Kinetic modeling of fenton oxidation of phenol and monochlorophenols

A kinetic model, consisting of 28 reactions, was proposed to understand the key mechanism of the Fenton oxidation of phenol and o-, m-, and p-chlorophenols. Particular attention is paid to the interactions of the organic intermediates with the Fe species. The proposed model reasonably predicts the decomposition kinetics and by-product formation for the different phenols at widely varying levels of Fe2+, H2O2, and the phenols. For the phenols and intermediates, change in concentrations with time was predicted within 20-30% deviation from the measured data. The single model predicts the overall kinetics of Fenton oxidation of all the tested phenols by adjusting the rate constant of hydroxyl radical for each phenol. Sensitivity analysis indicates that the key reactions are those that directly govern the levels of OH radical and Fe2+. Both the model prediction and the experimental results show that the decomposition rate could be complicated particularly by the availability of Fe2+. Understanding the interactions of the organic intermediates with Fe2+ is thus of critical importance to improve the decomposition performance.     

Monitoring of reduced sulfur compounds in the atmosphere of Gosan, Jeju Island during the Spring of 2001

The atmospheric concentrations of dimethylsulfide (DMS) and carbon disulfide (CS2) were measured concurrently with relevant environmental parameters at Gosan, Jeju Island, Korea during 5-26 April 2001. The mean concentrations for these two compounds were 18.7+/-17.9 and 6.4+/-9.9 pptv, respectively. Results of our analysis indicated that relative temporal variations between DMS and CS2 can be best described by dividing the whole data set into three different periods which reflect the variable transport patterns of air masses into the study area. (Periods I, II, and III denote: 5-10, 10-18, and 19-26 April.) The environmental conditions during those three periods varied greatly. The effects of continental and/or oceanic processes were evident for certain periods, yielding diverse relationships between DMS and CS2 in both absolute and relative terms. Most observed variations were best explained in terms of an interplay between source/sink processes and air mass transport patterns. The sea-to-air flux of DMS, when estimated using our measurement data during this study period, was approximately 4 micromole m(-2)d(-1).     

Transport characteristics of gas phase ozone in unsaturated porous media for in-situ chemical oxidation

Encapsulation technology is being investigated as a method for controlling pH in situ at contaminated groundwater sites where pH may limit remediation of organic contaminants. This study examined the effectiveness of using KH2PO4 buffer encapsulated in a pH-sensitive coating to neutralize pH in laboratory sand columns (1.5-1) under a simulated groundwater flow rate and characterized the pattern of capsule release in the flow-through system. Denitrification was used in the columns to increase the pH of the pore water. Each of three columns was equipped with three miniature mesh wells to allow contact of the buffer with column pore water, but capsules (15 g) were inserted into only one column (amended). The two other columns served as amendment (no buffer) and abiotic (no denitrification) controls. Oxidation-reduction potential, dissolved organic and inorganic carbon, NH4+, NO3- +NO2-, PO(4)3-, and pH were measured in the influent, two side ports, and effluent of the columns over time. Near complete conversion of 80 mg N/1 of nitrate and 152 mg/l of ethanol per day resulted in a mean pH increase from 6.2 to 8.2 in the amendment control column. The amended column maintained the target pH of 7.0 +/- 0.2 for 4 weeks until the capsules began to be depleted, after which time the pH slowly started to increase. The capsules exhibited pulses of buffer release, and were effectively dissolved after 7.5 weeks of operation. Base-neutralizing capacity contributed by the encapsulated buffer over the entire study period, calculated as cation equivalents, was 120 mM compared to 8 mM without buffer. This study demonstrates the potential for this technology to mediate pH changes and provides the framework for future studies in the laboratory and in the field, in which pH is controlled in order to enhance organic contaminant remediation by pH-sensitive systems.     

Pre-oxidation and coagulation of textile wastewater by the Fenton process

This paper evaluates the Fenton process, involving oxidation and coagulation, for the removal of color and chemical oxygen demand (COD) from synthetic textile wastewater containing polyvinyl alcohol and a reactive dyestuff, R94H. The experimental variables studied include dosages of iron salts and hydrogen peroxide, oxidation time, mixing speed and organic content. The results show that color was removed mainly by Fenton oxidation. The color removal reached a maximum of 90% at a reaction time of 5 min under low dosages of H2O2 and Fe2+. In contrast, the COD was removed primarily by Fenton coagulation, rather than by Fenton oxidation. The ratio of removal efficiency between Fenton process and ferric coagulation was 5.6 for color removal and 1.2 for COD removal. It is concluded that Fenton process for the treatment of textile wastewater favors the removal of color rather than COD.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

Atmospheric concentrations of PM2.5 trace elements in the Seoul urban area of South Korea

Fine particles (PM2.5) were collected during all four seasons, from April 2001 to February 2002, in Seoul, South Korea, using an annular denuder system. Elemental compositions of ambient PM2.5 were analyzed using the proton-induced X-ray emission method. The greatest contributors (> or = 2%) to the PM2.5 mass were sulfur (S), silicon (Si), chlorine (Cl), aluminum (Al), and iron (Fe) in the spring; S in the summer; and S and Cl in the fall. S, Cl, and Si were the major elements in the winter. S was the most abundant species among the elements, ranging from 5.3 to 7.9%, followed by Si and Cl. From analysis of variance, PM2.5 mass, Al, Si, potassium, calcium, and Fe showed significant seasonal differences during the four seasons (p < 0.001). Enrichment factor (EF) analysis was carried out to identify the sources affecting the aerosol in the Seoul area. On the basis of the mean EF values, elemental S, copper, zinc, and lead may be emitted from anthropogenic sources (EF > 50). Elemental Al, Si, titanium, and Fe may be emitted from crustal sources (EF < 3). Additionally, a correlation analysis was carried out for source identification. The results of the correlation analysis were confirmed by the results of the EF analysis.     

水环境中苯丙胺类物质的快速前处理方法

在国内外研究的基础上,应用固相萃取技术,建立并优化了适用于野外条件的3种常见精神活性物质（甲基苯丙胺、苯丙胺和麻黄碱）的快速前处理方法.比较了污水快速前处理条件（样品pH值和上样流速）对目标物回收率的影响.结果表明,在本文测试条件下,理想的快速前处理参数为使用Oasis HLB柱,在碱性条件、流速为20mL/min的情况下加载样品.与传统方法相比,快速前处理方法所得的目标物浓度稍有降低,但仍很好地反映了生活污水中的目标物浓度水平和变化特征.北京、广东两地的野外验证结果显示,该方法对南北两地生活污水和地表水样品的处理效果都比较稳定.     

改变碳输入对新疆天山雪岭云杉林土壤呼吸的短期影响

探究外源性碳输入改变对森林土壤呼吸的影响是深入解析森林碳循环的基础.本研究基于植物残体添加和去除控制实验,设置5种不同碳输入(对照组、双倍凋落物组、去根组、去凋落物组和去根去凋落物组)处理,研究了天山雪岭云杉林(Picea Schrenkiana)生长季土壤呼吸对碳输入改变的短期响应.结果表明,整个实验期间对照、双倍凋落物、去根、去凋和去根去凋处理土壤呼吸速率均值分别为3.38、 3.94、 2.65、 2.87和2.01μmol·(m~2·s)~(-1);与对照处理相比,双倍凋落物处理使累计土壤呼吸通量增加402.65 g·m~(-2),去根、去凋和去根去凋处理分别减少了515.00、 354.73和967.15 g·m~(-2),减少幅度为去根去凋去根去凋.整个实验期间相对于对照组,双倍凋落物处理下土壤呼吸速率平均增加20.35%,去凋、去根、去根去凋处理下土壤呼吸速率分别平均降低14.40%、 20.78%和40.83%.土壤矿质呼吸、凋落物呼吸和根系呼吸对土壤总呼吸的相对贡献率由大至小依次为:土壤矿质呼吸(59.46%)根系呼吸(21.49%)凋落物呼吸(14.79%).由主成分分析可知,土壤呼吸速率的变化与土壤温度、土壤湿度、全磷、pH值、土壤有机碳正相关,与土壤容重负相关,而全氮、碳氮比和土壤电导率对土壤呼吸速率影响不大.     

Characteristics and formation mechanism of regional haze episodes in the Pearl River Delta of China

To investigate the characteristics and the specific mechanism of continuous haze,comprehensive measurements were conducted from 15 October to 19 November in the Atmospheric Environment Monitoring Super-Station in Heshan of Guangdong province.Five haze episodes occurred in October and November 2014 in the Pearl River Delta(PRD)region. The meteorological parameters, gas data, chemical compositions, and optical parameters of the aerosols were obtained. Among these events, the second haze episode,with the highest concentration of PM2.5 of 187.51 μg/m~3, was the most severe. NO~3-was always higher than SO_4~(2-), which indicated that motor vehicles played an important role in the haze, even though the oxidation rate from SO_2 to SO_4~(2-)was faster than that of NOXto NO_3~-. The difference between the hourly averages of Na+and K+during the haze episode and clean days was small, implying that straw combustion and sea salt had no significant effect on the occurrence of haze, and the backward trajectories of the air masses also conformed with this result. The air pollutants were difficult to disperse because of the significant decrease in the planetary boundary layer(PBL) height. Relative humidity played a crucial role in the formation of haze by leading to hygroscopic growth of the diameter of aerosols.