Manganese and iron oxide immobilized activated carbons precursor to dead biomasses in the remediation of cadmium-contaminated waters

The aim of the present investigation was to exploit the high specific surface area of activated carbons in immobilizing the manganese and iron oxides as to obtain a suitable, efficient and cost effective and environment benign wastewater treatment process in the remediation of cadmium-contaminated waters. The manganese and iron oxides were impregnated in situ onto the surface and pores of the activated carbons precursors to the rice hulls and areca nut wastes. The solids were characterized with the help of Fourier transform infrared spectroscopy and X-ray diffraction analytical data, and the BET specific surface area as obtained. The surface morphology of these solids was discussed with the help of scanning electron microscopic images. The activated carbon samples along with the manganese and iron immobilized activated carbons were further employed in the batch and column reactor operations in the remediation of cadmium-contaminated waters. The batch data showed that an increase in sorptive pH from 2.0 to 10.0 and concentration from 1.0 to 20 mg/L favoured the uptake of cadmium by these solids. Moreover, the 1,000 times increase in background electrolyte concentrations NaNO₃ caused an insignificant decrease in cadmium uptake by these solids, which inferred that sorbing ions/species were sorbed specifically and forming ‘inner-sphere’ complexes onto the solid surface. The concentration dependence data were utilized to model various adsorption isotherms and indicated that Freundlich adsorption isotherm was reasonably fitted well. The kinetic data was fitted well to the pseudo-second-order rate equations; hence, the equilibrium sorption capacity was estimated. Furthermore, the dynamic experiments carried out by the column experiments and the breakthrough data were fitted well to the non-linear Thomas equations; accordingly, the loading capacity of the column was estimated. Iron or manganese immobilized activated carbons showed relatively higher loading capacity compared to its precursor activated carbons hence showing its possible implication in the remediation processes. Moreover, among these modified ACs, IIAC showed higher removal capacity than the MIAC solid.     

Adsorption of DBT and 4,6-DMDBTon nanoporous activated carbons: the role of surface chemistry and the solvent

Environmental Science and Pollution Research - Adsorption of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) from solutions in hexane and hexadecane respectively as well as in...     

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.     

Multivariate optimization of solid-phase extraction applied to iron determination in finished waters

In this work, Amberlite XAD-4 resin functionalized with salicylic acid was synthetized, characterized and applied as a new packing material for an on-line system to iron determination in aqueous samples. The detection method is based on the sorption of Fe(III) ions in a minicolumn containing the synthesized resin, followed by a desorption step using an acid solution and measurement of iron by vis-spectrophotometry (CAS method). The optimization of the solid-phase extraction system was performed using factorial design and Doehlert matrix considering six variables: sample percolation rate (0.5-9 ml min(-1)), sample metal concentration (20-200 microg l(-1)), flow-through sample volume (0-5 ml) (all three directly linked to the extraction step), elution flow-rate (0.5-9 ml min(-1)), concentration and volume of eluent (HCl 0.1-0.5M) (all three directly linked to the elution step). The aim of this study was to obtain a set of operating ranges for the six variables tested in order to obtain--by means of a mathematical function allowing maximisation of each response (desirability function)--at least 90% of iron recovery rates. Using the experimental conditions defined in the optimization, the method allowed iron determination with achieved detection limit of 2.3 microgl(-1) and precision (assessed as the relative standard deviation) of 9.3-2.8% for iron solutions of 10.0-150 microgl(-1). Real samples (coming from a water treatment unit) were used successfully when evaluating potentialities of the developed SPE procedure coupled to a spectrophotometric determination.     

铁氧化物/活性炭对饮用水中Sb(V)的吸附性能及机理

采用液相沉积法制备了铁氧化物/活性炭复合材料(Fe₂O₃@AC),通过单因素实验和正交实验优化了材料的制备条件,使用SEM、FTIR、XRD、XPS等分析方法对材料的形貌和性质进行了表征分析,通过吸附实验探究了Fe₂O₃@AC吸附除锑的效果及影响因素,并进一步对吸附除锑的机理进行了深入探讨。结果表明：最佳制备条件为纯水:乙醇:=4:1,Fe²⁺:Fe³⁺=1:1,总铁浓度为0.594 mol·L⁻¹,制备液pH=1.88。Fe₂O₃@AC吸附除锑的能力较其他金属基材料和活性炭有明显提高,锑原水质量浓度为38 μg·L⁻¹,Fe₂O₃@AC投加量为0.08 g·L⁻¹,吸附平衡后水中锑的去除率达97%,剩余锑质量浓度为1.06 μg·L⁻¹,满足国家饮用水卫生标准要求。微观表征显示铁氧化物颗粒成功负载于活性炭上,且铁氧化物晶体的结构完好。吸附反应符合准二级动力学和Langmuir等温模型,吸附反应以单层化学吸附为主,吸附类型为液膜扩散,颗粒内扩散,质量扩散的叠加形式。吸附方式为共沉淀,及溶解态锑与固相铁氧化物形成络合物,参与反应的官能团为—OH、—COOH、—Fe—OH、—Fe—O—Fe。     

Combined effect of microwave and activated carbon on the remediation of polychlorinated biphenyl-contaminated soil

The application of microwave and activated carbon for the treatment of polychlorinated biphenyl (PCB) contaminated soil was explored in this study with a model compound of 2,4,5-trichlorobiphenyl (PCB29). PCB-contaminated soil was treated in a quartz reactor by microwave irradiation at 2450MHz with the addition of granular activated carbon (GAC). In this procedure, GAC acted as microwave absorbent for reaching high temperature and reductant for dechlorination. A sheltered type-K thermocouple was applied to record the temperature rising courses. It was shown that the addition of GAC could effectively promote the temperature rising courses. The determination of PCB residues in soil by gas chromatography (GC) revealed that rates of PCB removal were highly dependent on microwave power, soil moisture content, and the amount of GAC added. GC with mass spectrum (MS) detector and ion chromatography were employed for the analysis of degradation intermediates and chlorine ions, respectively. It was suggested that microwave irradiation with the assistance of activated carbon might be a potential technology for the remediation of PCB-contaminated soil.     

活性炭三维电极电促吸附去除水中氟离子的研究

主要研究颗粒活性炭作为第三维电极电促吸附水中氟离子。通过在颗粒活性炭上施加不同电压,测定吸附容量和考察吸附动力学过程,结果表明,将电压控制在3~5 V范围内可有效增强三维电极的吸附容量,5 V电压下的电促吸附容量比开路电位下提高30%,同时此电促吸附反应符合一级反应动力学。在动态开放式实验中,所施加电压、含氟水样pH、电解质浓度、初始氟离子浓度和进水流量均对电促吸附容量产生影响。采用电子扫描电镜和氮气吸附脱附的方法比较吸附前后活性炭颗粒表面性质的变化,发现其表面并未发生氧化反应,孔容孔径也未发生明显变化,且孔径大小与电促吸附有一定的关联。综合这些实验结果表明,三维电极电促吸附可有效提高颗粒活性炭的吸附效果,这是由于活性炭电极表面产生双电层作用的结果,并非活性炭表面或者水溶液中产生氧化反应所至。     

凤眼莲-固定化氮循环细菌联合作用对富营养化水体原位修复的研究

应用生态工程技术和原理,在夏季利用凤眼莲（Eichhornia crassipes Mart.）结合固定化氮循环菌对富营养化水体进行原位修复研究。试验结果表明,凤眼莲+固定化氮循环细菌联合作用和单独的凤眼莲处理对富营养化水体总氮和铵态氮去除之间存在显著的差异,凤眼莲+固定化氮循环细菌联合作用对富营养化水体中总氮和铵态氮的去除率分别达77.2%和49.2%;而凤眼莲处理则分别达73.7%和32.3%;但两者对富营养化水体中硝态氮的去除没有显著差异。接种固定化氮循环微生物有利于水体中Chla、COD_Mn的降低和水体透明度的提高,但两者没有明显的差异。当凤眼莲处理系统接种固定化氮循环细菌时,除了氨化细菌变化不明显外,亚硝化菌,硝化菌,反硝化菌群数量比单独凤眼莲处理系统增加1～1.5个数量级,且接种固定化氮循环细菌还有利于凤眼莲生物量及其体内氮积累量的增加。     

A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons.

Disposal of sewage sludge is an increasingly expensive and environmentally sensitive problem throughout the world. Preparation of activated carbon from sewage sludge offers an attractive re-use alternative to the traditional disposal routes. The objective of this research work was to compare anaerobically digested sewage sludge (DS) and undigested sewage sludge (US) as source materials in the preparation of activated carbons. Prior to the preparation the properties of the two types of sewage sludges were determined and compared. Subsequently the sludge samples were activated with 5 M ZnCl2 solution and thereafter pyrolysed at heating temperature of 650 degrees C for 2 h with the heating rate of 15 degrees C/min under a nitrogen atmosphere. The produced activated carbons were characterised by surface area and porosity analysis, CHN elemental composition and ash contents determination, and aqueous phase phenol adsorption tests. The results indicate that in comparison with the DS, the US had a higher carbon content and lower ash content, and accordingly yielded a better activated carbon with a higher BET surface area, pore volume, carbon content and phenol adsorption capacity.     

Variability of dust iron solubility in atmospheric waters: Investigation of the role of oxalate organic complexation

Atmospheric dust deposition is a major external iron source for remote surface ocean waters. Organic complexation is known to play a role in the dissolution of iron-containing minerals. In this paper, we present our study on the effect of oxalate on dust iron solubility in simulated rainwater. Our results reveal that the solubility of iron carried by analogs of different African dusts varies with the dust source. Our experiments indicate a positive linear correlation between iron solubility and oxalate concentration. Soluble iron (SFe) increases from 0.0025(±0.0005)% to 0.26(±0.01)% of total iron, considering all dust sources and with oxalate concentrations ranging from 0 to 8 μM. These results show that the observed variability of iron solubility in aerosols collected over the Atlantic Ocean is, at least partly, due to an increase in dust iron solubility, with the presence of oxalate complexation, rather than to the presence of more soluble anthropogenic iron. Considering the mineralogical composition of those particles, experiments with pure minerals (hematite, goethite and illite) were performed to study the dissolution process. We found that oxalate promotes the solubility of iron contained in clay and hence confirmed that more than 95% of SFe from soil dust is provided by clay (illite). This experimental work enables us to establish a parameterization of iron solubility in dust as a function of oxalate concentration and based on the individual iron solubility of pure iron-bearing minerals usually present in dust particles. Finally, our results emphasize that oxalate contributes to iron solubility on the same order of magnitude as the acid processes. Organic complexation appears to be a process that increases iron solubility and likely enhances the bioavailability of iron from dust.     

新型活性炭固定化产品的制备及其处理焦化废水的特性

为解决优势菌种工程应用,研究不同固定化方法、载体和结构的固定化产品对焦化废水的降解特性。用活性炭粉末吸附菌种后,与聚乙烯醇和海藻酸钠混合制备了新型固定化球;用聚乙烯醇和海藻酸钠包埋吸附菌种的活性炭纤维毡,与立体弹性塑料填料连用,制备出3种不同形状的活性炭纤维膜片固定化产品复合填料。将游离菌和制备的4种活性炭固定化产品投入A/A/O工艺系统平行实验,考察处理焦化废水的效果。结果表明,活性炭纤维膜片固定化产品复合填料对焦化废水的降解能力优于其他固定化产品:缺氧池出水硝酸盐氮和亚硝酸盐氮浓度分别稳定在1.96 mg/L和0.49 mg/L,未产生氮的累积现象,COD去除率可达到60.92%。好氧池COD和氨氮降解效率分别为78.83%和85.52%,苯酚、氰化物降解效率均为97%以上。     

Single adsorption of diclofenac and ronidazole from aqueous solution on commercial activated carbons: effect of chemical and textural properties

Environmental Science and Pollution Research - The importance of the textural and physicochemical characteristics upon the adsorption capacity of the commercial activated carbons (ACs) Coconut,...     

Electrochemical and FTIR studies of the mutual influence of lead(II) or iron(III) and phenol on their adsorption from aqueous acid solution by modified activated carbons

Cyclic voltammetry and spectral FTIR studies of the influence of activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol from aqueous acidic solution were carried out. The diversity in surface chemical structure was achieved by applying different procedures of inorganic matter removal and by modifying the carbon samples in various ways: heating under vacuum, aminoxidation in an ammonia-oxygen atmosphere, oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb(2+) or Fe(3+)) and phenol from solutions containing cation or phenol separately or in a mixture were determined. The adsorption capacity from acidic aqueous acidic solution depends on the chemical properties of the activated carbon surface (e.g., decrease in phenol adsorption with relative lower basicity of the adsorbent). The electrochemical parameters of electrodes made from the carbon samples were estimated, and some possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte solution containing adsorbed species (separately or as a mixture). Relationships were found between metal ion adsorption and electrochemical behavior of Pb(2+)/Pb(4+) and Fe(3+)/Fe(2+) couples on the one hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption and/or coupling phenol molecules are discussed.     

Utilization of Arachis hypogaea hull, an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m(2)/g and 0.28 cm(3)/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

Synergic effect of calcium oxide and iron (III) oxide on the dechlorination of hexachlorobenzene

Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.     

Factors influencing the preparation of supported iron oxide in fluidized-bed crystallization

Our previous work applied a novel supported iron oxyhydroxide (FeOOH) catalyst to effectively treat benzoic acid by hydrogen peroxide. The FeOOH catalyst was prepared via the oxidation of Fe2+ by H2O2 in the acidic condition using a fluidized-bed crystallization reactor. The major components coated on the surface were identified as amorphous FeOOH and gamma-FeOOH. In terms of the crystallization conditions of FeOOH, some parameters including the operational pH, superficial velocity, specific iron loading, and influent H2O2 concentration were investigated to quantify their effects on the crystallization efficiency. All these parameters were found to significantly influence the crystallization efficiency. Two types of FeOOH catalysts were synthesized: FeOOH I was prepared at pH 3.5, and FeOOH II was formed by aging FeOOH I at pH 13. The percentages of surface amorphous FeOOH reduced from 70% to 30% after aging. The FeOOH II catalyst presented a higher reactivity toward H2O2 but lower stoichiometric efficiency in oxidizing benzoic acid than FeOOH I, similar to the result of the commercial goethite. Therefore, it is concluded that the crystalline property significantly affects the performance of catalytic oxidation.     

Electrokinetic remediation of organochlorines in soil: enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.