Removal of As(III) from Aqueous Solution Using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles: Process Modeling and Optimization Using Statistical Design

In this study, Extran (biodegradable surfactant) was used for the preparation of Fe₃O₄ nanoparticles by microemulsion process to improve removal efficiency of As(III) from aqueous solution. Fe₃O₄ nanoparticles were characterized by XRD, FTIR, FESEM, TEM, HRTEM, and VSM instrumental techniques. The effect of different parameters such as adsorbent dose, initial As(III) concentration, and solution pH were studied by response surface methodology (RSM) based on Box-Behnken design (BBD). The optimized condition for adsorption of As(III) from aqueous solution was obtained as adsorbent dose of 0.70 mg/g, solution pH of 7.7, and initial As(III) concentration of 33.32 mg/L. In this optimum condition, about 90.5% of As(III) was removed from the aqueous solution. Isotherm studies have been done at optimal condition, and it was observed that the Langmuir isotherm models were fitted well with experimental data having a high correlation coefficient of 0.993. From the Langmuir isotherm data, the maximum adsorption capacity of Fe₃O₄ nanoparticles was found to be 7.18 mg/g at pH 7.7 in room temperature. This study revealed that Fe₃O₄ nanoparticles can be used as an efficient, eco-friendly, and effective material for the adsorptive removal of As(III) from aqueous system.     

Removal of Cu(II) Ions from Aqueous Solution by Magnetic Chitosan-Tripolyphosphate Modified Silica-Coated Adsorbent: Characterization and Mechanisms

A magnetic chitosan-modified Fe₃O₄@SiO₂ with sodium tripolyphosphate adsorbent (MTPCS) was synthesized by surface modification of Fe₃O₄@SiO₂ with chitosan using sodium tripolyphosphate (STPP) as the cross-linker in buffer solution for the adsorption of Cu(II) ions from aqueous solution. The structure and morphology of this magnetic nanoadsorbent were examined by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), BET surface area measurements, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of initial pH, adsorbent amount, and initial concentration of heavy metal ions were investigated by batch experiments. Moreover, adsorption isotherms, kinetics, and thermodynamics were studied to understand the mechanism of adsorbing metal ions by synthesized MTPCS. The results revealed that adsorption kinetics was best depicted by the pseudo-second-order rate mode and intraparticle-diffusion models. The adsorption isotherm fitted well to the Langmuir model. Moreover, thermodynamic study verified the adsorption process was endothermic and spontaneous in nature. The maximum adsorption occurred at pH 5 ± 0.1, and the adsorbent could be used as a reusable adsorbent with convenient conditions.     

Critical Influence of Culture Medium and Cr(III) Quantification Protocols on the Interpretation of Cr(VI) Bioremediation by Environmental Fungal Isolates

The influence of culture medium composition on chromium(VI) quantification according to diphenylcarbazide (DPC) colorimetric determination was evaluated. Considering the eventual biospeciation of Cr(VI) as a mechanism of microbial bioremediation, the possibility to quantify Cr(III) in culture medium was also explored. Yeast nitrogen base (YNB) was identified as the least interferent culture medium for Cr(VI) quantification by DPC and it was applied to compare different strategies for Cr(III) oxidation. The most appropriate oxidation protocol consisted in the reaction with 80 mM KIO₄ at room temperature for 30 min prior to DPC. Parameters like basal culture medium (vitamins + salts + oligoelements), C and N source were systematically evaluated, either independently or in combination. Results demonstrated that C source was the most interferent culture medium component, being the use of sucrose preferable to glucose. A medium arbitrarily named as YNB′ (YNB without amino acids and ammonium sulfate plus 50 g L^?1 sucrose and 0.6 g L^?1 (NH₄)₂SO₄) was defined for Cr(VI)-amended fungal cultures. Kinetics of growth, Cr(VI) removal, and nutrient consumption for isolates A. pullulans VR-8, filamentous fungus PMF-1, and Lecythophora sp. NGV-1 were obtained. The order of Cr(VI) removal efficiency was as follows: A. pullulans VR-8 > Lecythophora sp. NGV-1 > filamentous fungus PMF-1, and a similar trend was observed for biomass yield and nutrients consumption. Studies on biospeciation by means of the selected Cr(III) oxidation protocol were unsuccessful, leading to Cr(VI) values much lower than expected. It revealed that this kind of protocols should be cautiously evaluated when studying microbial Cr(VI) bioremediation.     

Evaluation of the Combined Cr(VI) Removal Capacity of Sawdust and Sawdust-Immobilized Acinetobacter haemolyticus Supplied with Brown Sugar

The purpose of this study is to evaluate the combined Cr(VI) removal capacities of nonliving (untreated rubber wood sawdust, URWS) and living biomass (URWS-immobilized Acinetobacter haemolyticus) in a continuous laboratory scale downward-flow two column system. Synthetic solutions of Cr(VI) between 237 and 320 mg L^?1 were mixed with 1 g L^?1 brown sugar in a nonsterile condition. Final Cr(VI) of between 0 and 1.6 mg L^?1 indicate a Cr(VI) removal capacity of 99.8–100%. The bacterial Cr(VI) reduction capacity increased with column length. This study shows the feasibility of using the two column system consisting of living (bacteria) and nonliving biomass (URWS) as a useful alternative treatment for Cr(VI) contamination in the aqueous system.     

Hexavalent Chromium Removal by Candida sp. in a Concentric Draft-Tube Airlift Bioreactor

The main purpose of this work was to conduct a kinetic study on cell growth and hexavalent chromium [Cr(VI)] removal by Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor. The yeast was batch-cultivated in a 5.2-l airlift bioreactor containing culture medium with an initial Cr(VI) concentration of 1.5 mM. The maximum specific growth rate of Candida sp. FGSFEP in the airlift bioreactor was 0.0244 h^?1, which was 71.83% higher than that obtained in flasks. The yeast strain was capable of reducing 1.5 mM Cr(VI) completely and exhibited a high volumetric rate [1.64 mg Cr(VI) l^?1 h^?1], specific rate [0.95 mg Cr(VI) g^?1 biomass h^?1] and capacity [44.38 mg Cr(VI) g^?1 biomass] of Cr(VI) reduction in the airlift bioreactor, with values higher than those obtained in flasks. Therefore, culture of Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor could be a promising technological alternative for the aerobic treatment of Cr(VI)-contaminated industrial effluents.     

Preparation of High Surface Area Oxidized Activated Carbon from Peanut Shell and Application for the Removal of Organic Pollutants and Heavy Metal Ions

A peanut shell-derived oxidized activated carbon (OAC) with high surface area was prepared by zinc chloride (ZnCl₂) chemical activation and subsequent nitric acid oxidation. OAC was characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and N₂ adsorption-desorption. The results showed that OAC had the surface area of 1807 m² g^?1, with the total pore volume of 0.725 cm³ g^?1 and average pore diameter of 3.8 nm. More importantly, when OAC acted as an adsorbent, it exhibited high efficiency to remove basic blue 41 (BB-41), congo red (CR), phenol, Cr(VI), and Pb(II) from aqueous solution due to its universality in adsorption. Batch adsorption experiments were carried out to study the effect of various parameters such as pH, initial concentration, temperature, and contact time. Also, the isotherms, kinetic models, and thermodynamics of adsorption process were investigated. The equilibrium data for CR and Pb(II) were fitted to Langmuir isotherm model, while Freundlich model was suitable for the equilibrium isotherm of BB-41, phenol, and Cr(VI), respectively. As the result indicated, peanut shell was a suitable raw material to synthesize OAC which could be employed as an efficient and universal adsorbent for removing organic pollutants and heavy metal ions from wastewater.     

Response of wheat genotypes to foliar spray of ZnO and Fe2O3 nanoparticles under salt stress

This study evaluated the effects of iron oxide (Fe₂O₃) and zinc oxide (ZnO) on two wheat genotypes (Kavir and Tajan) at three levels (0, 75, and 150 mM sodium chloride (NaCl)) of salinity. Spray treatments included two forms of normal and nanoparticles of Fe₂O₃ and ZnO, a mixture of nanoparticles of Fe₂O₃ and ZnO (2 g L^?1) and a non-spray treatment. The pot experiment was arranged as factorial in a randomized complete block design with four replications. Two forms of Fe₂O₃ and ZnO significantly accelerated plant height, leaf area, shoot dry weight, and the concentration of iron (Fe) and zinc (Zn) in comparison with non-spray treatment. The highest plant height and leaf Fe concentration belonged to Fe₂O₃ nanoparticles; however, it seems that the spray of nanoparticles may not be superior compared with normal forms in alleviation of salinity impacts.     

Assessment on the Removal of Methylene Blue Dye using Tamarind Fruit Shell as Biosorbent

Tamarind fruit shell was used as a low-cost biosorbent for the removal of methylene blue from aqueous solution. The various factors affecting adsorption, such as agitation, pH, initial dye concentration, contact time, and temperature, were investigated. The dye adsorption capacity was strongly dependent on solution pH as well as temperature. The Langmuir isotherm model showed good fit to the equilibrium adsorption data, and the maximum adsorption capacity obtained was 1.72 mg g^?1 at 303 K. The kinetics of adsorption followed the pseudo-second-order model and the rate constant increased with increase in temperature, indicating endothermic nature of adsorption. The Arrhenius equation was used to obtain the activation energy (E _a) for the adsorption system. The activation energy was estimated to be 19.65 kJ mol^?1. Thermodynamic parameters such as Gibbs free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) were also investigated. Results suggested that adsorption of methylene blue onto tamarind fruit shell was a spontaneous and endothermic process. The present investigation suggests that tamarind fruit shell may be utilized as a low-cost adsorbent for methylene blue removal from aqueous solution.     

茶树枝叶制备生物炭负载纳米零价铁净化水中Cr(VI)

茶树废弃物引起的环境破坏和病虫害爆发问题日益突出,对其进行无害化和资源化利用具有重要意义。该研究以修剪的茶树枝叶提取液作为还原剂和封端剂,以提取后的残渣作为炭源,成功制备了一种可高效去除水中六价铬(Cr(Ⅵ))的生物炭负载纳米零价铁复合材料(nanoscale zero-valent iron embedded tea leaves,TLBC-nZVI)。分析了材料用量、溶液初始pH值和温度等对Cr(Ⅵ)去除效果的影响;利用扫描电子显微镜结合能量色散X射线光谱仪(SEMEDS)、傅立叶变换红外光谱仪(FTIR)、X射线粉晶衍射仪(XRD)和X射线光电子能谱仪(XPS)等对材料进行表征,结合吸附动力学、吸附等温线和吸附热力试验探讨了去除机制。结果表明酸性条件、高温、增加材料用量有利于TLBC-nZVI对Cr(Ⅵ)的去除。TLBC-nZVI吸附过程符合准二级动力学模型、颗粒内扩散模型和Freundlich吸附等温模型,该吸附是自发的化学吸热过程。TLBC-nZVI与Cr(Ⅵ)的反应机制为吸附在材料上的Cr(Ⅵ)被零价铁(Fe⁰)和还原性官能团还原为三价铬(Cr(Ⅲ))...     

Sorption Characteristics of Chromium and Its Phytotoxic Effect with or without City Compost on Maize and Spinach in a Vertisol of Central India

Abstract

Phytotoxicity, due to chromium [Cr (VI)] additions from low to very high levels in a swell–shrink clayey soil (Haplustert), in maize and spinach was studied in a pot culture experiment. Six levels of Cr (VI) (0, 5, 10, 25, 50, and 75 mg kg^?1 soil) for maize and five levels for spinach (0, 2, 5, 10, and 25 mg kg^?1 soil) were applied singly and in combination with two doses (0 and 20 t ha^?1) of city compost. At levels of more than 75 mg Cr (VI) kg^?1 soil for maize there was virtually no growth after germination, whereas 25 mg Cr (VI) kg^?1 soil hindered the germination of spinach crop. Initial symptoms of Cr (VI) toxicity appeared as severe wilting of the tops of treated plants. Maize plants suffering from severe Cr (VI) toxicity had smaller roots and narrow brownish red leaves covered with small necrotic spots. In spinach, severe chlorosis was observed in leaves. Higher levels of Cr (VI) inhibited the growth and dry‐matter yield of the crops. However, application of city compost alleviated the toxic effect of Cr (VI). The concentration of Cr (VI) in plant parts increased when Cr (VI) was applied singly but decreased considerably when used in combination with city compost. There was evidence of an antagonistic effect of Cr (VI) on other heavy‐metal (Mn, Cu, Zn, and Fe) concentrations in plant tops. Thus, when Cr (VI) concentration increases, the concentration of other beneficial metals decreases. Chromium (VI) concentration in maize roots ranged from traces (control) to 30 mg kg^?1and were directly related to soil Cr (VI) concentration. At 25 mg Cr (VI) kg^?1 soil, yield of maize was reduced to 41% of control plants, whereas in spinach, 10 mg Cr (VI) kg^?1 soil caused a 33% yield reduction. Experimental results revealed that the maize top (cereal) is less effective in accumulating Cr (VI) than spinach (leafy vegetables). Laboratory studies were also conducted to know Cr (VI) sorption capacity of a swell–shrink clayey soil with and without city compost, and it was found that Cr (VI) sorption reaction was endothermic and spontaneous in nature.     

Organic Matter Effects on the Cr(VI) Removal Efficiency and Tolerance of <Emphasis Type="Italic">Typha domingensis</Emphasis>

The removal efficiency and tolerance of Typha domingensis to Cr(VI) in treatments with and without organic matter (OM) addition were evaluated in microcosm-scale wetlands. Studied Cr(VI) concentrations were 15 mg L^?1, 30 mg L^?1, and 100 mg L^?1, in treatments with and without OM addition, arranged in triplicate. Controls (without neither metal nor OM addition—without metal with OM addition) were disposed. Cr(VI) was removed efficiently from water in all treatments. OM addition enhanced significantly Cr(VI) and total Cr removals from water. In the treatments with OM addition, significantly higher Cr concentrations were found in sediment than the treatments without OM addition. Plants of the treatments without OM addition showed significantly higher Cr concentrations in tissues but lower biomass increase than the treatments with OM addition. The highest Cr concentrations in tissues were observed in submerged parts of leaves, followed by roots. According to SEM analysis, in the 100 mg L^?1 treatments, the highest Cr accumulation was observed in the epidermis of old leaves. Although Cr(VI) produced changes in root morphology, the OM addition favored the plant growth. In T. domingensis, root morphological plasticity is an important mechanism to improve metal tolerance and Cr uptake in wetland systems minimizing the environmental impact.     

Reduction of Hexavalent Chromium in Soil and Ground Water Using Zero-Valent Iron Under Batch and Semi-Batch Conditions

Chemical remediation of soil and groundwater containing hexavalent chromium (Cr(VI)) was carried out under batch and semi-batch conditions using different iron species: (Fe(II) (sulphate solution); Fe⁰ _G (granulated elemental iron); ZVIne (non-stabilized zerovalent iron) and ZVIcol (colloidal zerovalent iron). ZVIcol was synthesized using different experimental conditions with carboxymethyl cellulose (CMC) and ultra-sound. Chemical analysis revealed that the contaminated soil (frank clay sandy texture) presented an average Cr(VI) concentration of 456?±?35 mg kg^?1. Remediation studies carried out under batch conditions indicated that 1.00 g of ZVIcol leads to a chemical reduction of ～280 mg of Cr(VI). Considering the fractions of Cr(VI) present in soil (labile, exchangeable and insoluble), it was noted that after treatment with ZVIcol (semi-batch conditions and pH 5) only 2.5% of these species were not reduced. A comparative study using iron species was carried out in order to evaluate the reduction potentialities exhibited by ZVIcol. Results obtained under batch and semi-batch conditions indicate that application of ZVIcol for the “in situ” remediation of soil and groundwater containing Cr(VI) constitutes a promising technology.     

Characterization of Reactive Red-120 Decolorizing Bacterial Strain Acinetobacter junii FA10 Capable of Simultaneous Removal of Azo Dyes and Hexavalent Chromium

Continual discharge of textile wastewaters loaded with a variety of synthetic dyes and metals is considered as a huge threat to surrounding ecosystems. In order to treat these undesirable pollutants, microbial bioremediation is considered as an efficient and economical technique. This study was conducted to evaluate the use of bacterial strains for simultaneous removal of azo dyes and hexavalent chromium [Cr(VI)]. Fifty-eight bacterial strains were isolated from Paharang drain wastewater and tested for their potential to decolorize reactive red-120 (RR-120) in the presence of 25 mg L^?1 of Cr(VI). Among the tested isolates, FA10 decolorized the RR-120 most efficiently and was identified as Acinetobacter junii strain FA10. Based on quadratic polynomial equation and response surfaces given by the response surface methodology (RSM), Cr concentration and pH were found to be the main factors governing the RR-120 decolorization by FA10. The strain FA10 also exhibited a substantial salt resistance since it showed a considerable decolorization of RR-120 even in the presence of 150 g L^?1 of NaCl. Moreover, the strain FA10 also showed the potential to simultaneously remove the Cr(VI) and the selected azo dyes in the same medium. More than 80 % of the initially added Cr(VI) was removed over 72 h of incubation along with the appreciable decolorization efficiency. The strain FA10 also exhibited good tolerance to considerable levels of different heavy metals. The findings of this study suggest that the strain FA10 might serve as an efficient bioresource to develop the biotechnological approaches for simultaneous removal of different azo dyes and heavy metals including Cr(VI).     

Treatment of Cr(VI)-spiked soils using sulfur-based amendments

The objective of this research was to assess the hexavalent chromium (Cr(VI)) reducing efficiency of sulfur-based inorganic agents including calcium polysulfide (CPS), iron sulfide (FeS), pyrite (FeS₂) and sodium sulfide (Na₂S) in three soils. An alkaline soil (soil 1), a neutral soil (soil 2) and a slightly acid soil (soil 3) constituted the investigated soils. The soils were spiked with two levels of Cr(VI) (100 and 500 mg Cr(VI) kg^?1 soil) and incubated at field capacity (FC) for one month. Then, CPS, FeS, FeS₂ and Na₂S were added at 0, 5 and 10 g kg^?1 and the concentrations of exchangeable Cr(VI) were measured after 0.5, 4, 48 and 168 h in a batch experiment. The pH and organic carbon content of the soils played predominant role in Cr(VI) self-reduction by the soil itself. Complete self-reduction of Cr(VI) from soils 1, 2 and 3 was achieved at maximum Cr(VI) levels of 1, 50 and 500 mg kg^?1, respectively. Therefore, the concentration of Cr(VI) should not exceed the given levels in order to ensure that Cr(VI) is not released into the environment from contaminated sites. Moreover, decreasing pH in the alkaline soil caused significant increase of Cr(VI) reducing efficiency. Na₂S, CPS and FeS, in contrast to FeS₂, were efficient Cr(VI) reducing agents in all three soils. For all added amendments the following order of Cr(VI) reducing capacity was observed: Na₂S > CPS > FeS > FeS₂ in soil 1, Na₂S ? CPS ~ FeS > FeS₂ in soil 2 and Na₂S ? FeS > CPS ~ FeS₂ in soil 3.     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Feasibility Assessment of Chromium Removal from Groundwater for Drinking Purposes by Sorption on Granular Activated Carbon and Strong Base Anion Exchange

The goal of this study was to compare the performances of strong base anion (SBA) exchange and activated carbon adsorption in the removal of hexavalent chromium, Cr(VI), from a real groundwater matrix exploited for drinking purposes. Two SBA resins and three granular activated carbons (GAC) were tested by batch experiments for kinetics and equilibrium isotherm determination. SBA resins showed higher affinity toward Cr(VI) (present in raw water at about 20 μg L^?1) with respect to the GACs, with faster kinetics and higher equilibrium adsorption capacities. Among GACs, vegetal-based carbons showed higher Cr(VI) removal efficiencies than the mineral-based carbon, which can be related to the more developed textural properties. SBA resins also displayed relevant removal capacities towards nitrate and sulfate (present at mg L^?1 concentration levels), while boron (present at about 60 μg L^?1) was effectively removed by GACs. Batch experiment results were elaborated to estimate the chromium throughputs for the studied materials, to preliminary compare their performances in a real-scale application. The monitoring of a real-scale GAC adsorption stage permitted to validate throughputs estimation and confirmed that, despite being effective toward synthetic organics, GAC adsorption is a not feasible solution for Cr(VI) removal, with extremely early breakthrough. SBA exchange process resulted to be the most suitable solution, providing the best sorbent usage rates. However, SBA resin usage rates can strongly increase when considering the removal of nitrate and sulfate ions, requiring much shorter cycle times.     

Application of Novel Fulvic Acid-Coated Magnetite Nanoparticles for CO<Subscript>2</Subscript><Superscript>−</Superscript>-Mediated Photoreduction of Cr(VI)

We here isolate fulvic acids from vermicompost to prepare and characterize novel fulvic acid-coated magnetite nanoparticles. UV-A irradiation of suspensions of the nanoparticles under different experimental conditions led to photo-reduction of Cr(VI). In anoxic conditions in the presence of formic acid, after 60 min of irradiation ca. 100% of Cr(VI) was reduced. Under these conditions, the carbon dioxide radical anions, CO₂ ^.- , mediated the photo-reduction of Cr(VI). However, the high reduction potential of Cr(VI) and the variety of reactive species generated upon UV-A irradiation make this nanomaterial also suitable for Cr(VI) photo-reduction also under aerobic conditions in the presence of formic acid or under anoxic conditions without the addition of formic acid. The possible photodegradation routes involved are discussed in detail.     

Selective Determination of Chromium(VI) in Industrial Wastewater Samples by Micro-Electromembrane Extraction Combined with Electrothermal Atomic Absorption Spectrometry

This study describes application of free liquid membrane (FLM) in micro-electromembrane extraction (μ-EME) of Cr(VI) from wastewater samples. Amount of Cr(VI) was quantified by electrothermal atomic absorption spectrometry. The transportation of Cr(VI) across the FLM was explored by electrokinetic migration and ion-exchange process. FLM and acceptor solution types, pH of donor and acceptor solutions, applied electrical potential, as well as FLM thickness were optimized. Presence of an anion exchange carrier (methyl trialkyl-ammonium chloride, Aliquat 336) in FLM facilitated Cr(VI) transportation. The best performance was observed for 1-octanol (containing 5% Aliquat 336) with thickness of 1 mm used as FLM, under applied electrical potential of 75 V, when 0.5 M NaClO₄ and 0.1 M HCl were used as the acceptor and donor phases, respectively; and the extraction time was set to 5 min. Linearity was obtained in the working range of 0.5–14.0 ng mL^?1 Cr(VI) (R²?>?0.98). The calculated limit of detection was below 0.06 ng mL^?1. Application of this method to wastewater samples showed that relative recoveries of the spiked Cr(VI) in the samples were in the range of 73.8–85.1%, based on the standard addition method.     

Influences of Humic Acid on Cr(VI) Removal by Zero-Valent Iron From Groundwater with Various Constituents: Implication for Long-Term PRB Performance

A 9-month-long continuous flow column study was carried out to investigate Cr(VI) removal by Fe⁰ with the presence of humic acid. The study focused on the influences of humic acid promoted dissolved iron release and humic acid aggregation in Fe⁰ columns receiving synthetic Cr(VI) contaminated groundwater containing various components such as bicarbonate and Ca. The effects of humic acid varied significantly depending on the presence of Ca. In Ca-free columns, the presence of humic acid promoted the release of dissolved iron in the forms of soluble Fe-humic acid complexes and stabilized fine Fe (hydr)oxide colloids. As a result, the precipitation of iron corrosion products was suppressed and the accumulation of secondary minerals on Fe⁰ surfaces was diminished, and a slight increase in Cr(VI) removal capacity by 18% was record compared with that of humic acid-free column. In contrast, in the presence of Ca, as evidenced by the SEM and FTIR results, humic acid greatly co-aggregated with Fe (hydr)oxides and deposited on Fe⁰ surfaces. This largely inhibited electron transfer from Fe⁰ surfaces to Cr(VI) and reduced the drainable porosity of the Fe⁰ matrix, resulting in a significant decrease in Cr(VI) removal capacity of Fe⁰. The Cr(VI) removal capacity was decreased by 24.4% and 42.7% in humic acid and Ca receiving columns, with and without bicarbonate respectively, compared with that of Ca and humic acid-free column. This study yields new considerations for the performance prediction and design of Fe⁰ PRBs in the environments rich in natural organic matter (NOM).     

A Hybrid Approach for PAHs and Metals Removal from Field-Contaminated Sediment Using Activated Persulfate Oxidation Coupled with Chemical-Enhanced Washing

The aim of this study was to investigate the removal of both polycyclic aromatic hydrocarbons (PAHs) and heavy metals from field-contaminated sediments by activated persulfate oxidation. Various chemicals, including hydroxypropyl-??-cyclodextrin (HPCD), S,S-ethylenediaminedisuccinic acid (EDDS), tetrasodium pyrophosphate (Na₄P₂O₇), and hydrochloric acid (HCl), were applied individually before or after activated persulfate oxidation to enhance the co-removal of both types of pollutants. It was found that the organic removal efficiency was not significantly enhanced by increasing the concentration of HPCD from 2.5 to 5.0?mM. The removal efficiency of heavy metals was not improved even at an excess amount of EDDS after activated persulfate oxidation. However, the addition of EDDS acted as the Fe²⁺ carrier for activated persulfate oxidation. In addition, no significant enhancement of heavy metal removal was observed by increasing the concentrations of Na₄P₂O₇ and HCl from 0.01 to 0.1?M after activated persulfate oxidation. However, comparing 0.1?M HCl with 0.1?M Na₄P₂O₇, HCl was shown to be more effective in promoting the removal of organic pollutants. With further adjustments on the experimental conditions, the highest removal amount of metals and PAHs was achieved by adding 2?M of HCl with 3?days mixing, followed by Fe²⁺-activated persulfate oxidation (PS/Fe²⁺ molar ratio at 4:1) for further 6?h mixing. The removal efficiency of low and high molecular weight PAHs was about 70 and 20?%, respectively, while the removal efficiency of metals was 70, 100, 40, 65, 65, 80, and 100?% for Cr, Cu, Hg, Mn, Ni, Pb, and Zn, respectively.