Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.     

热活化过硫酸钠耦合甲酸技术研究——处理水溶液中四氯化碳与六价铬污染

以甲酸为活化剂,耦合热活化过硫酸钠技术产生还原性二氧化碳阴离子自由基（CO₂^·-）,从而还原去除水溶液中四氯化碳（CT）和Cr（VI）,考察过硫酸钠和甲酸初始浓度的影响以及复合污染处理效果.结果表明：当过硫酸钠与甲酸浓度均为100mmol/L时,单独CT或Cr（VI）分别在120min、60min内基本完全去除（50℃）,且污染物去除效率随过硫酸钠及甲酸浓度升高而增强.在CT和Cr（VI）复合污染体系中,Cr（VI）的存在能够抑制CT降解,且抑制程度随Cr（VI）初始浓度升高而提高,但Cr（VI）去除率随CT初始浓度增大而升高.加入CO₂^·-猝灭剂（甲基紫精）能够抑制CT降解,但促进Cr（VI）去除,表明有机物的存在能够增强Cr（VI）去除效率.     

Hepatoprotective and antioxidant effects of Bridelia retusa against carbon tetrachloride-induced hepatotoxicity

The aim of present study was to validate hepatoprotective and antioxidant activities of the bark of Bridelia retusa. The aqueous ethanol extract of B. retusa exhibited highest in vitro hepatoprotective effects as evident from the significantly reduced serum glutamate oxaloacetate transaminase (SGOT) and serum glutamate pyruvate transaminase (SGPT) into the incubation medium of rat hepatocytes with carbon tetrachloride (CCl₄), over the other organic extracts (chloroform, ethylacetate, and methanol). CCl₄ administered through subcutaneous injection produced a marked elevation in the serum levels of GOT, GPT, lactate dehydrogenase, alkaline phosphatase, bilirubin, thiobarbituric acid reactive substances, and decreased in the levels of reduced glutathione, superoxide dismutase, catalase, glutathione-S-transferase, glutathione reductase, glutathione peroxidase, and total protein content. The biochemical activities were normalized in the pretreatment of rats induced by CCl₄ with different doses (250 and 500 mg kg^?1) of the aqueous ethanol extract of B. retusa. Histopathological changes induced by CCl₄ were also significantly attenuated by aqueous ethanol extract of B. retusa treatment. The activity of the aqueous ethanol extract of B. retusa at the dose of 500 mg kg^?1 was comparable to the standard drug, silymarin (25 mg kg^?1). The overall data indicated that B. retusa possesses a potent protective effect against CCl₄-induced hepatic damage and oxidative stress.     

Fabrication of bimetallic Ag/Fe immobilized on modified biochar for removal of carbon tetrachloride

As an effective conventional absorbent, biochar exhibited limited adsorption ability toward small hydrophobic molecules. To enhance the adsorption capacity, a novel adsorbent was prepared by immobilizing nanoscale zero-valent iron onto modified biochar (MB) and then the elemental silver was attached to the surface of iron (Ag/Fe/MB). It''s noted that spherical Ag/Fe nanoparticles with diameter of 51 nm were highly dispersed on the surface of MB. As the typical hydrophobic contaminant, carbon tetrachloride was selected for examining the removal efficiency of the adsorbent. The removal efficiencies of carbon tetrachloride by original biochar (OB), Ag/Fe, Ag/Fe/OB and Ag/Fe/MB were fully investigated. It''s found that Ag/Fe/MB showed higher carbon tetrachloride removal efficiency, which is about 5.5 times higher than that of the OB sample due to utilizing the merits of high adsorption and reduction. Thermodynamic parameters revealed that the removal of carbon tetrachloride by Ag/Fe/MB was a spontaneous and exothermic process, which was affected by solution pH, initial carbon tetrachloride concentration and temperature. The novel Ag/Fe/MB composites provided a promising material for carbon tetrachloride removal from effluent.     

钛盐混凝剂调理对活性污泥絮体理化性质的影响作用机制

研究了预制的不同形态钛盐混凝剂对污泥的调理效果,结果表明不同碱化度[B值,即n(OH)/n(Ti)]聚合氯化钛(PTC)单一调理污泥时,在相同投加量时,PTC_(0.5)调理后污泥比阻、可压缩性以及EPS中有机物含量均低于其他形态钛盐,其最佳投加量以TSS计,为0.005 g·g~(-1),该投加量远低于传统的铁盐和铝盐混凝剂.不同B值PTC调理污泥脱水能力的强弱顺序为:PTC_(0.5)PTC_(1.5)Ti Cl_4PTC_(2.5).同时分析了调理过程中污泥絮体粒径(d_(0.5))和分形维数(D_F)的变化特征.采用三维荧光光谱和高效体积排阻色谱,解析了钛盐混凝剂对污泥胞外聚合物(EPS)分布和组成的影响,EPS蛋白峰的荧光强度和有机物相对分子质量峰分布变化规律与污泥比阻、可压缩性和脱水能力变化规律有一定相关性.     

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO₂) and uranium tetrachloride (UCl₄) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415–475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480–560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

四氯化碳显色法测定溶解氧

本文介绍了一种测定溶解氧的新方法。此方法快速、准确、分析结果直观、适合应急监测。     

Enhanced reductive degradation of carbon tetrachloride by carbon dioxide radical anion-based sodium percarbonate/Fe(II)/formic acid system in aqueous solution

Complete CT degradation was achieved by SPC/Fe(II)/FA system.Formic acid established the reductive circumstance by producing CO₂·^–.CO₂·^– was the dominant active species responsible for CT degradation.CT degradation was favorable in the pH range from 3.0 to 9.0.SPC/Fe(II)/FA system may be suitable for CT remediation in contaminated groundwater.The performance of sodium percarbonate (SPC) activated with ferrous ion (Fe(II)) with the addition of formic acid (FA) to stimulate the degradation of carbon tetrachloride (CT) was investigated. Results showed that CT could be entirely reduced within 15 min in the system at a variety of SPC/Fe(II)/FA/CT molar ratios in experimental level. Scavenging tests indicated that carbon dioxide radical anion (CO2·^–) was the dominant reactive oxygen species responsible for CT degradation. CT degradation rate, to a large extent, increased with increasing dosages of chemical agents and the optimal molar ratio of SPC/Fe(II)/FA/CT was set as 60/60/60/1. The initial concentration of CT can hardly affect the CT removal, while CT degradation was favorable in the pH range of 3.0–9.0, but apparently inhibited at pH 12. Cl^– and HCO₃^– of high concentration showed negative impact on CT removal. Cl^– released from CT was detected and the results confirmed nearly complete mineralization of CT. CT degradation was proposed by reductive C-Cl bond splitting. This study demonstrated that SPC activated with Fe(II) with the addition of FA may be promising technique for CT remediation in contaminated groundwater.