Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate

An environment-friendly and cost-effective extraction method has been studied for the removal of arsenic from contaminated soil. A yellow-brown forest soil was contaminated with arsenic(V) and used as a model soil. Among various potassium and sodium salts, potassium phosphate was most effective in extracting arsenic, attaining more than 40% extraction in the pH range of 6–8 with minimum damage to the soil properties. Exchange mechanism is proposed for the extraction of arsenic from soil by phosphate. Sequential extraction shows that phosphate is effective in extracting arsenic of Al- and Fe-bound forms. Arsenic of residual form was not extracted. Arsenic was efficiently extracted by phosphate solution of pH 6.0 at 300 mM phosphate concentration and at 40°C.     

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.     

Evaluation of the stability of arsenic immobilized by microbial sulfate reduction using TCLP extractions and long-term leaching techniques

An investigation was conducted to evaluate the stability or leachability of arsenic immobilized by microbial sulfate reduction. Anoxic solid-phase samples taken from a bioreactor previously used to treat metal and As contaminated water using sulfate reducing bacteria (SRB) were subjected to the toxicity characteristic leaching procedure (TCLP) and long-term column leaching tests. The results from TCLP experiments showed that the concentration of As leached from solid-phase sulfide material (SSM) samples after an 18 h extraction time was <300 microgl(-1), which is below the current maximum Australian TCLP leachate value for As, and thus would not be characterized as a hazardous waste. In terms of percent total As leached, this was equivalent to <8.5% for SSM samples initially containing 61.3 mgkg(-1) As. The levels of As extracted by the TCLP was found to be significantly lowered or underestimated in the presence of dissolved oxygen, with As concentrations increasing with decreasing headspace-to-leachant volume ratios. The concentration of As was also consistently higher in nitrogen purged extractions compared to those performed in air. This was attributed to the dissolution of Fe-sulfide precipitates and subsequent oxidation of Fe(II) ions and precipitation of ferric(hydr)oxides, resulting in the adsorption of soluble As and corresponding decrease in As concentrations. According to the experimental data, it is recommended that TCLP tests for As leachability should be performed at least in zero-headspace vessels or preferably under nitrogen to minimize the oxidation of Fe(II) to ferric(hydr)oxides. In long-term leaching studies (approximately 68 days), it was found that the low solubility of the SSM ensured that rate of release of As was relatively slow, and the resulting leachate concentrations of As were below the current Australian guideline concentration for arsenic in drinking water.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Arsenic and heavy metal mobility in iron oxide-amended contaminated soils as evaluated by short- and long-term leaching tests

Several iron-bearing additives were evaluated for their effectiveness in the attenuation of arsenic (As) in various contaminated soils. These were selected for their known or potential ability to adsorb As anions, thus changing the speciation of As in a soil system. Three soils with different sources of As contamination were investigated (canal dredgings, coal fly ash deposits, and low-level alkali waste). The amendments used were goethite (alpha-FeOOH), iron grit, iron (II) and (III) sulphates (plus lime), and lime, applied to the soils at a rate of 1% w/w. A series of leachate extraction tests (UKEA, ASTM and modified Dutch column leaching test) were conducted on the equilibrated amended soils. These were used to firstly evaluate the potential of the amendments as immobilising agents, and secondly to compare the short- and long-term durability of their effects. Column tests demonstrated the efficiency of iron oxides over the longer time scale; these treatments significantly reduced concentrations of arsenic in leachates from all treated soils. Amended soils were also observed to contain higher levels of lead (Pb) and cadmium (Cd) in their leachates, signifying that certain Fe-oxides potentially increased heavy metal mobility in treated soils. The conclusions were that whilst Fe-oxides may be used as effective in situ amendments to attenuate As in soils, their effects on other trace elements, such as Pb and Cd, require careful consideration.     

Arsenic hyperaccumulation by Pteris vittata from arsenic contaminated soils and the effect of liming and phosphate fertilisation

Pot experiments were carried out to investigate the potential of phytoremediation with the arsenic hyperaccumulator Pteris vittata in a range of soils contaminated with As and other heavy metals, and the influence of phosphate and lime additions on As hyperaccumulation by P. vittata. The fern was grown in 5 soils collected from Cornwall (England) containing 67-4550 mg As kg(-1) and different levels of metals. All soils showed a similar distribution pattern of As in different fractions in a sequential extraction, with more than 60% of the total As being associated with the fraction thought to represent amorphous and poorly-crystalline hydrous oxides of Fe and Al. The concentration of As in the fronds ranged from 84 to 3600 mg kg(-1), with 0.9-3.1% of the total soil As being taken up by P. vittata. In one soil which contained 5500 mg Cu kg(-1) and 1242 mg Zn kg(-1), P. vittata suffered from phytotoxicity and accumulated little As (0.002% of total). In a separate experiment, neither phosphate addition (50mg P kg(-1) soil) nor liming (4.6 g CaCO3 kg(-1) soil) was found to affect the As concentration in the fronds of P. vittata, even though phosphate addition increased the As concentration in the soil pore water. Between 4 and 7% of the total soil As was taken up by P. vittata in 4 cuttings in this experiment. The results indicate that P. vittata can hyperaccumulate As from naturally contaminated soils, but may be suitable for phytoremediation only in the moderately contaminated soils.     

Evaluation of remediation process with plant-derived biosurfactant for recovery of heavy metals from contaminated soils

A washing process was studied to evaluate the efficiency of saponin on remediating heavy metal contaminated soils. Three different types of soils (Andosol: soil A, Cambisol: soil B, Regosol: soil C) were washed with saponin in batch experiments. Utilization of saponin was effective for removal of heavy metals from soils, attaining 90-100% of Cd and 85-98% of Zn extractions. The fractionations of heavy metals removed by saponin were identified using the sequential extraction. Saponin was effective in removing the exchangeable and carbonated fractions of heavy metals from soils. In recovery procedures, the pH of soil leachates was increased to about 10.7, leading to separate heavy metals as hydroxide precipitates and saponin solute. In addition recycle of used saponin is considered to be effective for the subsequent utilization. The limits of Japanese leaching test were met for all of the soil residues after saponin treatment. As a whole, this study shows that saponin can be used as a cleaning agent for remediation of heavy metal contaminated soils.     

Dynamic studies on the mobility of trace elements in soil and sediment samples influenced by dumping of residues of the flood in the Mulde River region in 2002

In the analysis of soil samples, batch sequential extraction procedures are traditionally used for the fractionation of trace elements to access their mobility and potential risk for the contamination of groundwater. In the present work a continuous-flow technique has been used that enables not only the fast and efficient leaching of trace elements but as well as time-resolved studies on the mobilization of arsenic and selected heavy metals in different forms to be made. Rotating coiled columns (RCC) earlier used mainly in countercurrent chromatography have been successfully applied to the dynamic leaching of heavy metals from soils contaminated by flooding sludge's. The sample was retained in a PTFE rotating column as the stationary phase whereas aqueous solutions were continuously pumped through. The contents of elements were determined by on-line coupling of RCC and inductively coupled plasma atomic emission spectrometry (ICP-AES). This enables real-time data on the leaching process to be obtained. Dynamic and traditional batch procedures were compared. It has been shown that the aqueous elution under centrifugal forced conditions is much more effective for the mobilization of heavy metals. Hence, the dynamic leaching is characterized by a substantially more intensive interaction between solid and water and is besides substantially more time-saving than the conventional batch procedure. The RCC procedure was also employed for preliminary leaching studies with a simulated "acid rain". In comparison with the water leaching, the mobilization of heavy metals and arsenic from soil samples with employment of simulated acid rain as eluent was less effective.     

Effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile

The effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile was studied. Two soils were sequentially extracted for arsenic with a five-step method that accounts for the following arsenic forms: non-specifically adsorbed (F1), specifically adsorbed (F2), amorphous and poorly crystallized Fe and Al oxides (F3), well-crystallized Fe and Al oxides (F4) and residual (F5). The arsenic residual fraction was predominant in Pintué soil, whereas in Graneros soil, arsenic was mostly associated to amorphous Fe and Al oxides. Graneros soil exhibited a higher As(V) adsorbing capacity than Pintué soil, which relates to the higher clay and iron and aluminum oxides contents, confirming that these components participation is essential for the adsorption of this metalloid. Biosolid application at a rate of 100Mg ha(-1) caused an increase in arsenic bound to amorphous Fe and Al oxides and in the residual fraction, in Pintué soil. When Pintué soil was spiked with arsenic, aged for two months, and treated with biosolid (100Mg ha(-1)), the content of arsenic in the most labile fractions decreased, thus showing a favorable effect in its application to soils with few specific sites for arsenic adsorption. Arsenic speciation was carried out in the first two fractions of the sequential extraction procedure. As(V) was the main form in both fractions. Biosolid incorporation at a rate of 100Mg ha(-1) caused a significant increase in organic arsenic forms.     

In situ remediation of soils contaminated with toxic metal ions using microwave energy

Following onto our work on the in situ remediation of soils contaminated with PAH's, PCB's and other polychlorinated organic compounds using microwave energy, we now report a preliminary investigation on the in situ remediation of soils contaminated with toxic metal ions: Cd(II), Mn(II), Th(IV), Cr(III) and mainly Cr(VI). The soil is partially vitrified in the process, and extraction with hot (70 degrees C) 35% nitric acid for 4.5 h leads to the recovery of very small amounts of the metals which had been spiked into the clean soil: Cd, Mn, and Cr(III) are completely immobilized (unextractable), Th is mostly unextractable, and Cr(VI) partially extractable at very high levels of spiking, but almost completely unextractable using the US EPA Toxicity Characteristic Leaching Procedure. This suggests that contaminated soils which are not going to be used for agricultural purposes can be remediated safely to preset depths without fear of the toxic metal ions leaching out for a long time.     

Occurrence of arsenic in brown rice and its relationship to soil properties from Hainan Island, China

The acquaintance of arsenic concentrations in rice grain is vital in risk assessment. In this study, we determined the concentration of arsenic in 282 brown rice grains sampled from Hainan Island, China, and discussed its possible relationships to the considered soil properties. Arsenic concentrations in the rice grain from Hainan Island varied from 5 to 309 μg/kg, with a mean (92 μg/kg) lower than most published data from other countries/regions and the maximum contaminant level (MCL) for As_i in rice. The result of correlation analysis between grain and soil properties showed that grain As concentrations correlated significantly to soil arsenic speciation, organic matter and soil P contents and could be best predicted by humic acid bound and Fe-Mn oxides bound As fractions. Grain arsenic rises steeply at soil As concentrations lower than 3.6 mg/kg and gently at higher concentrations.     

Removal of heavy metals and arsenic from contaminated soils using bioremediation and chelant extraction techniques

A combined chemical and biological treatment scheme was evaluated in this study aiming at obtaining the simultaneous removal of metalloid arsenic and cationic heavy metals from contaminated soils. The treatment involved the use of the iron reducing microorganism Desulfuromonas palmitatis, whose activity was combined with the chelating strength of EDTA. Taking into consideration that soil iron oxides are the main scavengers of As, treatment with iron reducing microorganisms aimed at inducing the reductive dissolution of soil oxides and thus obtaining the release of the retained As. The main objective of using EDTA was the removal of metal contaminants, such as Pb and Zn, through the formation of soluble metal chelates. Experimental results however indicated that EDTA was also indispensable for the biological reduction of Fe(III) oxides. The bacterial activity was found to have a pronounced positive effect on the removal of arsenic, which increased from the value of 35% obtained during the pure chemical treatment up to 90% in the presence of D. palmitatis. In the case of Pb, the major part, i.e. approximately 85%, was removed from soil with purely chemical mechanisms, whereas the biological activity slightly improved the extraction, increasing the final removal up to 90%. Co-treatment had negative effect only for Zn, whose removal was reduced from 80% under abiotic condition to approximately 50% in the presence of bacteria.     

Fate and bioavailability of arsenic in organo-arsenical pesticide-applied soils. Part-I: incubation study

A laboratory incubation study was conducted to estimate geochemical speciation and in vitro bioavailability of arsenic as a function of soil properties. Two chemically-variant soil types were chosen, based on their potential differences with respect to arsenic reactivity: an acid sand with minimal arsenic retention capacity and a sandy loam with relatively high concentration of amorphous Fe/Al-oxides, considered a sink for arsenic. The soils were amended with dimethylarsenic acid (DMA) at three rates: 45, 225, and 450 mg/kg. A sequential extraction scheme was employed to identify the geochemical forms of arsenic in soils, which were correlated with the "in vitro" bioavailable fractions of arsenic to identify the most bioavailable species. Arsenic bioavailability and speciation studies were done at 0 time (immediately after spiking the soils with pesticide) and after four-months incubation. Results show that soil properties greatly impact geochemical speciation and bioavailability of DMA; soils with high concentrations of amorphous Fe/Al oxides retain more arsenic, thereby rendering them less bioavailable. Results also indicate that the use of organic arsenicals as pesticides in mineral soils may not be a safe practice from the viewpoint of human health risk.     

Arsenic contaminated site at an abandoned copper smelter plant: waste characterization and solidification/stabilization treatment

A preliminary survey of an arsenic contaminated site from an abandoned copper smelting facility and feasibility study of using solidification/stabilization (S/S) process to treat the contaminant waste were undertaken. It was found that the waste, located in the three-flue gas discharge tunnels, contained 2-40% arsenic. The pH of the contaminated waste is extremely low (ranging from 1.8 to 3.6). The X-ray diffraction evidence indicates that the arsenic particles present in the flue gas mainly exist as As(III), or As(2)O(3). The total amount of arsenic contaminated waste is estimated to be 700 ton in the studied area. About 50% of the particle sizes are less than 2 mm. Arsenic is easily extracted from wastes with a variety of leaching solutions. In order to meet the arsenic leaching standard of the toxicity characteristic leaching procedure (TCLP), an extremely high cement dosage is required in the S/S process (cement/waste weight ratio>6). The waste with lower particle size having higher specific surface area exhibits somewhat positive effect on the S/S performance. The use of fly ash from municipal waste incinerators, in conjunction with the reduced amount of cement, is able to meet the TCLP arsenic and lead standards. The use of lime alone could meet the TCLP arsenic standard, but lead leaching concentrations exceeded leaching Pb standard. The results of semi-dynamic leaching tests of some solidified samples indicate higher accumulated arsenic leaching concentrations after only a few leachant renewals.     

Effects of compost and phosphate amendments on arsenic mobility in soils and arsenic uptake by the hyperaccumulator,Pteris vittata L

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.     

An approach for arsenic in a contaminated soil: Speciation, fractionation, extraction and effluent decontamination

The fractionation and speciation of As in a contaminated soil were investigated, and a remediation strategy was tested. Regarding speciation, we found that As(V) prevails over As(III) whereas more than 40% of total arsenic is in organic form. The fractionation of As was investigated with two sequential extraction methods: a low mobility was found. Then we tested the possibility of using phosphoric acid to extract As from the soil and cleaning the washing effluents by sorption onto montmorillonite. The efficiency of the extraction and of the adsorption onto the clay were also investigated for Cr, Cu, Fe, Mn, Ni, Pb and Zn, whose total concentrations and fractionation in the soil are reported here. The extraction percentages for As and metals ranged from 30 to 65%; the residual proportions in the soil are presumably in very unreactive forms. Montmorillonite showed a good uptake capacity towards the investigated pollutants.     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Remediation of arsenic-contaminated soils and washing effluents

Laboratory experiments were conducted to determine the distribution of various arsenic species in tailings and soils. Other specific goal of the tests were to evaluate the extraction efficiency of arsenic using alkaline or acid washing, to determine optimum operational parameters of alkaline washing, and to evaluate the arsenic precipitation of washing effluents by pH adjustment or ferric chloride addition. Alkaline washing using sodium hydroxide was found to be favorable in removing arsenic from tailings or soils having a higher portion of arsenic in the operationally defined crystalline mineral fraction of crystalline oxide and amorphous aluminosilicates. This is due to the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic because predominant negatively charged crystalline oxides do not attract the negatively charged oxyanions. For tailings, sodium hydroxide had 10-20 times higher extraction efficiencies than hydrochloric- or citric acid. The optimum concentration of sodium hydroxide for soil washing was determined to be 200 mM for all samples, while the optimum ratios were 10:1 and 5:1 for tailings and field/river sedimentary soils, respectively. The washing effluent of river soil was effectively treated by adjusting pH to 5-6 with hydrochloric acid, resulting in arsenic concentrations of <50 microgl(-1). In the case of field soil effluent, an addition of ferric chloride with a minimum mass ratio of 11 (Fe/As) was needed to reduce the arsenic below 50 microgl(-1).     

Arsenic in the soils of Zimapán, Mexico

Arsenic concentrations of 73 soil samples collected in the semi-arid Zimapán Valley range from 4 to 14 700 mg As kg(-1). Soil arsenic concentrations decrease with distance from mines and tailings and slag heaps and exceed 400 mg kg(-1) only within 500 m of these arsenic sources. Soil arsenic concentrations correlate positively with Cu, Pb, and Zn concentrations, suggesting a strong association with ore minerals known to exist in the region. Some As was associated with Fe and Mn oxyhydroxides, this association is less for contaminated than for uncontaminated samples. Very little As was found in the mobile water-soluble or exchangeable fractions. The soils are not arsenic contaminated at depths greater than 100 cm below the surface. Although much of the arsenic in the soils is associated with relatively immobile solid phases, this represents a long-term source of arsenic to the environment.     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.