Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration,humidity effect and reduced electric field dependency

Green leaf volatiles (GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds (BVOCs). Proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field, etc. In this study the influence of gas humidity and the effect of reduced field (E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to 10 ncps/ppbv (normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity (RH) at 21°C, with the exception of (E)-2-hexenol. Product ion branching ratios were also affected by humidity, with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field (E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.     

涕灭威农药废水治理技术和应用

根据涕灭威农药恶臭废水的特点,依据资源化治理的思路,对废水采用了物理化学和生物处理相结合的治理方法.治理工艺路线如下:废水先通过盐酸酸化,可回收H2S、CH3SH,然后通过Cl2氧化和铁炭法进一步预处理来提高其可生化性,最后进入生化处理设施.涕灭威农药废水经资源化治理和Cl2氧化、铁炭预处理后,小试和中试过程中,COD平均去除率分别为90.7%与87.3%,BOD5/COD分别从0上升到0.38与0.31,废水的可生化性能得到了很好的改善,解决了农药生产有机废水生化处理存在的可生化性差的问题.生化出水COD达到国家污水综合排放标准GB 8978-1996中的一级标准100mg/L以下.该工艺在华阳集团每天处理10t废水的中试铁炭预处理实验装置中得到应用.     

BTF系统处理兼氧池高浓度恶臭废气的工程应用

在制药厂建立了生物滴滤处理兼氧池高浓度恶臭废气工程装置.兼氧池恶臭成分主要是H2S,同时含有甲苯及四氢呋喃等气态有机物.设计进气量为8 000 m3/h,有效EBRT为12.0 s,当H2S进气质量浓度为394.26～776.52 mg/m3、平均为524.36 mg/m3时,H2S去除率保持在86.53%～94.79%,平均去除率为90.60%;去除负荷为59.14～122.63 g/(m3·h),平均去除负荷为81.47 g/(m3·h).对甲苯和四氢呋喃的平均去除率为66.84%和59.89%.技术经济分析表明,处理1 000 m3废气投资费用为13.32万元,H2S处理费用为5.23元/kg.     

珠江虎门河口表层沉积物中酸可挥发性硫化物的重金属同步提取

测定了珠江虎门河口16个站位的表层沉积物样品中的酸可挥发性硫化物(AVS)和同步提取重金属(SEM)Cu、Co、Cr、Pb、Zn、Cd、Ni、Ba和V的含量。结果表明,AVS的浓度范围为0.13～31.68μmol/g,平均值为8.54μmol/g;SEM的浓度范围为0.37～5.54μ/g,平均值为1.84μ/g。采用SEM/AVS比值评价方法和SEM-AVS差值评价方法预测沉积物中重金属的生物有效性,结果表明,除P3、P13、P16、P19、P20的表层沉积物中重金属对水生生物可能具有中等毒性水平外,其余站点的表层沉积物中重金属对水生生物无不良影响。     

石油化工企业硫化氢泄漏事故环境风险分析

采用风险预测模型SEVEX,在各种不利气象条件下,对硫磺回收装置酸性气管线泄漏的硫化氢的扩散情况进行了模拟分析.结果表明:风险影响区域不仅与硫化氢泄漏的源强有关,而且与事故状态下的气象条件密切相关,在风速大、不稳定的气象条件下,硫化氢泄漏形成的高浓度区多分布在事故源的近距离处;而在静小风、稳定的气象条件下,高浓度区分布范围较大.据此,可以制定应急计划和撤离方案,减轻事故带来的不良影响.     

锰钾矿氧化硫化物特性与动力学研究

锰钾矿是表生环境中常见的氧化锰矿物,影响土壤溶液中硫化物的迁移、转化和归趋,考察了无氧条件下锰钾矿氧化硫化钠溶液的反应过程,采用分光光度法、离子色谱法分析S^2-及其氧化产物的浓度和变化趋势,用XRD、SEM表征锰钾矿粉末反应前后的晶体结构和微观形貌,探讨了溶液温度、pH值、矿物用量以及锰钾矿锰氧化度（AOS）对S。初...     

粤北某矿横石河流域周围土壤重金属预测与生态风险预警评估

以粤北某矿横石河流域周围表层土壤2010年和2013年两批区域调查数据为基础,对其土壤中重金属含量变化趋势进行预测,并进行生态风险预警评估。结果显示,3年间土壤中Cd、Cu、Pb、Zn等元素含量降低明显,现累积速率分别为-0.001、2.88、3.71和3.11mg/(kg·a),相对累积速率以Cd最快,Zn、Cu、Pb次之;生态风险预警评估显示凉桥村和水楼下村的生态风险达到重警,上坝村为轻警。在无突变情景下,根据现累积速率预测了未来30年内的生态环境质量变化,并提出建议。     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide(COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations(R2 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes(ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

基于化学反应动力学机理的中等尺寸甲烷湍流扩散火焰的数值模拟

通过代码修改,在大涡模拟(LES)中嵌入气相化学反应速率、组分热力学性质和输运特性三大机理文件,严格意义上实现甲烷燃烧的四步简化机理与火灾动力学模拟软件(FDS)的成功对接。燃烧模型采用针对多组分燃料的涡耗散概念(EDC)模型,模拟0.3m直径的甲烷湍流扩散火焰,并分别与基于无限快反应速率的总包单步和两步化学反应预测结果对比。分析预测结果可知:四步机理能够很好的适应FDS框架,其模拟结果具有可靠性,时均温度、速度和主要反应物的预测结果高度一致;机理导入后可以预测CO2、H2O以及中间产物CO和H2的浓度,更合理地描述了火灾中气相产物的产生与输运过程。不同反应机制下主产物CO2和H2O浓度对比结果理想,在高温反应区内存在一定的差异,在高温反应区外呈现出高度的一致性。     

Numerical and reduced-scale experimental investigation of blast wave shape in underground transportation infrastructure

When an explosion occurs in a tunnel, the study of the blast wave quickly becomes complicated, owing to the multiple propagation patterns of the blast wave (incident wave, regular and Mach reflections) and to the geometrical conditions. Considering this problem, two patterns can be revealed. Near the explosive, the well-known free-field pressure wave can be observed. After multiple reflections on the tunnel's walls, this overpressure behaves like a one-dimensional (1D) wave. One aim of this paper is to determine the position of this transition spherical-to-planar wave propagation in a tunnel using both numerical and reduced-scale experiments, and thereby validate the dedicated law established in a previous work.For this purpose, a detonation of TNT in a tunnel with a cross-section of up to 55 m² is considered. Results show good agreement between the numerical simulations and experiments. The transition zone between the three-dimensional (3D) and the 1D wave is well detected. An application to a simplified subway station is also investigated which shows that significant planar waves can be transmitted to the neighboring stations via the junction tunnels.