Competing esterification and oligomerization reactions of typical long-chain alcohols to secondary organic aerosol formation

Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations.The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH-groups to form carbenium ...     

Monitoring requirements for groundwaters under the influence of reclaimed water

Monitoring groundwaters under the influence of reclaimedwater must consider the major constituents of concern inreclaimed water. This research focused on the fate ofdissolved organic carbon and nitrogen species at field siteslocated throughout the Southwestern United States. Awatershed approach was developed to predict the fate ofdissolved organic carbon as a function of the drinking waterdissolved organic carbon concentration and the totaldissolved solids concentration in the reclaimed water. Extensive characterization of the dissolved organic carbonrecovered from groundwaters under the influence of reclaimedwater was done. With the exception of fluorescencespectroscopy, the dissolved organic carbon present ineffluent organic matter was similar in structure, characterand reactivity as compared to natural organic matter. Evidence for sustainable nitrogen removal mechanisms duringgroundwater recharge with reclaimed water was obtained. Theautotrophic reaction between ammonia and nitrate appears to amechanism for the removal nitrogen in a carbon-depletedenvironment. The monitoring tools and methodologiesdeveloped in this research can be used to assure protectionof public health and determine the sustainability of indirectpotable reuse projects.     

UV/NO3-光化学降解水中的磺胺甲恶唑

本文研究了UV/NO₃^-体系对水中磺胺甲恶唑（SMX）的降解;考察了NO₃^-用量、pH值、SMX初始浓度、水体成分中常见的无机阴离子（Cl^-、SO₄^2-和HCO₃^-）和天然有机物（NOM）对SMX去除的影响;最后探讨了SMX在该体系中的降解产物和转化机理.结果表明：相比于单独UV,UV/NO₃^-对SMX的去除效果更优,这可能归因于UV激发NO₃^-产生的羟基自由基（HO^·）,通过加入HO^·淬灭剂甲醇,有力地证明了体系中HO^·的存在及其对SMX的降解作用.SMX在UV/NO₃^-体系中的降解符合准一级反应动力学.SMX的去除效率随着NO₃^-浓度的增加而逐渐提高,随着其初始浓度的增大而减小.溶液pH值对UV/NO₃^-降解SMX的影响显著,SMX去除效率表现为酸性>中性>碱性.向UV/NO₃^-体系中加入不同浓度的Cl^-和SO₄^2-对SMX的降解基本没有影响;HCO₃^-对SMX的去除有显著的促进作用,这可能归因于HO^·同HCO₃^-反应产生的碳酸根自由基（CO₃^·-）;NOM的存在会抑制SMX的降解,且NOM浓度越高,抑制越明显.在UV/NO₃^-降解SMX的反应中,根据检出的5种产物,提出SMX可能的转化机理包括4种不同的反应路径,分别为断键反应、脱氨羟基化、羟基化和亚硝化.     

总大肠菌群测定中如何避免出现不定值

现行的环境监测分析方法与有关技术规范中总大肠菌群检数表里所列的几个不定值(“<”或“>”)给区域环境综合分析与评价工作带来一定的困难.为了避免在实测数据中出现不定值,实验分析人员应充分了解待检水样的环境因素以便确定合适的分析方法.对污染较重的水样要适当提高稀释倍数直至出现阴性反应.能否选择出正确的稀释度是实验成败的关键.     

Simulator study of young driver's instinctive response of lower extremity to a collision

Objective: A driver's instinctive response of the lower extremity in braking movement consists of two parts, including reaction time and braking reaction behavior. It is critical to consider these two components when conducting studies concerning driver's brake movement intention and injury analysis. The purposes of this study were to investigate the driver reaction time to an oncoming collision and muscle activation of lower extremity muscles at the collision moment. The ultimate goal is to provide data that aid in both the optimization of intervention time of an active safety system and the improvement of precise protection performance of a passive safety system.

Method: A simulated collision scene was constructed in a driving simulator, and 40 young volunteers (20 male and 20 female) were recruited for tests. Vehicle control parameters and electromyography characteristics of eight muscles of the lower extremity were recorded. The driver reaction time was divided into pre-motor time (PMT) and muscle activation time (MAT). Muscle activation level (A_COL) at the collision moment was calculated and analysed.

Results: PMT was shortest for the tibialis anterior (TA) muscle (243～317 ms for male and 278～438 ms for female). Average MAT of the TA ranged from 28-55 ms. A_COL was large (5～31% for male and 5～23% for female) at 50 km/h, but small (<12%) at 100 km/h. A_COL of the gluteus maximus was smallest (<3%) in the 25 and 100 km/h tests. A_COL of RF of men was significantly smaller than that of women at different speeds.

Conclusions: Ankle dorsiflexion is firstly activated at the beginning of the emergency brake motion. Males showed stronger reaction ability than females, as suggested by male's shorter PMT. The detection of driver's brake intention is upwards of 55ms sooner after introducing the electromyography. Muscle activation of the lower extremity is an important factor for 50 km/h collision injury analysis. For higher speed collisions, this might not be a major factor. The activations of certain muscles may be ignored for crash injury analysis at certain speeds, such as gluteus maximus at 25 or 100 km/h. Furthermore, the activation of certain muscles should be differentiated between males and females during injury analysis.     

Thermal runaway criterion for chemical reaction systems: A modified divergence method

The chemical reaction in certain range of operating conditions may exhibit parametric sensitivity where small changes in one or more of the input parameters lead to changes in the output variables (eg. reaction temperature). The sharp rise of the reaction temperature is a critical behavior that may lead to runaway conditions. Thus, it is of vital importance to determine the critical operating parameters consisting of the parametric sensitivity region under the consideration of intrinsic safety. In this paper, a modified divergence criterion is proposed based on the trace of Jacobian matrix at the maximum temperature. The nonlinear differential equations describing the dynamic behavior of the chemical reaction is linearized locally in the vicinity of the equilibrium point by the small perturbation analysis. The relationship between the perturbation equation and parametric sensitivity of the reaction system is investigated. The critical values computed by the modified divergence criterion are compared with Morbidelli and Varma criterion (MV criterion), Adler and Enig criterion (AE criterion) and divergence criterion (Div criterion). The comparison demonstrates the validity of the new criterion. In addition, the critical explosion pressures of two kinds of hazardous chemicals are computed by the various critical criteria and compared with published experimental data. The results show that the modified divergence criterion could give smaller computational error compared with the previous criteria.     

大气汞均相和非均相化学反应过程研究进展

作为环境中汞传输的最重要通道,大气在汞的全球生物地球化学循环和传输扩散中起着极其关键的作用.大气环境成分复杂,汞在随大气环境传递过程中会经历复杂的化学反应,并导致不同形态之间相互转化,这也成为影响大气汞远距离传输尺度的关键因素.本文主要对大气汞在不同相界面之间的分配过程和主要影响因素(包括相界面的物理化学性质和外部环境条件等)进行了总结;对大气Hg0主要氧化反应过程(卤族元素氧化和O_3、OH·氧化)进行了阐述;对大气Hg~(2+)还原反应过程,尤其是光致还原反应等进行了梳理.如何综合运用野外监测分析和室内模拟等,利用微观分子表面分析等新技术明确大气汞均相、非均相反应过程,并将反应机理与大气汞传输过程模拟系统融合,将是未来大气汞研究的重要内容之一.     

温和水热法合成钛酸盐纳米管及其对水中重金属离子的吸附研究

采用温和水热法一步快速合成了钛酸盐纳米管(TNTs),并应用于对水中重金属离子Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的吸附.通过选择纳米级锐钛矿替代P25型二氧化钛作为反应原材料,成功将水热反应时间从72 h缩短至6 h.TEM,XRD和FT-IR等表征证实了新合成材料的为管状钛酸盐结构.TNTs对3种重金属离子的吸附动力学均符合准二级动力学方程,吸附等温线均符合Langmuir模型,且对Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的理论最大吸附量分别高达525.58、214.41和69.65 mg·g~(-1).p H=5时,吸附动力学实验表明对于初始浓度分别为200、100和50 mg·L~(-1)的Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ),在TNTs上的平衡吸附量分别为513.04、212.46和66.35 mg·g~(-1),吸附性能优于传统吸附材料.合成的TNTs结构为三联的[Ti O6]八面体骨架和层间H+/Na+,其吸附机理为金属阳离子与TNTs层间Na+的离子交换.同时,共存离子对吸附的影响实验表明TNTs对重金属离子的吸附存在选择性,即使在较高的共存离子浓度下(10 mmol·L~(-1))TNTs对目标重金属离子的吸附性能依然优异.该研究提供了一种应用钛酸纳米材料高效去除水体重金属离子的方法.     

Phosphorus-doped graphene supported palladium (Pd/PG) electrocatalyst for the hydrogen evolution reaction in PEM water electrolysis

PEM water electrolysis is one of the most efficient methods for the production of hydrogen because of produced high purity of the gases and environmentally friendly. In the present study, Phosphorus-doped Graphene (PG) was synthesized by thermal annealing of triphenylphosphine (TPP) and graphene oxide (GO). The PG supported palladium (Pd/PG) electrocatalysts were synthesized by chemical reduction method and used as the cathode for hydrogen evolution reaction (HER) electrode. Structural properties and electrochemical performances of the synthesized Pd/PG electrocatalyst were studied by FE-SEM, EDS, ICP, FT-IR, XRD, and Cyclic voltammetry (CV) methods, respectively. The membrane electrode assemblies (MEA’s) were fabricated using Pd/PG as cathode for HER electrode and RuO₂ as anode for OER electrode. Also, their electrochemical performances along with the corresponding hydrogen yields were evaluated in single cell PEM water electrolyzer at various experimental conditions such as different current densities from 0.1 to 2.0 A cm^?2 and temperatures (28–80°C). The synthesized Pd/PG electrocatalyst was observed a current density of 1 A cm^?2 with 1.95 V at 80°C. Further, long-term stability studies were carried out continuously up to 2000 h which showed a reasonable stability. Hence, the synthesized Pd/PG can be used as an alternative to Pt-based electrocatalysts for the HER in PEM water electrolysis.     

Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.