Comparison of Several Amendments for In-Site Remediating Chromium-Contaminated Farmland Soil

Hexavalent chromium (Cr(VI)), which has been classified as a Group A human carcinogens list by the United States Environmental Protection Agency, possesses stronger biological toxicity, and its discharge into farmland has become a pressing environmental problems. To screen the cost-efficient Cr(VI)-contaminated soil in situ amended materials, the effects of ordinary zero-valent iron (ZVI), nanoscale zero-valent iron (nZVI), biochar (B), biochar/zero-valent iron (BZVI), and biochar/nanoscale zero-valent iron (BnZVI) on the immobilization of Cr(VI) in spiked soil (Cr(VI) = 325 mg kg^?1, Cr_total = 640 mg kg^?1) were compared in this paper. After 15 days remediation by those materials, toxicity characteristic leaching procedure and physiological-based extraction test showed that the Cr(VI) leachability and bioaccessibility were reduced by 14–92% and 4.3–92% respectively, and the order of immobilization was found to be nZVI > BnZVI > BZVI > ZVI > B. Moreover, sequential extraction procedure indicated that all materials can increase the proportion of the residual Cr, and nZVI had the most significant effect. Plant seedling growth test proved that the nanoscale zero-valent iron was able to reduce the toxicity of chromium in plants greatly in a short time, while BnZVI treatment is more favorable to the growth of plants. To sum up, the nano zero-valent iron and biochar combined treatment not only removed Cr(VI) and immobilized total chromium efficiently but also enabled plant growth in relative high chromium-containing soil.     

Assessment of the stability of chromium in remedied soils by Pannonibacter phragmitetus BB and its risk to groundwater

Purpose

Acid rain can accelerate the acidification of the chromium-contaminated soils, resulting in chromium releasing into soil solution and causing ecological risk. The current study aims to investigate the release of chromium in the remedied soils by Pannonibacter phragmitetus BB under the simulated acid rain leaching and to assess its risk to groundwater.

Materials and methods

P. phragmitetus BB was utilized to remedy the Cr(VI)-contaminated soils at two levels (80 and 1,276 mg kg^?1) by the column leaching experiment, and the chemical remediation with ferrous sulfate was used as a control. The remedied soils by P. phragmitetus BB and ferrous sulfate were leached under the simulated acid rain to evaluate the release of chromium. Furthermore, the risk of chromium release from the remedied soils to the groundwater was assessed by a fuzzy comprehensive evaluation method.

Results and discussion

The average concentrations of water-soluble Cr(VI) in the remedied soils by P. phragmitetus BB were reduced to less than 5.0 mg kg^?1. Under leaching situation with the simulated acid rain, the release of total chromium and Cr(VI) from the remedied soils by P. phragmitetus BB and ferrous sulfate declined rapidly with the extended leaching time. However, the release amounts of total chromium and Cr(VI) from the remedied soil by P. phragmitetus BB more efficiently deceased as compared with that by ferrous sulfate remediation. Carbonate-bounded, exchangeable, and organics-bonded chromium were the major chromium-releasing sources under the simulated rain leaching. After microbial remediation with P. phragmitetus BB and chemical remediation with ferrous sulfate, the risk grades of the remedied soils to groundwater declined from classes 11 to 5 and 6, respectively.

Conclusions

The risks of the remedied soils by both microbial remediation with P. phragmitetus BB and chemical remediation with ferrous sulfate to groundwater effectively decreased and microbial remediation more significantly declined the chromium risk to groundwater than chemical remediation.     

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.     

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.     

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.     

Remediation of Atrazine-contaminated Soil and Water by Nano Zerovalent Iron

Atrazine-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of nano zerovalent iron (nano ZVI) to dechlorinate atrazine (2-chloro-4ethylamino-6-iso-propylamino-1,3,5-triazine) in contaminated water and soil. This study determined the effects of iron sources, solution pH, Pd catalyst and presence of Fe or Al sulfate salts on the destruction of atrazine in water and soil. Our results indicate nano ZVI can be successfully used to remediate atrazine in water and soil. Aqueous solution of atrazine (30 mg l^?1) was treated with 2% (w/v) of nano ZVI and 5% (w/v) of commercial ZVI. Although, iron dose in nano ZVI treatment was less than that in commercial ZVI treatment, atrazine destruction kinetic rate (k _obs) of nano ZVI treatment (1.39 days^?1) was around seven times higher than that of commercial ZVI treatment (0.18 days^?1). Reductive dechlorination was the major process in destruction of atrazine by nano ZVI. The dechlorination product was 2-ethyl-amino-4-isopropylamino-1,3,5-triazine. Lowering the pH from 9 to 4 increased the destruction kinetic rates of atrazine by nano ZVI. Moreover, nano ZVI/Pd enhanced destruction kinetic rates of atrazine (3.36 day^?1). Pd played the important role as a catalyst during treatment of atrazine by nano ZVI. Atrazine destruction kinetic rates were greatly enhanced in both contaminated water and soil treatments by nano ZVI when sulfate salts of Fe(II), Fe(III) or Al(III) was add with the following order of removal rates: Al (III) (2.23 day^?1) > Fe (III) (2.04 day^?1) > Fe(II) (1.79 day^?1). The same results were found in atrazine-nano ZVI-soil incubation experiments.     

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.     

Isolation and characterization of multi-potential Rhizobium strain ND2 and its plant growth-promoting activities under Cr(VI) stress

Soil contaminated by chromium (Cr) is a major concern for sustainable agriculture. Considering this as a basis, the present study was designed to isolate Cr(VI)-reducing and plant growth-promoting bacterial strain from contaminated sampling sources. In this study, Rhizobium strain ND2 was isolated from the root nodules of Phaseolus vulgaris grown in leather industrial effluent contaminated soil. The strain ND2 exhibited strong resistance to different heavy metals and reduced 30 and 50 µg ml^?1 concentrations of Cr(VI) completely after 80 and 120 h of incubation, respectively, as well as chromium adsorption and immobilization were confirmed by scanning electron microscopic equipped with energy X-ray spectroscopy. In addition, the strain produced 21.73 and 36.86 µg ml^?1 of indole-3-acetic acid at 50 and 100 µg ml^?1 of L-tryptophan supplimentations, respectively. Strain ND2 positively affected the exo-polysaccharide, ammonia, protease and catalase production and stimulated root length of various test crops under Cr(VI) stress. Moreover, Rhizobium strain ND2 has the potential to colonize the diverse agricultural crops. Thus, the present findings strongly suggested that the multipotential properties of ND2 could be exploited for bioremediation of contaminated sites with Cr(VI) as well as potential bio fertilizer for enhancing the agricultural productivity.     

Chromium Speciation in Water by Sorption on Calcite and Determination by Electrothermal Atomic Absorption Spectrometry

Abstract

A rapid, sensitive, and accurate method for the separation and speciative determination of chromium (Cr)(VI) and Cr(III) in water samples has been developed using sorption as the separation technique in conjunction with final determination by electrothermal atomic absorption spectroscopy (ETAAS). The present method, where granular calcite is used as selective sorbent, separates Cr(III) with retention values up to 99%, resulting in high accuracy determination of Cr(VI). Total Cr was likewise determined by ETAAS after an efficient reduction of Cr(VI) to Cr(III) using ascorbic acid as reducing agent, deriving Cr(III) concentration from the difference between total Cr and Cr(VI). The parameters of the separation technique, solution pH (4.5–5.5), solution flow rate through the calcite column (0.14–0.42 mL min^?1), and calcite column internal diameter (1.5–3.0 cm), were evaluated. Best results were achieved with pH of 5.5, flow rate of 0.42 mL min^?1, and column internal diameter of 1.5 cm. Optimum determination conditions were found using magnesium nitrate [Mg(NO₃)₂] as chemical modifier, pyrolysis, and atomization temperatures of 1400 and 2200°C, respectively. In such conditions, the detection limits (n=10) were 1.5 and 0.8 µg L^?1 for Cr(III) and Cr(VI), respectively.     

Influence of Chromium with Vermicompost on Growth and Accumulation by Brahmi

Abstract

A pot experiment was conducted under glasshouse conditions during 2004 on brahmi (Bacopa monnieri) at the Central Institute of Medicinal and Aromatic Plants (CIMAP) in Lucknow. The study was conducted to evaluate the influence of different levels of chromium (Cr), with and without vermicompost, on growth and yield, as well as on accumulation of Cr by Bacopa. Rooted cuttings of Bacopa were grown under three levels of Cr (10, 20, and 40 ppm), two levels of vermicompost (2.5 and 5 g kg^?1 soil), and a combination of both. The results indicated that herb yield increased with the joint application of vermicompost and chromium, as compared to compost and Cr alone. Application of Cr only decreased nitrogen (N) and increased phosphorus (P) concentration in plants with increase in its supply, whereas application with vermicompost raised N concentration. Chromium concentration in plant tissue was found to be highest at supply of Cr at 40 ppm+vermicompost 5 g kg^?1 soil. Increase in the supply of Cr only (10, 20, and 40 ppm) decreased iron (Fe), copper (Cu), and zinc (Zn) concentration in plants. The experiment suggests that brahmi, because of its high accumulation ability, could be used as a scavenger to clean Cr‐contaminated soil.     

Emerging resistant microbiota from an acidic soil exposed to toxicity of Cr, Cd and Pb is mainly influenced by the bioavailability of these metals

Purpose

The effect of pollutants in soil microorganisms is an important issue in order to understand their toxic effects in the environment, as well as for developing adequate bioremediation strategies. In this sense, the main objective of this study was to assess the involvement of the indigenous microbiota of an acidic forest Mediterranean soil by artificial pollution with heavy metals, and to detect and isolate resistant microorganisms that could be useful for bioremediation.

Materials and methods

Samples from a previously unpolluted acidic forest soil were amended with Cr(VI), Cd(II) or Pb(II) at total amounts ranging from 0.1 to 5,000 mg?kg^?1. These soil microcosms were incubated under controlled laboratory conditions for 28 days. Soluble fractions of metals were determined from aqueous extracts. Both activity and composition of the microbial community were assessed, respectively, by respirometric assays and molecular analysis (polymerase chain reaction denaturing gradient gel electrophoresis). The isolation of metal-resistant microorganisms was attempted by culture plating from microcosms incubated with high concentrations of metals. Isolated strains were tested in cultures with minimal medium to check for their metal resistance and their capacity to reduce the presence of toxic Cr(VI).

Results and discussion

A decrease in the soil respirometric activity and changes in the microbial community composition were detected from 10/100 mg?kg^?1 Cr and 1,000 mg?kg^?1 Cd and Pb. Presumably resistant bacterial and fungal populations developed in most of these polluted microcosms; however, the microbiota was severely impaired at the highest additions of Cr. Even though Cr was the most damaging metal in soil microcosms, if the soluble fractions of metals are considered instead of their total added amounts, the comparison among their toxic effects suggests a similar potential toxicity of Cr and Pb. Isolated multiresistant microorganisms were related mainly to Actinobacteria, Firmicutes and Ascomycota. Some of them showed the capacity to reduce Cr(VI) concentrations between 54 % and 70 % of the initial value. These strains were affiliated to several species of Streptomyces and Bacillus.

Conclusions

The combination of respirometric assays with molecular methods has been useful to assess the effect of metals on the soil microbial community, which can greatly be explained by their differential bioavailability. Cultivation-dependent and -independent approaches have proved the presence and development of multiresistant microorganisms in a previously unpolluted soil. Due to their properties, some of the isolated strains are potentially useful for soil bioremediation.     

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.     

Effect of Application of Chromium Feedstock Compost on the Growth and Bioavailability of Some Trace Elements in Lettuce

A pot experiment was conducted to investigate the effect of chromium compost (0, 10, 30, and 50%) on the growth and the concentrations of some trace elements in lettuce (Lactuca sativa L.) and in the amended soils. Compost addition to the soil (up to 30%) increased dry matter yield (DMY); more than 30% decreased DMY slightly. The application of compost increased soil pH; nitric acid (HNO₃)–extractable copper (Cu), chromium (Cr), lead (Pb), and zinc (Zn); and diethylenetriaminepentaacetic acid (DTPA)–, Mehlich 3 (M3)–, and ammonium acetate (AAc)–extractable soil Cr and Zn. The addition of Cr compost to the soil increased tissue Cr and Zn but did not alter tissue cadmium (Cd), Cu, iron (Fe), manganese (Mn), nickel (Ni), and Pb. The Cr content in the lettuce tissue reached 5.6 mg kg^?1 in the 50% compost (326 mg kg^?1) treatment, which is less than the toxic level in plants. Our results imply that compost with high Cr could be used safely as a soil conditioner to agricultural crops.     

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.     

Remediation of As-Contaminated Soils in the Guadiamar River Basin (SW, Spain)

In 1998, the pond containing the ore wastes from a pyrite mine in Aznalcóllar (SW, Spain) broke open, spilling some 36×10⁵ m³ of acidic waters and 9?×?10⁵ m³ of tailings containing high concentrations of As and heavy metals. The affected area was around 55 km² of predominantly agricultural soils. After the clean-up of the tailings, many remediation actions were undertaken and the use of blocking agents to immobilize the As was one of the most extended measure. The first experiment performed was to determine the most important soil components in As adsorption under acidic conditions. A second experiment was conducted to neutralize the acidity caused by the solution coming from the tailings undergoing oxidation; an adequate liming material (sugar-refinery scum) was selected and the application rates were established. After the remediation measures, the zone was monitored for three years. A detailed study in four experimental plots located in the most polluted sector was carried out to test the influence of iron oxides in the As immobilization. The use of red soils of the area (rich in free-iron oxides Fe_d) was established as an appropriate material in the remediation of the area.     

Sequencing Zerovalent Iron Treatment with Carbon Amendments to Remediate Agrichemical-Contaminated Soil

Agrichemical spills and discharges to soil can cause point-source contamination of surface and ground waters. When high contaminant concentrations inhibit natural attenuation in soils, chemical treatments can be used to promote degradation and allow application of treated soils to agricultural lands. This approach was used to remediate soil containing >650 mg atrazine, >170 mg metolachlor and >18,000 mg nitrate kg^?1. Results indicated a decrease in metolachlor concentration to <1 mg kg^?1 within 95 days of chemical treatment with zerovalent iron (Fe⁰, 5% w/w) and aluminum sulfate (Al₂(SO₄)₃, 2% w/w) but after one year >150 mg atrazine and >7000 mg nitrate kg^?1 remained. Laboratory experiments confirmed that subsequent additions of sucrose (table sugar) to the chemically pretreated soil promoted further reductions in atrazine and nitrate concentrations. Field-scale results showed that adding 5% (w/w) sucrose to windrowed and pretreated soil significantly reduced atrazine (<38 mg kg^?1) and nitrate (<2,100 mg kg^?1) concentrations and allowed for land application of the treated soil. These results provide evidence that zerovalent iron in combination with Al₂(SO₄)₃ and sucrose can be used for on-site, field-scale treatment of pesticide- and nitrate-contaminated soil.     

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.     

Zero-Valent Iron Removal Rates of Aqueous Cr(VI) Measured Under Flow Conditions

The rates of Cr(VI) removal from the aqueous phase by zero-valent iron, Fe(0), was measured under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a groundwater remediation technology that replaces the sand in a filter pack of a conventional well with a reactive material, such as Fe(0). Dissolved Cr(VI) concentration, dissolved O₂ concentration, and Eh data indicated that Cr(VI) removal from the aqueous phase was mass-transfer limited. All pseudo-first-order regression fits to the data were significant (P≤0.05), however, they did not capture many of the salient aspects of the data, including that the removal rate often decreased as contact time increased. As such, application of these rate coefficients to predict long-term Cr(VI) removal were compromised. The rate coefficients measured under flow conditions were comparable to those measured previously under batch conditions with significantly greater solution:solid ratios. Between the range of 20 and 100 wt-% Fe(0) in the column, there was little measurable change in the reaction kinetics. Thus, it may be possible to include sand into the reactive filter packs in the event it is necessary to increase filter pack porosity or to decrease the accumulation of secondary reaction products that may lead to filter pack plugging. Background water chemistry (0.2 M NaHCO₃, distilled water, and a carbonate-dominated groundwater) had only marginal, if any, effects on reaction rate coefficients. The reaction rates measured in this study indicated that an Fe(0) filter pack could be used to lower Cr(VI) concentrations by several orders of magnitude in a once-through mode of operation of the Reactive Well Technology.     

Integrated effects of cattle manure-derived biochar and soil moisture conditions on soil chemical characteristics and soybean yield

ABSTRACT

A greenhouse experiment was carried out to evaluate the effect of 0, 25, 50 and 100 ton ha^?1 of cattle manure-derived biochar (BC) and soil moisture conditions (SMC) of 100%, 70% and 55% of water-holding capacity (WHC) on soybean production. Most of the macro and micronutrient, soil chemical characteristics and yield production of soybean were significantly affected by BC. Under drought, BC was more effective than that of the non-stressed conditions. Interaction effect of SMC and BC on soil iron (Fe), zinc (Zn), manganese (Mn), calcium (Ca), magnesium (Mg), phosphorus (P) and nitrogen (N) concentrations was also significant indicating that different levels of water supply might show different impact under different levels of BC. Under drought, the higher BC applied, the higher grain yield obtained. Application of 0 to 75 ton BC ha^?1 under WHC caused a high grain yield but 100 ton BC ha^?1 significantly decreased it as compared with the other levels of BC. Positive impacts of BC may be more pronounced under drought. High level of BC in non-stressed conditions may reduce grain yield as occurred in this study. The statistical techniques indicated that higher content of macro and micronutrients negatively associated with yield production of soybean.     

Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.