氢气还原海绵铁去除水体中硝酸盐的研究

利用小球烧结和氢气还原工艺制备了粒径1mm～5mm的多孔性球形海绵铁,对球形海绵铁去除水体中硝酸盐的效率及去除动力学进行了研究。结果表明:溶液初始pH值对硝酸盐去除效率的影响显著,初始pH值小于3时,硝酸盐的去除率随溶液初始pH的增加而逐渐降低;初始pH值大于3时,硝酸盐的去除率又随之升高。硝酸盐浓度低于10mgN/L时,硝酸盐去除率随着硝酸盐初始浓度的增加而增加,硝酸盐的残余量保持在0.4mgN/L左右;硝酸盐浓度高于20mgN/L时,硝酸盐的去除率随初始硝酸盐浓度的增加而略有降低。球形海绵铁去除硝酸盐为一级动力学反应,反应级数为0.970～1.378,表观反应速率常数为0.314h-1～0.536h-1。海绵铁还原硝酸盐的主要产物为氨氮,随着还原反应的进行,溶液pH值快速增加,氨氮以分子态氨的形式从水中逸出。进行归纳总结和对比,并以多环芳烃的提取为例列举了各方法的应用步骤,从而为其他环境样品其他有机物分析预处理提供参考。     

纳米铁系材料与反硝化细菌复合去除地下水硝酸盐氮研究

采用不同液相还原法制备了纳米Fe、纳米Fe/Ni和油酸钠包覆型纳米Fe粒子,并将其与反硝化细菌复合应用于地下水中硝酸盐氮的去除研究中.分别考察了不同纳米铁系材料与反硝化细菌复合体系去除硝酸盐氮的反应速率及对脱氮产物生成的影响.同时,从核糖核酸(RNA)水平考察了不同纳米铁系材料对反硝化细菌的影响.结果表明,纳米Fe/Ni复合体系脱氮速率最快,6d内对硝酸盐氮的去除率可达到100%,最终产物主要为氨氮,占体系总氮的69%;而纳米Fe和油酸钠包覆型纳米Fe复合体系9d可将硝酸盐氮100%去除,氨氮的转化率分别为52%和16%.另外,从反应前后反硝化细菌总RNA浓度的变化情况看,纳米Fe/Ni复合体系、纳米Fe复合体系和油酸钠包覆型纳米Fe复合体系的反硝化细菌总RNA浓度分别降低了93%、40%和34%,可见3种纳米铁系材料对反硝化细菌毒性大小顺序为:纳米Fe/Ni纳米Fe油酸钠包覆型纳米Fe.     

纳米催化剂Pd/SnO_2的制备及催化还原硝酸盐反应的调控

采用热分解法制备了SnO2载体,并用浸渍法制备了Pd/SnO2催化剂.同时,采用X射线衍射仪(XRD)、透射电镜(TEM)、扫描电镜(SEM)及BET比表面积仪等对所制载体和催化剂材料进行了分析表征.结果表明,热分解法和浸渍法都能够获得纳米材料,SnO2及Pd/SnO2的粒径均在9～10nm左右,比表面积分别达到144.99m·2g-1和147.36m·2g-1.在以甲酸为还原剂的Pd/SnO2催化还原硝酸盐体系中,在Pd与SnO2负载比为2%～7%,反应温度为20～50℃和甲酸投加量4.0～24.0mmol·L-1的条件下,催化活性为0.70～9.48mg·min-·1g-1,且催化活性随着负载比、温度和甲酸投加量的增大而增大,随着pH的升高先升后降,最佳pH为3.反应温度升高及pH降低都能够提高Pd/SnO2的选择性.甲酸-Pd/SnO2催化还原硝酸盐体系中还原反应的调控策略为:反应温度宜控制在40～50℃内,这样可同时获得较高的催化活性和选择性,温度过高对催化活性和选择性影响很小,温度过低则会同时降低催化活性和选择性;控制pH为3时,可以获得最大的催化活性及较好的选择性,pH升高会降低Pd/SnO2的催化活性和选择性,pH降低会导致催化活性迅速降低,但对选择性影响不大;甲酸与硝酸盐的物质的量比宜大于4:1,此时可以有效地抑制pH的上升,同时获得较高的催化活性和选择性,甲酸与硝酸盐的物质的量比小于4:1时,会同时降低Pd/SnO2的催化活性和选择性.     

Investigative consequence analysis: A case study research of beirut explosion accident

Around 15:00 GMT on August 4th, an explosion occurred in the warehouse facility storing Ammonium Nitrate (AN) at Beirut port, Lebanon. The explosion resulted in more than 178 fatalities and injured more than 6500 people, and also left an estimated 300,000 people homeless and registered as an equivalent to a 3.3 magnitude earth quake. The accident was considered to be the largest of its kind and the most severe anthropological disaster of the decade, the financial loss the nation was subjected to post the explosion was estimated to be around $ 15 billion as informed by the governor. The storage conditions of ammonium nitrate at Beirut port is not definitively known to anyone, and there is no documentation provided so far from the authorities regarding the same. This work focuses on the investigation & consequence analysis of the explosion using TNT equivalent approach. The overpressure and the impulse obtained from TNT calculations are used in probit models to assess the damages caused on human beings and structures. The results obtained in this investigative approach are then utilized to provide an analytical inference relative to the damage proxy map reported by the advance rapid imaging analysis team from NASA. Also, this work examines the existing standards, fire safety measures and legal regulations for ammonium nitrate facilities in the region. AN explosion during storage like other fire and explosion accidents are definitely preventable owing to the technological advancements and developments to prevent or extinguish controllable fires. The significance of this work relates to the methods for calculation of consequences of explosion that are happening due to the storage of highly hazardous explosive materials in excessive quantities and insists the necessity of incorporating adequate safety measures while storing such reactive and hazardous materials.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

岩溶地下河反硝化作用的有限性——一个碳酸盐岩管道的实验研究

反硝化作用是公认的去除水体中硝酸盐的路径,但相比于多孔介质,岩溶地下河中反硝化效果具有不确定性.为更好地认识岩溶地下河中反硝化效果,本研究利用天然碳酸盐岩管道几何模型,以乙醇为可利用电子供体(碳源),示踪了控制流速条件下管道流中反硝化作用,并辅以多孔介质流实验进行对比.反应示踪、地球化学印迹和微生物检测结果表明:当碳源缺乏时,反硝化作用没有明显启动的迹象;一旦补充了碳源,溶解氧、硝酸盐浓度和质量都出现了明显衰减,并且有中间产物亚硝酸盐产生,水体碱度增加.然而,即使在碳源充足情况下,管道流中反硝化强度却明显比多孔介质流中强度低,两者硝酸盐生物去除率分别为39.4%和大于99%,生物降解速率分别为0.113和10.8 mg·L~(-1)·h~(-1).推测其原因,一是碳酸盐岩管道内固体表面积与水体积比值低,固体吸着条件不利于微生物生长与发育,降低了硝酸盐去除率;二是管道富含的溶解氧可能延迟了反硝化作用启动,溶解氧降至3.0 mg·L~(-1)左右时硝酸盐浓度才有明显衰减.相比之下,其它环境因素如p H值和温度没有出现明显变化.该研究意义在于:岩溶管道流反硝化去除硝酸盐的潜能是存在的,但即使可利用碳源充足仍具有明显的局限性,这可能意味着岩溶地下河一旦遭受硝酸盐污染,其作为饮用水源的安全风险更大.     

用CARIX工艺去除饮用水中硝酸盐的改进研究

针对硬度低而硝酸盐含量高的原水,采用阴离子交换柱研究了用改进型ＣＡＲＩＸ工艺提高了对于下水中硝酸盐的去除,除盐过程中,水中硝酸根和硫酸根等阴离子被碳酸氢根离子置换;再生阶段,用二氧化碳和氧化镁粉末,使树脂转变为重碳酸盐型。     

饮用水中硝酸盐去除方法比较

本文综述了饮用水中硝酸盐的各种去除方法及其优缺点.通过分析比较,认为离子交换法和生物反硝化法都可用于大规模生产饮用水,但最有发展前途目前研究最多的是生物反硝化法.该法将硝酸盐转化为氮气,无废液产生,处理费用低.但异氧反硝化法需进行复杂的后处理除去过量的有机物,自养反硝化法会造成出水硫酸盐含量增高.     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Main particulate matter components in Saxony (Germany)

Aerosol filter samples have been collected nearby the industrialised basin of Leipzig in Saxony (Germany) at the research station Melpitz of the Institut für Troposphärenforschung e.V. (IfT). Time series (1992–1998) and a three year comparison (1995–1997) of two different aerosol filter sampling systems, the Sierra-Andersen-PM 10 high volume sampler (daily sample, PM 10 inlet) and the Rupprecht and Patashnik Co. Inc. Model Partisol 2000 (weekly sample, PM 10 and PM 2.5 inlet) are presented and discussed. The comparison of the different sampling systems and strategies yields small differences between the daily and weekly samples for mass and different ions, which may be influenced by sampling duration and flow rates. A general trend of change in aerosol composition was observed: Soot and Sulphate concentrations decreased whereas Nitrate and Ammonium concentrations increased. During summers the mass of coarse particles is higher than in other seasons. One reason could be found in the occurence of longer periods of dry ground surfaces enabling reemission of crustal and biological material. The time series have been integrated in a longer historical aerosol mass trend for Saxony and do show a good agreement. Since 1990 a significant downward trend in gravimetric mass concentration was found.