Particle-facilitated lead and arsenic transport in abandoned mine sites soil influenced by simulated acid rain

The role of acid rain in affecting Pb and As transport from mine tailings was investigated by pumping simulated acid rain at a infiltration rate of 10.2 cm/h through soil columns. Simulated acid rain with pH of 3.0, 4.5 and 5.6 were used as leaching solutions. Results showed that 86.9–95.9% of Pb and 90–91.8% of As eluted from the columns were adsorbed by particles in the leachates. Scanning electron microscopy (SEM) analysis showed that particles released from the columns were mainly composed of flocculated aggregates and plate or rod shaped discrete grains. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray analysis (EDX) showed that these particles were predominantly silicate minerals. Results from our experiments demonstrated that when rapid infiltration conditions or a rainstorm exist, particle-facilitated transport of contaminants is likely to the dominant metal transport pathway influenced by acid rain.     

Leaching potential of some phenylureas and their main metabolites through laboratory studies

BACKGROUND, AIMS AND SCOPE: Laboratory studies were conducted with the aim of defining the leaching potential of some phenylureas and their metabolites. A first study was performed for calculating their leaching index (as GUS) on the base of intrinsic properties: persistence (as DT50) and mobility (as Koc) in soil. Another study consisted of aged column leaching experiments whose meaning was to semi-quantify the occurrence of the tested compounds in the leachates, so simulating in field conditions. METHODS: The tested compounds were: diuron, linuron and monolinuron (parents); 3,4-dichloroaniline (DCA), 4-chloroaniline (CLA), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), 1-(4-chlorophenyl)urea (CPU) and monuron, this latter considered both as a metabolite and parent compound. The Koc values of the examined substances were determined by the HPLC screening methods, according to the OECD TG 121. DT50 determinations and aged column leaching experiments were carried out according to SETAC procedures. RESULTS AND DISCUSSION: The examined compounds showed a rather wide range of persistence in soil, with DT50 values less than 2 days for DCA and CLA, close to 8 days for DCPU and CPU and from 16 (diuron) up to 24.8 (DCPMU) days for the others. Their mobility was generally high, based on their Koc values, which ranged from 33 (CPU) to 406 (linuron). The GUS indices indicated that monuron has a clear potential to contaminate groundwater (> 2.8); DCPMU, monolinuron, CPU and diuron are intermediate contaminants (1.8-2.8). Linuron, DCPU, CLA and DCA exhibited a non-leaching behaviour (< 1.8). The aged leaching column experiments showed that parents were found in the leachates at very high percentages respect to the doses applied. The metabolites reached much less percentages, the highest values were observed for monuron from diuron (5.7), CPU (7.2) and DCPMU (8.2%). CONCLUSION: Diuron, Monuron, CPU and DCPMU on the basis of their intrinsic properties, formation from their parents and occurrence in leachates from aged column leaching studies, seem to possess the characteristics of groundwater contaminants. The methodological approach of this study is relatively easy and rapid, hence it can represent a tool for a first screening of compounds such as pesticide metabolites (generally available only in small quantities and for which a field study is not conceivable) or other compounds for which not adequate environmental data are available.     

Utilization of fly ash to improve the quality of the acid mine drainage generated by oxidation of a sulphide-rich mining waste: column experiments

The production of Acid Mine Drainage (AMD) as a result of the oxidative dissolution of sulphides is one of the main pollution problems affecting natural watercourses in mining environments with sulphide-rich residues. In this work, the generation of AMD was prevented by means of the addition of fly ash to sulphide-rich residues in non-saturated column experiments. A column experiment filled with a pyrite-rich sludge with artificial irrigation leached acid drainages (pH approx. 2) containing high concentrations of sulphate, iron and other metals. However, non-saturated column experiments filled with pyritic-rich sludge and fly ash drained leachates characterized by alkaline pH (pH up to 10), low sulphate concentration, and lack of iron and other metals in solution. The pyrite oxidative dissolution at high pH, as a consequence of the leaching of fly ash, favours the metal precipitation inside the column (mainly iron), the coating of pyrite grains, and the attenuation of the oxidation process, resulting in a great improvement in the quality of the leachates.     

Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

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.     

Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process

Abstract

Leaching studies of mecorprop (R,S)‐2‐(4‐chloro‐2‐methylphenoxy)propanoic acid, and dichlorprop, (R,S)‐2‐(4‐chloro‐2,4‐dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods     

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.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Coagulation-flocculation pretreatment of sanitary landfill leachates

Sanitary landfill leachates are considered as heavily polluted industrial wastewaters, presenting significant time and spatial variations of their physical-chemical parameters. Special care is required for their efficient treatment and disposal. The main aim of this work was to examine the application of coagulation-flocculation for the treatment of raw and partially stabilized leachates. Jar-test experiments were employed in order to determine the optimum conditions for the removal of organic matter and color, i.e. coagulant-flocculant combination, effective dosage and pH control. Ferric chloride, aluminium sulphate and lime were tested as conventional coagulants, whereas four commercial polyelectrolytes were co-examined: one anionic, two cationic and a non-ionic polymer. High chemical oxygen demand (COD) removal capacities (about 80%) were obtained during the addition of ferric chloride to the partially stabilized leachates, whereas low COD reductions (i.e. lower than 35%) were measured during the addition of coagulants in the raw samples. The addition of polyelectrolytes and pH adjustment in the alkaline region were found to affect slightly the removal of pollutants. The physico-chemical process may be used as a useful pretreatment step, especially for fresh leachates, prior to biological treatment, or as a post-treatment (polishing) step for partially stabilized leachates.     

Exposure of an anoxic and contaminated canal sediment: Mobility of metal(loid)s

A derelict canal contains an estimated 9800 tonnes of anoxic sediment with highly elevated concentrations of trace elements. Lack of maintenance, reduced water levels and vegetation colonization threaten the stability of pollutants by removing existing waterlogged reduced conditions. A column leaching study of the sediment under increasingly oxidized conditions showed reductions in As mobility but increased heavy metal concentrations. In a reduced state, As mobility was higher (as a consequence of enhanced Fe and organic carbon solubility) whilst heavy metal concentrations in leachates were lower (due to markedly higher pH). Over 10 contiguous wetting and drying cycles, the consequences were profound; all trace elements were continuously leached with enhanced flushing of Fe, As, Zn and Cu. This raises concern over possible mobilization of pollutants to the wider environment, including groundwater. Options for management to stabilize contaminants are discussed that point to the importance of limiting water flow through the sediment.     

Comparison of Laboratory Batch Methods and Large Columns for Evaluating Leachate from Monofilled Solid Wastes

Analyte concentrations in aqueous leachates from polyethylene tanks filled with five different solid wastes were compared with those in extracts from five laboratory batch procedures. Solid wastes used in the study included: electroplating sludge, electric arc furnace dust, paint Incinerator ash, mine tailings, and municipal refuse incinerator ash. Batch extraction procedures used to extract the solid wastes Included: Monofilled Waste Extraction Procedure (MWEP), U.S. EPA Extraction Procedure (EP), Ham Procedure C (HAM-C), Acetate Buffer Extraction Procedure (ABEP), and Saturated Paste Procedure (PASTE).

Analyte concentrations in leachate from the large columns were reproducible and characteristic of each solid waste. In most Instances, analytes in column leachate reached a peak concentration at a liquld-to-solid ratio of 1:1 followed by a gradual to rapid decrease with continued leaching. Analyte concentrations found in large column leachate were related qualitatively to those found in extracts from the batch procedures which used delonlzed water as the extraction medium (i.e., MWEP, HAM-C, and PASTE). Batch extraction procedures using leaching medium containing acetic acid (I.e., EP) or sodium acetate buffer (i.e., ABEP) generally did not reflect analyte concentrations in leachate from the large columns. These results suggest that batch extraction procedures using acetic acid or acetate buffer are less effective for assessing the teachability of monofilled wastes than extraction methods using deionized water as the extraction fluid.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Leaching Dynamics Studies of Municipal Solid Waste Incinerator Ash

Abstract

An assessment of the short- and long-term hazards from municipal solid waste incinerator (MSWI) ash is made through the elemental analysis of 40 to 50 elements in the ash and leachates produced by several leaching procedures. The ash was analyzed using neutron activation analysis (NAA) and x-ray fluorescence (XRF). The leachates were analyzed using NAA and inductively-coupled plasma atomic emission spectroscopy (ICP). The leaching dynamics of an ash monofill were modelled with a series of extractions using simulated acid rain. An initial spike of the metals Ag, Ba, Be, Cr, Cu, Mo, Pb, Sr, and Zn in the leachates appears to be the greatest hazard posed by MSWI ash monofills. The elements As, Cd, Cu, Hg, Pb, S, and Zn were identified as potential long term hazards utilizing a sequential extraction procedure which approximates the total amount of the elements available over the lifetime of the monofill.

The pH of the resulting leachate is the single greatest factor governing the concentration of metals in solution, more important than the concentration of the element in the ash. These results are applied to an assessment of the suitability of the Toxicity Characteristic Leaching Procedure (TCLP) in measuring leaching potential of an MSWI ash monofill.     

Potential of fly ash for neutralisation of acid mine drainage

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO₃?tonne^?1) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca²⁺, SO₄ ^2?, Na⁺ and Cl^? in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.     

Arsenic mobility in contaminated lake sediments

An arsenic contaminated lake sediment near a landfill in Maine was used to characterize the geochemistry of arsenic and assess the influence of environmental conditions on its mobility. A kinetic model was developed to simulate the leaching ability of arsenic in lake sediments under different environmental conditions. The HM1D chemical transport model was used to model the column experiments and determine the rates of arsenic mobility from the sediment. Laboratory studies provided the information to construct a conceptual model to demonstrate the mobility of arsenic in the lake sediment. The leaching ability of arsenic in lake sediments greatly depends on the flow conditions of ground water and the geochemistry of the sediments. Large amounts of arsenic were tightly bound to the sediments. The amount of arsenic leaching out of the sediment to the water column was substantially decreased due to iron/arsenic co-precipitation at the water-sediment interface. Overall, it was found that arsenic greatly accumulated at the ground water/lake interface and it formed insoluble precipitates.     

Effect of soil amendments on sorption and mobility of metribuzin in soils

Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one), is weakly sorbed to soil therefore, leaches easily to lower soil profiles. Soil amendments play a significant role in the management of leaching losses of pesticides. Therefore, present study reports the effect of organic manure and fly ash amendments on metribuzin downward mobility in sandy loam soil columns. Application of animal manure [T-1(OM) and T-2(OM)] and fly ash [T-1(FA) and T-2(FA)] at 2.5% and 5.0% levels increased the metribuzin retention in the soil. Freundlich constant [K(f)(1/n)] values of metribuzin for treatments T-1(OM) and T-2(OM) were 0.70 and 1.11, respectively, which were significantly higher than the value (0.27) in natural soil (T-0). The respective values for treatments T-1(FA) and T-2(FA) were 1.80 and 4.61. Downward mobility of metribuzin was studied in packed soil columns [300 mm (l)x59 mm (i.d.)]. Both the amendments significantly reduced the downward mobility of metribuzin and affected breakthrough time and maximum concentration of metribuzin in the leachate. Leaching losses of metribuzin were decreased from 97% in natural soil (T-0) column to 64% [T-1(OM)] and 42% [T-2(OM)] for animal manure-amended columns and 26% [T-1(FA)] to 100% [T-2(FA)] for fly ash-amended columns, as metribuzin did not leach out of 5% fly ash-amended column. Study indicates that both animal manure and fly ash were quite effective in reducing the downward mobility of metribuzin in packed soil columns of a sandy loam soil.     

Enhanced solubilization of arsenic and 2,3,4,6 tetrachlorophenol from soils by a cyclodextrin derivative

The application of extracting aqueous solutions with cyclodextrins in several soil remediation technologies has been increasingly studied but little is known about their removal capacities toward the inorganic species. Herein, the effectiveness of cyclodextrins (CDs) in extracting arsenic, copper, and iron from a mining soil is presented. In a preliminary test of four types of CD aqueous solutions, only the addition of carboxylmethyl-beta-cyclodextrin CMCD (a cyclodextrin derivative) led to a significant enhancement in arsenic removal. An increase in the concentration of copper and iron in the leachates was also observed with CMCD. Kinetic study of arsenic release was carried out at two temperatures (20 and 35 degrees C). The arsenic concentration in the leachates increases with increasing cyclodextrin concentration. At an 80 mM CMCD concentration, arsenic, copper, and iron released in filtrates were about 20-, 1,000-, and 4,000-fold greater, respectively, than that obtained using deionized water. In the soil system, the CMCD capacity removal was found to be higher for cations than for arsenic. Because the tetrachlorophenol can co-occur with arsenic and copper in several contaminated sites, its solubilization by CMCD was also investigated. Extraction experiments were performed to extract 2,3,4,6 tetrachlorophenol (TeCP) in spiked soil with CMCD. The results of batch experiments have shown that CMCD could significantly increase the TeCP extraction from soil. CD sorption on soils as quantified by a fluorescence technique was low, indicating no significant loss of CD during the leaching experiments. The use of CMCD as a flushing agent to enhance the removal of both inorganic and organic pollutants from mixed-contaminated soils appears as a promising remediation method.     

Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43–55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20–43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption–desorption through column experiments

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.