Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide

Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous oxidation with hydrogen peroxide(H2O2) has been suggested to be a potential pathway for secondary organic aerosol(SOA) formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol(MBO321), an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4–H2O2mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients(γ) were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol(MBO232) and yield isoprene in acidic media. Organic hydroperoxides(ROOHs) were found to be generated through the acid-catalyzed route,which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.     

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of 8180 and 82H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature （Tair）, with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial- temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world.     

Production and emission of phosphine gas from wetland ecosystems

Phosphine is a part of an atmospheric link of phosphorus cycle on earth, which could be an important pathway for phosphorus transport in environment.Wetland ecosystems are important locations for global biogeochemical phosphorus cycle.In this study, production and emission fluxes of free phosphine from four wetlands types in southern China were observed in different seasons.The results showed that the concentration of phosphine liberated from wetlands was at pg/m3-ng/m3 level.The emission concentrations of different wetlands followed the sequence:paddy field(51.83 ± 3.06) ng/m3 marsh(46.54 ± 20.55) ng/m3 lake(37.05 ± 22.74) ng/m3 coastal wetland(1.71 ± 0.73) ng/m3, the positive phosphine emission flux occurred in rice paddy field(6.67 ± 5.18) ng/(m2·hr) and marsh(6.23 ± 26.9) ng/(m2·hr), while a negative phosphine flux of(-13.11 ± 35.04) ng/(m2·hr) was observed on the water-air interface of Lake Taihu, suggesting that paddy field and marsh may be important sources for phosphine gas in atmosphere, while lake may be a sink of atmospheric phosphine gas during the sampling period.Atmospheric phosphine levels and emission flux from Yancheng marsh and rice paddy field varied in different seasons and vegetational zones.Both diffusion resistance in aqueous phase and temperature were dominating factors for the production and transportation of phosphine to atmosphere.     

Kinetics study on photochemical oxidation of polyacrylamide by ozone combined with hydrogen peroxide and ultraviolet radiation

An investigation on the process of ozone combined with hydrogen peroxide and ultraviolet radiation has been carried out in order to establish the kinetics for photochemical oxidation of polyacrylamide （PAM） in aqueous solution. Effects of operating parameters, including initial PAM concentration, dosages of ozone and hydrogen peroxide, UV radiation and pH value on the photochemical oxidation of PAM, have been studied. There was an increase in photochemical oxidation rate of PAM with increasing of dosages of 03, H2O2 and ultraviolet radiation. Upon increasing of the initial PAM concentration, the photochemical oxidation rate of PAM decreased. Slight effect of pH value on the photochemical oxidation rate of PAM was observed in the experiments. The kinetics equation for the photochemical oxidation of PAM by the system has been established.     

Gas separation using porous cement membrane

Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.     

Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols

Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298 ± 1 K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were(1.91 ± 0.19) × 10~(-17),(1.89 ± 0.20) × 10~(-17), and(0.83 ± 0.08) × 10~(-17)cm~3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon–carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.     

Direct radiative forcing of urban aerosols over Pretoria (25.75°S, 28.28°E) using AERONET Sunphotometer data: First scientific results and environmental impact

The present study uses the data collected from Cimel Sunphotometer of Aerosol Robotic Network（AERONET） for the period from January to December, 2012 over an urban site,Pretoria（PTR; 25.75°S, 28.28°E, 1449 m above sea level）, South Africa. We found that monthly mean aerosol optical depth（AOD, τa） exhibits two maxima that occurred in summer（February） and winter（August） having values of 0.36 ± 0.19 and 0.25 ± 0.14,respectively, high-to-moderate values in spring and thereafter, decreases from autumn with a minima in early winter（June） 0.12 ± 0.07. The Angstrom exponents（α440–870） likewise,have its peak in summer（January） 1.70 ± 0.21 and lowest in early winter（June） 1.38 ± 0.26,while the columnar water vapor（CWV） followed AOD pattern with high values（summer） at the beginning of the year（February, 2.10 ± 0.37 cm） and low values（winter） in the middle of the year（July, 0.66 ± 0.21 cm）. The volume size distribution（VSD） in the fine-mode is higher in the summer and spring seasons, whereas in the coarse mode the VSD is higher in the winter and lower in the summer due to the hygroscopic growth of aerosol particles.The single scattering albedo（SSA） ranged from 0.85 to 0.96 at 440 nm over PTR for the entire study period. The averaged aerosol radiative forcing（ARF） computed using SBDART model at the top of the atmosphere（TOA） was- 8.78 ± 3.1 W/m2, while at the surface it was- 25.69 ± 8.1 W/m2 leading to an atmospheric forcing of ＋ 16.91 ± 6.8 W/m2, indicating significant heating of the atmosphere with a mean of 0.47 K/day.     

Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere and troposphere

The hydroxyl radical (?OH) has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health. Nevertheless, high reactivity, low atmospheric abundance, determination of hydroxyl, and hydroperoxyl radical's quantity is very difficult. In the atmosphere and troposphere, hydroperoxyl radicals (HO₂) are closely demanded in the chemical oxidation of the troposphere. But advances in technology have allowed researchers to improve the determination methods on the research of free radicals through some spectroscopic techniques. So far, several methods such as laser-induced fluorescence (LIF), high-performance liquid chromatography (HPLC), and chemical ionization mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals. In this systematic review, we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals. The primary goal of this review is to deepen our understanding of the functions of the most critical free radical (?OH, HO₂) and also understand the currently used methods to quantify them in the atmosphere and troposphere.     

酶催化光度法测定雨水中微量H_2O_2的研究

研究了过氧化氢酶/4-氨基安替比林/苯酚/过氧化氢催化体系显色反应的最佳条件,实验发现:在温度为25℃,pH为7.0的条件下催化反应30min,所形成的催化反应产物在505nm处有最大吸收,H2O2在0.003～0.3000μmol/mL呈良好线性关系,其检测限达0.002μmol/mL(S/N=3),相对标准偏差RSD=0.24%(C=0.1000μmol/mL,n=10)。该法具有所用仪器简单,操作方便,灵敏度高等特点,应用于雨水中微量过氧化氢的测定,结果满意。     

经丁二酮肟修饰的改性皂土对废水中镍的吸附

采用十六烷基三甲基溴化铵(CTMAB)对皂土改性,用丁二酮肟(DMG)对其表面修饰,并制备了新型固态吸附剂.研究了该吸附剂对水中Ni2+的吸附行为.结果表明,该固态吸附剂对水中Ni2+具有较强的吸附能力.吸附量受介质pH值、温度和吸附时间的影响.其吸附行为符合Langmuir吸附等温模型和HO准二级动力学方程,吸附焓变(△H)为58.759kJ/mol,各温度下,吸附自由能变(△G)均＜0,熵变(△S)均＞0,该吸附反应为吸热的自发过程.吸附了Ni2+的丁二酮肟修饰改性皂土,可用0.1mol/L的HNO3溶液洗脱再生.     

双氧化剂光催化降解水中邻苯二甲酸酯类污染物

采用过硫酸钠/双氧水双氧化体系光催化氧化降解水中邻苯二甲酸酯类有机污染物,考察了过硫酸钠/双氧水的投加比例、紫外光强、溶液pH以及邻苯二甲酸二辛酯(DOP)的初始浓度等因素对降解率的影响,并在优化条件下对降解反应的动力学进行了考察。结果表明:室温下,过硫酸钠和双氧水浓度均为0.2mol/L且体积比为1:1,pH=7.0,光照距离为0.5cm,反应80min,DOP降解率达98%以上,反应动力学研究表明,过硫酸钠/双氧水双氧化体系光催化氧化降解水中DOP反应为表观一级。优于相同条件下两种氧化剂单独使用对DOP的降解效果。     

UV/H2O2/草酸铁处理垃圾渗滤液的研究

利用UV(125 W)/H₂O₂/草酸铁处理已经过生化处理的垃圾渗滤液(CODCr为450 mg/L)时,反应较佳条件是pH值为4.0及总药剂用量为14 mL/L.草酸铁的用量要适当,投加量过少,混凝效果较差,有效光子不能完全转化为化学能,处理效果不理想;投加量过多,溶液形成棕色混浊,使紫外光的吸收降低,造成光散射,降低反应速度.而H₂O₂的投加量过多,将使铁的络合物更加稳定,H₂O₂的分解速率受到限制,投加量过少,效果也会降低.当总药剂用量为14 mL/L(其中30%过氧化氢6 mL/L,0.1 mol/L草酸铁溶液8 mL/L)时,反应30 min后,CODCr去除率可达80%左右,脱色率可达90%以上.      

活性炭催化双氧水氧化处理分散橙结晶废母液

采用Fe2+/H2O2、活性炭(AC)/H2O2和AC/H2O2/Fe2+三种氧化体系对高浓度、高酸度和高盐分的分散橙结晶废母液进行处理,探讨了H2O2投加量、n(H2O2)/n(Fe2+)比值和初始pH对TOC去除率影响,比较三种氧化体系对TOC和色度的去除效果。结果表明:AC/H2O2/Fe2+氧化体系对TOC去除率最高,AC/H2O2氧化体系对色度去除率最高。即使在强酸环境中下,AC对H2O2仍然具有较高的催化活性,并可多次重复利用。AC/H2O2氧化体系为分散橙结晶废母液处理及资源化利用提供了新途径。     

CoTPPS4催化处理敌敌畏生产废水的研究

用CoTPPS4作催化剂,Na2S2O8/H2O2为混合氧化剂处理含DDVP农药生产废水.探讨了氧化刺种类、混合氧化剂比例、催化剂投加量、农药初始浓度和pH值等因素对催化处理活性的影响,并对催化处理反应动力学进行了研究.结果表明,在pH＝9溶液中,农药初始浓度为28.93 mg/L、CoTPPS4加入量为2.4×10-...     

糖厂污泥中高效产氢菌的分离鉴定及产氢优化

从甘蔗糖厂污泥样品中,分离纯化得到一株革兰氏阳性厌氧产氢菌。经16S rDNA分子生物学鉴定,该菌株为Clostridium sp.60E(注册号:JF708079)。对该菌株生长及产氢特性的研究发现,其产氢主要发生在细胞生长对数期的中后期和稳定期。温度及pH值单因素实验显示,Clostridium sp.60E为一株中温产氢菌,有较好的耐酸能力。采用正交实验研究方法优化产氢条件,发现起始pH值为5,培养温度为35℃,碳源选择葡萄糖时,其总产氢量最高可达到(208±8.01)mL H2/100 mL培养基,比优化前提高了142%,产氢纯度最高达到55.32%,最高产氢速率为(188±8.72)mL H2/(L.h)、15.99 mmo(l H)2g(/dry cell.h)。以上研究表明,从糖厂污泥中筛选的Clostridium sp.60E是一株良好的厌氧发酵产氢菌,将其应用于废水处理,可以实现有机废水的高效制氢,是实现废水和有机废物资源化的一条有效途径。     

O3/H2O2降解水中致嗅物质2-MIB的效能与机理

采用O3/H2O2工艺对水中致嗅物质二甲基异莰醇(2-methylisoborneol,2-MIB)的去除效能与机理进行了研究,探讨了H2O2与O2的投加方式、摩尔比以及溶液pH值和水质等因素对2-MIB降解的影响,并通过Gc-MS对2-MIB的氧化降解中间产物进行了分析.实验结果显示,H202能明显促进O3对水中2-MIB的氧化降解.单独臭氧氧化2Omin时2-MIB的降解率为38.7%;在同样体系中加入适量的H202后2.MIB的降解率最大能提高到89.2%,H202与O3最佳投加摩尔比为0.6左右.低浓度(0.5 mg·L-1)腐殖酸对O3/H2O2体系2.MIB的降解速率有比较明显的促进作用,高浓度的腐殖酸则会产生较明显的抑制作用;自由基捕获剂叔丁醇对O3/H2O2体系中2-MIB氧化降解具有明显的抑制作用.鉴定出2-MIB的氧化降解产物有4-羟基-1,7,7-三甲基双环[2,2,1]庚烷-2-酮、1,7,7-三甲基双环[2,2,1]庚烷-2,4-二酮、1,7,7-三甲基双环[2,2,1]庚烷-2-酮等,并对2-MIB氧化机制和降解的可能途径进行了推导.     

一株耐酸产氢突变株Pantoea agglomerans的筛选与产氢特性

以红树林污泥中分离的厌氧发酵产氢细菌Pantoea agglomerans BH18为出发菌株,利用转座子Tn7随机插入菌株基因组DNA,通过卡那霉素筛选与PCR扩增验证,获得一批转座子插入突变菌株.起始pH4.0培养条件下,以产氢量为指标分离获得一株耐酸产氢突变菌株TB220.多次传代结果表明,突变菌株TB220具有稳定的产氢遗传特性.起始pH3.5~7.0范围内,突变菌株TB220最适产氢pH值为6.0,产氢量为(2.39±0.08)mol H2/mol葡萄糖.起始pH4.0和葡萄糖浓度10g/L的海水培养条件下,突变菌株TB220产氢量为(0.47 ± 0.02)mol H2/mol葡萄糖,比野生菌株高70%,表现出较强耐酸性.