,笔者对与旧标准相比的主要变化、标准具体内容进行了归纳整理,并对实际应用中应注意的问题加以解析。     

珠三角地区城市雨洪过程模拟与计算——以佛山市南海区北村水系为例

受城市化快速发展及其内在的土地利用、水系调整、高架桥建设等复杂因素影响,城市降雨、入渗、蒸发、径流及其污染物输移过程已发生很大改变,由此导致的城市内涝与水环境污染等问题已经成为制约当地经济社会可持续发展的重要因素.基于城市雨洪径流传输过程模拟模型SWMM(Storm Water Management Model)对广东省佛山市南海区北村水系雨洪过程进行模拟计算,分析得到不同降雨和土地利用条件下北村水系雨洪可利用量及径流过程、地表污染物入河量及输移过程规律.结果表明,随降雨频率的减小,北村水系主要控制点的径流总量增大,面源污染物总量增大,通过增加城市绿地面积可以有效地减少洪水总量以及消减洪峰流量.     

Occurrence and behaviour of nonylphenol and octylphenol in Nanming River, Guiyang City, China

Occurrence, variation and behaviour of nonylphenol (NP) and octylphenol (OP) were studied in surface water and groundwater in Guiyang, Guizhou Province, southwestern China. Discharge of wastewater from Guiyang City was the main source of alkylphenols (APs) entering the aquatic environment. The concentrations of NP and OP in river water ranged from 40 to 1582 ng L(-1) and from below the lowest limit of detection (LOD) to 67 ng L(-1), respectively. NP and OP were also detected in groundwater. Both NP and OP exhibited spatial and temporal variations in river water and groundwater. It was found that concentrations of NP and OP in river water was low upstream and dramatically increased downstream, and higher concentration of NP was found in winter compared to that in summer. Proportions of NP and OP were trapped by suspended particulate matter (SPM), which accounted for 7.6-50.0% and 3.4-25.6% of their total concentration in the river water system, respectively. Seasonal changes in water flow were responsible for the temporal variations of APs. To determine the behaviour of APs along the river, a mass balance equation based on chloride was used. The results showed that a mixing process was the predominant factor to determine upstream APs concentrations; while the discharge of wastewater controlled the concentrations of APs downstream. Considering the adverse effect of APs on organisms, combined effect modeling was used to assess the toxicity to fish. It was found that the predicted mixture effect for APs in river water on fish vitellogenin induction was low upstream and medium downstream, respectively.     

Matrix-bound phosphine and phosphorus fractions in paddy soils

Phosphine (PH(3)) is a natural gaseous carrier of phosphorus (P) in its geochemical cycles, and it might be important to the P balance of natural ecosystems. Paddy fields are thought to be one of the main sources responsible for the production and emission of PH(3) in to the environment. The relationships between matrix-bound PH(3) (MBP) and different P fractions, as well as selected metals were investigated to explore the possible production of MBP and its link to P cycle in the paddy soils. MBP range from 20.8 (-1) to 502 ng kg(-1) with an average of 145 ng kg(-1). Concentrations at the milk stage are significantly higher than at the jointing stage. The total P range from 333 mg kg(-1) to 592 mg kg(-1). Average P fractions decrease in the order: Ca-P (69.9%) > Organic P (16.5%) > occluded P (6.50%) > Fe-P (5.93%) > dissolved P (0.80%) > exchangeable P (0.32%) > Al-P (0.02%). Different levels of nitrogen fertilizer have little effect on the contents of MBP, P fractions and metals. A significant positive correlation between MBP and Ca-P (p = 0.002), as well as between MBP and Ca (p = 0.008) could be observed, suggesting that Ca-P mainly affects the production of MBP in the paddy soils. It is suggested that soil MBP is strongly linked to Ca-P fertilizer use because soil spiked with P-fertilizer produced an additional 758 ± 142 ng of MBP per kg of soil, compared to only 81.7 ± 12.3 ng of MBP per kg of unspiked soil. No correlations are found between MBP and other P fractions, or between MBP and Al, Fe and Mn.     

Mobilization and plant accumulation of prometryne in soil by two different sources of organic matter

Prometryne is a selective herbicide of the s-triazine chemical family. Due to its weak absorption onto soil, it readily leaches down through the soil and contaminates underground water. Application of organic manure to soil has become a widespread practice as a disposal strategy to improve soil properties. In this study, we demonstrated the effect of pig manure compost (PMC) and lake-bed sludge (SL) on the sorption/desorption, mobility and bioavailability of prometryne in soil using comprehensive analysis approaches. Downward movement of prometryne was monitored in the packed soil column. Addition of PMC or SL decreased considerably the mobility and total concentration of prometryne in the soil leachate. Bioavailability analyses with wheat plants revealed that addition of the organic matter reduced accumulation of prometryne in tissues and increased plant elongation and biomass. These results indicate that the organic amendments are effective in modifying adsorption and mobility of the pesticide in soil.     

矿山地质环境质量评价数学模型研究概述

在对大量文献和典型矿山地质调查资料研究的基础上,从矿山环境地质问题所导致的结果(资源损毁、地质灾害、环境污染)出发,筛选出合理的评价因子并建立评价指标体系.采用不同的评价方法,通过进行现状—预测—综合评价最终确定矿山地质环境质量评价数学模型;并将评价方法应用于实际矿山地质环境质量评价中,获得了较好的一致性.     

莱州湾西南部岸线变迁对海域水动力影响的数值研究

20世纪70年代以来,盐田、养殖围堤、港口堤坝建设等开发活动使莱州湾西南部岸线变迁尤为显著,从而引起了海湾水动力环境的改变。为探究近50年莱州湾水动力环境对海湾西南部岸线变迁的响应,本文建立二维数值模型,研究莱州湾西南部3个时段岸线变迁对海湾潮流、纳潮量和水交换的影响。结果表明,1968－2020年莱州湾西南部流速变化以减小为主,流速变化较大的区域主要位于盐田或养殖围垦区和新建港口附近海域。近50年,莱州湾纳潮量呈逐年减小趋势,大潮、中潮、小潮和全潮平均纳潮量分别减少5.85%、7.28%、8.85%和6.47%,围填海是导致纳潮量减小的主要原因。1968－2010年莱州湾整体的水交换能力有所提高,2010－2020年则相差很小;从局部看,1990－2020年港口附近海域的水交换能力均显著降低。