Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

The influence of organic ligands on the retention of lead in soil

Organic acids are commonly produced and exuded by plant roots and soil microorganisms. Some of these organic compounds are effective chelating agents and have the potential to enhance metal mobility. The effect of citrate and salicylate on the leaching of lead in soil was investigated in a laboratory experiment. In short-term batch experiments, adsorption of lead to soil was slightly enhanced with increasing salicylate concentration (500-5000 microM) but decreased significantly in the presence of citrate. These observations suggested that citrate may enhance Pb leaching, but this was not observed in the column study. Soluble Pb in the presence and absence citrate or salicylate (up to 5000 microM) was added to soil columns at a moderate flow rate, but no Pb was observed to emerge from the soil in any of the soil columns. Rapid biodegradation of citrate in soil eliminated potential complexing ability. Breakthrough of Pb from soil was noted only when using small columns at high flow rates (>20 pore volumes per day). Under these conditions of physical and chemical non-equilibrium, citrate was not degraded and significantly enhanced Pb mobility. As in the batch adsorption experiments, the presence of salicylate reduced Pb leaching. Considering the extreme conditions required to induce Pb leaching, it is likely that Pb will remain relatively immobile in soil even in the presence of a strong complexing agent such as citrate.     

Modelling of atrazine transport in the presence of surfactants

Laboratory experiments were conducted to examine the effect of detergents on transport of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] through loam and sandy loam soils under saturation conditions. The Convection Dispersion Equation (CDE) was used to model and quantify the effects of detergents on atrazine model parameters: the retardation factor (R), pore velocity (v) and dispersion coefficient (D). The transport parameters were estimated using moment technique and partition coefficient obtained from batch experiments and compared with best-fitted parameters, R and D, keeping pore velocity constant. Results indicated the CDE model was not successful in predicting atrazine transport in the presence of surfactants at high concentrations. In the case of anionic surfactant with Elora loam, the average predicted R and D from moment technique of 3.4 and 11.1 cm2/h, respectively were significantly different than fitted parameters (R = 39 and D = 227 cm2/h). The poor performance of CDE in the presence of surfactants results from physiochemical changes in herbicide solubility and retention to the soil matrix rather than changes in soil hydraulic properties since the predicted pore water velocities from moment technique were similar to those measured during leaching experiments. Nevertheless, BTC analysis with CDE showed that land application of anionic surfactant (sulphonic) significantly increased R and D and decrease v for both soils. Addition of sulphonic increased R of atrazine by 12 and 26 folds for loam and sandy loam soils, respectively. On the other hand non-ionic surfactants seemed to decrease R, especially in sandy loam soil, thus facilitating atrazine leaching through soil. Non-equilibrium conditions seemed to govern atrazine transport in the presence of surfactants; double peaks in breakthrough curves were observed, indicating a need for mathematical models to account for such phenomena. Atrazine dispersion and tailing seemed to be higher through Elora loam compared to Caledon sandy loam due to higher aggregation of the Elora soil.     

Mobility of adsorbed arsenic in two calcareous soils as influenced by water extract of compost

The mobility of arsenic (As) in soil affects both the bio-toxicity of As and the groundwater quality, which in turn indirectly affects the quality of edible part of crops and human health, if the crops were irrigated with As contaminated groundwater. A vertical soil column simulates the depth of a soil profile in a real soil environment. Thus soil column experiment is much more pertinent to soil environment than a batch experiment to simulate solute movement as well as leaching through soil profile. A laboratory soil column experiment was conducted to determine the extent of As leaching from soil percolated with influent that contained organic substances. The water extract of compost (WEC) was used as the source of organic substances. The results of As breakthrough curves (BTCs) showed that less pore volumes of influents were required to reach the relative concentration ratio of 1 (C/C0=1) for the two calcareous soils treated with influent that contained WEC. The concentrations of As in the column effluents of soils percolated with 0.01M KCl in WEC were significantly higher than those percolated with 0.01M KCl with the same volumes of effluents collected. This clearly indicates that dissolved as well as deprotonated organic substances which are negatively charged have higher potential for competing the adsorption sites with As on soils, leading to increasing mobility of As in soil and associated environments. Further, it is observed that the characteristics of soil components related to As adsorption affected the adsorption as well as desorption processes and subsequent mobility of As in soil environment as influenced by organic substances.     

Influence of kinetic sorption and diffusion on pesticide movement through aggregated soils

Laboratory studies were carried out to investigate solute leaching at different times from application in relation to temperature and initial soil moisture. Aggregates of a heavy clay soil were treated with a non-interactive solute (bromide) and the herbicides chlorotoluron, isoproturon and triasulfuron. The soil was incubated at 90% field capacity and either 5 or 15 degrees C. The influence of application to initially dry and initially wet aggregates on the behaviour of isoproturon was also investigated. At intervals, samples were either leached in small columns, centrifuged to characterise the fraction of chemical available in pore water under natural moisture conditions or extracted with organic solvents to assess total residues in soil. Bromide concentrations in leachate and in pore water extracted by centrifugation were constant with time. In contrast, availability for leaching and concentration in pore water of the herbicides decreased with increasing time from application in soil incubated at 15 degrees C. The effect of residence time was much smaller at 5 than at 15 degrees C. At the higher temperature, pesticide concentrations in leachate and pore water declined faster than would be expected from degradation alone, probably due to slow diffusion of the pesticides into soil aggregates where they are less available for leaching and/or slow sorption-desorption. The faster decline in availability for leaching at 15 than at 5 degrees C was attributed to faster degradation of the readily available fraction. There was no significant influence of initial soil moisture on either the leaching behaviour of isoproturon or its availability in soil water.     

Effect of seepage conditions on chemical attenuation of arsenic by soils across an abandoned mine site

The effect of seepage velocity on the As leaching/adsorption by soils collected from abandoned mine sites was evaluated under batch equilibrium and different seepage settings. The breakthrough curves (BTCs) of As leaching from the mine soil column initially displayed the peak export and gradually leveled off over the leaching experiment. A similar As peak was observed after a flow interruption period. Adsorption by downgradient soils was clearly nonlinear, as Freundlich N was <1. In the BTCs of the layered columns, where downgradient soils were overloaded above the mine soil, the extended lag period of As appearance and lower steady-state As concentration observed for slow seepage velocity supported the idea of kinetically limited As attenuation driven by soil adsorption. The perturbation of As concentration was insignificant when the intra-column As concentration gradient was higher. The As concentration drop and time to recovery were greater for less adsorptive soil and fast seepage velocity. Desorption of As from soils retrieved from both batch adsorption and column experiment demonstrate hysteric behavior. The results of this work demonstrated that the risk of As leaching from an abandoned mine site can be greatly attenuated by intermediate downgradient soils via chemical adsorption, which tends to be kinetically limited and energetically hysteric (i.e., non-identical energy pathway).     

Arsenic concentration in porewater of an alkaline coal ash disposal site: Roles of siderite precipitation/dissolution and soil cover

The geochemical behavior of As in porewaters of an alkaline coal ash disposal site was investigated using multilevel samplers. The disposal site was in operation from 1983 until 1994 and was covered with 0.3–0.5 m thick soils in 2001 when this study was initiated. Sequential extraction analyses and batch leaching experiments were also performed using the coal ash samples collected from the disposal site. The results suggest the important roles of siderite (FeCO₃) precipitation/dissolution and soil cover, which have been ignored previously. Arsenic levels in the porewater were very low (average of 10 μg L⁻¹) when the site was covered with soil due to coprecipitation with siderite. The soil cover enabled the creation of anoxic conditions, which raised the Fe concentration by the reductive dissolution of Fe-(hydr)oxides. Because of the high alkalinity generated from the alkaline coal ash, even a small increase in the Fe concentration (0.66 mg L⁻¹ on average) could cause siderite precipitation. When the soil cover was removed, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as (hydr)oxides. As a result, the dissolution of previously precipitated As-rich siderite caused higher As concentration in the porewater (average of 345 μg L⁻¹).     

Influence of hydrological regime on pore water metal concentrations in a contaminated sediment-derived soil

Options for wetland creation or restoration might be limited because of the presence of contaminants in the soil. The influence of hydrological management on the pore water concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn in the upper soil layer of a contaminated overbank sedimentation zone was investigated in a greenhouse experiment. Flooding conditions led to increased Fe, Mn, Ni and Cr concentrations and decreased Cd, Cu and Zn concentrations in the pore water of the upper soil layer. Keeping the soil at field capacity resulted in a low pore water concentration of Fe, Mn and Ni while the Cd, Cu, Cr and Zn concentrations increased. Alternating hydrological conditions caused metal concentrations in the pore water to fluctuate. Formation and re-oxidation of small amounts of sulphides appeared dominant in determining the mobility of Cd, Cu, and to a lesser extent Zn, while Ni behaviour was consistent with Fe/Mn oxidation and reduction. These effects were strongly dependent on the duration of the flooded periods. The shorter the flooded periods, the better the metal concentrations could be linked to the mobility of Ca in the pore water, which is attributed to a fluctuating CO(2) pressure.     

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.     

Potential for microbially mediated redox transformations and mobilization of arsenic in uncontaminated soils

Surface soil samples, which had no significant As contamination, were examined for As(V) reduction, As(III) oxidation and As mobilization capability. All five soil samples tested exhibited microbial As(V)-reducing activities both in aerobic and anaerobic conditions. Under aerobic conditions when As(V) reduction had almost ceased, oxidation of As(III) to As(V) occurred, whereas only As(V) reduction was observed under anaerobic conditions. In cultures incubated with As(III), As(III) was oxidized by indigenous soil microbes only under aerobic conditions. These results indicate that microbial redox transformations of As are ubiquitous in the natural environment regardless of background As levels. Mobilization through microbially mediated As(V) and Fe(III) reduction occurred both in the presence and absence of oxygen. Significant variation in dissolved As occurred depending on the Fe contents of soils, and re-immobilization of As arose in the presence of oxygen, presumably as a consequence of dissolved As(III) and Fe(II) oxidation. There was no apparent correlation between dissolved Fe(II) and As, suggesting that reductive dissolution of Fe(III) minerals does not necessarily determine the extent of As release from soils.     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Experimental Zn(II) retention in a sandy loam soil by very small columns

The use of column experiments, usually performed to better approximate field conditions, may provide information that is not available from batch experiments. In such experiments heavy metals are often adsorbed until saturation followed by desorption experiments. When the affinity of the metal to soil is high, the retention factor (R) could be greater than thousands and the duration of experiments can become impractically long. In order to use reasonable laboratory time, the flow rate should be increased or the column size decreased. The increase in flow rate produces undesirable kinetic and dispersion effects, so we used very small soil columns (pore volume = 0.31–0.70 ml) and relatively high flow rates (0.03–0.12 ml min⁻¹) in studies of Zn(II) adsorption and retention in soils. Conservative tracer flow column experiments under saturation conditions were carried out to determine flow parameters for different flow rates. Column pore volume (V_p), Peclet numbers (Pe) and longitudinal dispersion coefficients (D_L) were determined from breakthrough curves. The effect of type of electrolyte and ionic strength on the Zn(II) retention onto soil was determined. The influence of flow rate and bed height on the retention coefficient and on the mass transfer zone was also studied. The effect of different influent Zn(II) concentrations on the R values obtained was analyzed. Freundlich parameters from column experiments were compared with batch ones. The leaching efficiency of different electrolytes, salts of weak organic acids and EDTA was also studied.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Arsenic mobility in brownfield soils amended with green waste compost or biochar and planted with Miscanthus

Degraded land that is historically contaminated from different sources of industrial waste provides an opportunity for conversion to bioenergy fuel production and also to increase sequestration of carbon in soil through organic amendments. In pot experiments, As mobility was investigated in three different brownfield soils amended with green waste compost (GWC, 30% v/v) or biochar (BC, 20% v/v), planted with Miscanthus. Using GWC improved crop yield but had little effect on foliar As uptake, although the proportion of As transferred from roots to foliage differed considerably between the three soils. It also increased dissolved carbon concentrations in soil pore water that influenced Fe and As mobility. Effects of BC were less pronounced, but the impacts of both amendments on SOC, Fe, P and pH are likely to be critical in the context of As leaching to ground water. Growing Miscanthus had no measurable effect on As mobility.     

Relation of enhanced Pb solubility to Fe partitioning in soils

It is well documented that Pb solubility may be related to Fe chemistry in soils and enhanced Pb solubility may occur under certain reducing conditions; however, quantification of such relationships is unavailable. Based on metal classification, Pb (II) and Fe (II) are similar in some chemical characteristics. Thus, competition between Pb and Fe for ligands in soils may be important in determining Pb solubility. In this paper, Pb solubility was examined in a sandy soil after spiking with Pb and incubating for 40 days under water-flooded or non-water-flooded conditions. Solution chemistry in soil columns was adjusted using different concentrations of NaCl, CaCl(2) and deionized water of varying pH before incubation. The results showed that Pb solubility in the soil was not correlated well with pH, dissolved organic C or aqueous Fe concentrations. However, an index of Fe partition behavior using the ratio of aqueous Fe to sorbed Fe was related to Pb solubility. Enhanced Pb solubility occurred only when the index was < approximately 2 kg l(-1). The index can be a simple measure of Fe's ability to compete with Pb for ligands in solution. The ability of Fe to compete with Pb decreases as the index decreases and as the ratio approached its minimum, substantial increases in Pb solubility will be expected. In general, the index was not sensitive to changes in solution chemistry. A similar trend was observed using one data set published in the literature.     

Arsenic mobility and speciation in a contaminated urban soil are affected by different methods of green waste compost application

Application of green waste compost (GWC) to brownfield land is now common practice in soil restoration. However, previous studies have demonstrated both beneficial and detrimental effects on arsenic and metal mobility. In this paper, trace element behaviour was investigated following GWC application, either as surface mulch to, or mixed into soil from a previously described brownfield site in the U.K. Significant differences in arsenic mobility were observed between treatments. Mulching caused most disturbance, significantly increasing soil pore water As, together with Fe, P, Cr, Ni and dissolved organic carbon, the latter was a critical factor enhancing As mobilization. Arsenate was the main inorganic As species in soil pore water, increasing in concentration over time. An initial flush of potentially more toxic arsenite decreased 4 weeks after compost application. Biological processes appeared to play an important role in influencing As mobility. The results point to the necessity for careful management of As-contaminated soils.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.