Practical applications of the fenton reaction to the removal of chlorinated aromatic pollutants

BACKGROUND: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. METHODS: Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). RESULTS AND DISCUSSION: The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. CONCLUSIONS: The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70 degrees C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). RECOMMENDATIONS AND OUTLOOK: In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.     

Acute toxicity of DMAH to Oryzias latipes as modified by some influential factors

As a new insecticide,less information about the aquatic biological toxicity of DMAH [N-(2,4-dimethylphenyl)-N'-methylamidine hydrochloride]is known.Acute 96h static bioassays were conducted with Oryzias latipes to assess the toxicity of DMAH and the influence of environ- mental factors.The results indicated that,at 23℃,the 24h,48h and 96h LC⁵⁰ are 14.6 mg/L,13. 06 mg/L and 12.39 mg/L,respectively,the safe concentration (SC)of DMAH to Oryzias latipes is 1.16-1.32 mg/L.The changes of temperature,pH value and hardness of water will significantly influence the toxicity of DMAH to fish.     

Sampling and determination of carbonyls in stack gas

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Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.     

大气甲醛稳定碳同位素分析方法研究

利用气相色谱/燃烧/同位素比值质谱(GC/C/IRMS)技术,采用2,4-二硝基苯肼(DNPH)衍生化,初步研究了单体化合物稳定碳同位素方法研究大气甲醛来源问题.根据不同同位素组成的甲醛与DNPH反应,模拟大气采样,具体讨论了甲醛与DNPH衍生化过程的同位素效应及分析方法的重现性与精确度.结果表明,每个甲醛2,4-二硝基苯腙样品分析的最大标准偏差为0.3‰;不同同位素组成的甲醛衍生化产物甲醛2,4-二硝基苯腙与理论值的平均偏差为0.24‰±0.14‰(从0.03‰到0.35‰),小于仪器分析误差0.5‰,该衍生化过程不存在同位素分馏.采用该方法对酒店大厅内外大气甲醛碳同位素组成进行了初步研究,结果表明不同来源的甲醛同位素组成具有显著差异,可以为大气甲醛的来源分析提供非常有效的信息.     

Fenton氧化处理爆炸物污染土壤的实验研究

采用摇瓶和玻璃柱试验考察了Fenton氧化处理爆炸物污染土壤中2,4-DNT、2,6-DNT以及COD等的去除效果及其最佳参数.当3%H2O2投加量达到26.46mmol、FeSO4和H2O2的物质的量之比约为1∶73.56时,2,4-DNT和2,6-DNT均可被完全氧化,COD去除率可达到87%.对于2,4-DNT和2,6-DNT,反应时间只需要2h,但要同时去除其它芳香族硝基化合物,则反应时间需要超过8h.土壤直接Fenton氧化的效果并不理想,而对洗出液进行Fenton氧化可以取得很好的效果.通过反应动力学分析和丙酮抑制试验得出,2,4-DNT比2,6-DNT容易氧化.GC-MS分析结果表明,不仅土壤中的2,4-DNT、2,6-DNT可被氧化,其它的硝基芳香族有机化合物也可被氧化去除.     

纳米级Fe3O4-Pd/Fe复合材料催化脱氯2,4-D研究

采用共沉淀法制备纳米级Fe_3O_4,将其包覆在纳米Pd/Fe颗粒表面制成纳米级Fe_3O_4-Pd/Fe复合材料,并用于2,4-二氯苯氧乙酸(2,4-D)的催化脱氯.同时,采用透射电镜(TEM)、扫描电镜(SEM)等方法对复合材料的结构进行分析,并考察了初始pH、钯化率、反应温度、纳米Fe_3O_4投加量等实验参数对n Fe_3O_4-Pd/Fe复合材料催化脱氯2,4-D的影响.结果发现,纳米Fe_3O_4粒径小于Pd/Fe纳米颗粒,具有一定的磁性,包覆于纳米Pd/Fe表面,提高了纳米材料的稳定性及分散性,并有利于复合材料的回收和循环利用.此外,纳米Fe_3O_4具有一定的导电性,可作为良好的电子通道为纳米Pd/Fe颗粒传递电子,促进反应的进行,增强2,4-D的去除效果.实验结果表明,较高的钯化率、反应温度、Fe_3O_4∶Fe质量比及中性pH条件均有利于反应的进行.当纳米Fe投加量为1.0 g·L-1,m(Fe_3O_4)∶m(Fe)为1∶1,初始pH为7.0,钯化率为0.15%,反应温度为25.0℃时,反应90 min后,40.0 mg·L-1的2,4-D的去除率达到100%,苯氧乙酸(PA)的生成率达99.8%.     

Organoclays for Aquifer Bioremediation: Adsorption of Chlorobenzene on Organoclays and its Degradation by RHODOCOCCUS B528

The adsorption and degradation of chlorobenzene on partially modified organoclays and by the autochthonous microorganism Rhodococcus B528 were studied by means of the batch technique. Organoclays were prepared from Na-montmorillonite (MM) by using dodecyltrimethylammonium (C₁₂) and dioctadecyldimethylammonium (2C₁₈) bromides. The degree of modification was 35 (2C₁₈-35-MM) and 89% (C₁₂-89-MM) of the cation exchange capacity of MM. The adsorption experiments were carried out using headspace GC. The intercalation of chlorobenzene into the interlayers of organo-MM was detected by X-ray diffraction. The adsorption isotherms found were of the S1 type indicating a cooperative effect. Chlorobenzene showed a higher affinity for 2C₁₈-35-MM than C₁₂-89-MM, which could not only be explained by the organic carbon content. The comparison with 2,4-dichlorophenol adsorption has implied that for the studied systems the different adsorption mechanisms are primarily governed by the different molecular properties and not by the type of absorbent. The presence of 2C₁₈-35-MM caused no negative effect on the investigated microorganisms and complete biodegradation of chlorobenzene was achieved without desorption limitation for growth, demonstrating the applicability of partially modified organoclays for bioremediation.     

太阳光下TiO2/SiO2气凝胶复合光催化剂光催化降解2,4-二硝基酚

以正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶法(so1-ge1)和常压干燥法制备SiO2气凝胶,在此基础上,将硅气凝胶掺杂进入TiO2溶胶中制备出TiO2/SiO2气凝胶复合光催化剂.利用xRD、TEM和FI-IR等技术对其晶型、形貌和结构进行表征,研究了太阳光下TiO2/SiO2气凝胶复合光催化荆对2,4-二硝基苯...