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.     

Synthetic zeolites as amendments for sewage sludge-based compost

The effects of incorporating a synthetic zeolite (Zeolite P) in a range of concentrations (0.1-1.0 w:w) into an experimental horticultural compost, derived from sewage sludge, have been investigated. The impact of zeolite treatment on time-related changes of the labile zinc, copper, iron and manganese pools within the compost was compared to lime incorporation (5% w:w) and to a proprietary unamended peat-based compost. Addition of 0.5% and 1.0% zeolite significantly reduced labile zinc over a 90 day period. The highest zeolite treatment was more effective than liming; 0.5% zeolite was as effective as lime. Plant growth trials measuring transfer of metals to ryegrass (Lolium perenne L. cv Elka) in successive harvests demonstrated that both 1.0% zeolite and 5% lime treatment caused significant reduction in total metal transfer from soil-plant over a 116 day growth period. It is concluded that the use of synthetic zeolite as an amendment for compost of this type significantly reduces potential for soil metal mobility and soil-plant transfer.     

低浓度含砷污酸处理工艺的比较研究

比较研究了石灰中和法和石灰-铁盐法对硫化后含低浓度砷(20～50 mg/L)污酸的处理效果。结果表明,单纯采用石灰法,废水难以达标排放;而两段石灰-铁盐(氯化铁)法满足达标排放的同时,一段及二段沉淀物的浸出液中砷、镉、铜、铅和锌含量均低于危险废物鉴别标准要求(GB 5085.3-2007);其最优工艺参数为一段终了pH=2,反应时间为2 h,二段终了pH=8、Fe/As=8、反应时间为60 min、氧化剂投加量(Ca(ClO)2/As)为6∶1;正交实验结果中各参数对铁盐除砷效果影响顺序为终了pH>反应时间>Fe/As>氧化剂投加量。     

Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries

This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.     

Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing phyllosilicates

Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinylchloride (VC)) by iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite) was characterized to obtain better understanding of the behavior of these contaminants in systems undergoing remediation by natural attenuation and redox manipulation. Batch experiments were conducted to evaluate dechlorination kinetics and some experiments were conducted with addition of Fe(II) to simulate impact of microbial iron reduction. A modified Langmuir-Hinshelwood kinetic model adequately described reductive dechlorination kinetics of target organics by the iron-bearing phyllosilicates. The rate constants stayed between 0.08 (+/-10.4%) and 0.401 (+/-8.1%) day(-1) and the specific initial reductive capacity of iron-bearing phyllosilicates for chlorinated ethylenes stayed between 0.177 (+/-6.1%) and 1.06 (+/-7.1%) microM g(-1). The rate constants for the reductive dechlorination of TCE at reactive biotite surface increased as pH (5.5-8.5) and concentration of sorbed Fe(II) (0-0.15 mM g(-1)) increased. The appropriateness of the model is supported by the fact that the rate constants were independent of solid concentration (0.0085-0.17 g g(-1)) and initial TCE concentration (0.15-0.60 mM). Biotite had the greatest rate constant among the phyllosilicates both with and without Fe(II) addition. The rate constants were increased by a factor of 1.4-2.5 by Fe(II) addition. Between 1.8% and 36% of chlorinated ethylenes removed were partitioned to the phyllosilicates. Chloride was produced as a product of degradation and no chlorinated intermediates were observed throughout the experiment.     

Heavy metal accumulation in wheat plant grown in soil amended with industrial sludge

The concentrations of different forms of Zn, Cu, Mn, Ni, Cd, Cr, Pb and Fe metals were determined for the roadside sludge collected from pickling-rolling and electroplating industrial area. In sludge the relative abundance of total heavy metals were Fe>Mn>Cr>Ni>Cu>Pb>Zn>Cd and DTPA-extractable metals were in the order--Fe>Ni>Mn>Cr>Cu>Zn>Pb>Cd. Pot-culture experiment was conducted in soils amended with sludge (0%, 10%, 20%, 30%), pretreated with lime (0%, 0.5% and 1%). The soils were alkaline in nature (pH>8.3) with organic carbon contents were 0.34% and 0.72%. The most abundant total and bio-available metal was Fe. Two wheat seedlings were grown in each pot containing 3kg sludge-amended or control soil and the experiment was conducted till harvesting. Application of sludge increased both total and bio-available forms of metals in the soils, while lime application decreased the bioavailability of heavy metals in sludge-amended soils. The content of organic carbon showed positive correlation with all metals except Zn, Cr and Pb. CEC also showed a strong positive correlation (R2>0.7) with Fe, Mn, Cu, Ni and Cd. Though wheat plants are not accumulators, the translocation efficiency was appreciably high. The translocation factor from shoot to grain was found smaller than that of root to shoot of wheat plants. This makes an implication that the heavy metal accumulation was proportionally lesser in grain than in shoot. In, 10% sludge with 0.5% lime-amended soils; each of these toxic heavy metals was found to be within permissible range (USEPA). Hence, on the basis of present study, the best possible treatment may be recommended.     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。     

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.     

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.     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

Evaluation of various chemical extraction methods to estimate plant-available arsenic in mine soils

Elevated levels of bioavailable As in mining soils, agricultural areas and human habitats may cause potential toxicity to human health, plants and microbe. Therefore, it is essential to determine proper soil chemical extraction method in order to estimate plant-available As in mining soils and protect agricultural and environmental ecosystems by evaluation of environmental risk and implementation of remediation measures. In this study, six single soil chemical extraction processes and four-step sequential chemical extraction protocol were used to determine the relative distribution of As in different chemical forms of soils and their correlations with total As in plants grown in mining areas and greenhouse experiments. The strongest relationship between As determined by single soil chemical extraction and As in plant biomass was found for sodium acetate and mixed acid extractant. The mean percent of total As extracted was: ammonium oxalate (41%)>hydroxylamine hydrochloride (32%)>mixed acid (16%)>phosphate (6%)>sodium acetate (1.2%)>water (0.13%). This trend suggests that most of the As in these soils is inside the soil mineral matrix and can only be released when iron oxides and other minerals are dissolved by the stronger chemical extractant. Single soil chemical extraction methods using sodium acetate and mixed acids, that extract As fractions complexed to soil particles or on the surface of mineral matrix of hydrous oxides of Fe, Mn and Al (exchangeable+sorbed forms) can be employed to estimate and predict the bioavailable As fraction for plant uptake in mining affected soils. In sequential chemical extraction methods, ammonium nitrate and hydroxylamine hydrochloride may be used to provide closer estimates of plant-available As in mining soils.     

Comparative effects on arsenic uptake between iron (hydro)oxides on root surface and rhizosphere of rice in an alkaline paddy soil

The iron (Fe) (hydro)oxides deposited around rice roots play an important role in arsenic (As) sequestration in paddy soils, but there is no systematic study on the relative importance of Fe (hydro)oxides on root surface and in rhizosphere soil in limiting As bioavailability. Twenty-seven rice genotypes were selected to investigate effects of Fe (hydro)oxides on As uptake by rice in an alkaline paddy soil. Results indicated that the As content was positively correlated with the Fe content on root surface, and most of As (88–97%) was sequestered by poorly crystalline and crystalline Fe (hydro)oxides in the alkaline paddy soil. The As sequestration by Fe (hydro)oxides on root surface (IAS_root 16.8–25.0 mg As/(g Fe)) was much higher than that in rhizosphere (IAS_rhizo 1.4–2.0 mg As/(g Fe)); therefore, in terms of As immobilization, the Fe (hydro)oxides on root surface were more important than that in rhizosphere. However, the As content in brown rice did not have significant correlation with the As content on root surface but was significantly correlated (R²?=?0.43, P?<?0.05) with the partition ratio (PR_As?=?IAS_root/IAS_rhizo) of As sequestration on root surface and in rhizosphere, which suggested that Fe (hydro)oxides on root surface did not play the controlling role in lowering As uptake, and the partition ratio PR_As would be a better indicator to evaluate effects of Fe (hydro)oxides around roots on As uptake by rice.

     

Metal concentrations in used engine oils: Relevance to site assessments of soils

Used engine oils contain metals, which upon entering soils may pose risks to human health or the environment. In this study, previously published concentrations of 23 metals in 213 used engine oil samples from the early 1970s to the mid-1990s are statistically evaluated. Neat (100%) used engine oils were found to contain relatively high concentrations of lead, calcium, and zinc, attributable to piston blow-by of leaded gasoline, calcium salt detergent additives, and zinc-bearing anti-corrosion/anti-oxidation additives, respectively. Wear metal concentrations were lower. The lead concentration in used engine oils in the U.S. declined between the 1970s and early 1990s, potentially providing a basis to constrain the “age” of used engine oil(s) in soils. The concentrations of 23 metals in used engine oils were compared to soil risk benchmarks in 15 representative jurisdictions in the U.S., Canada, Australia, and Europe. The maximum concentrations in neat (100%) used engine oil of eight metals – Be, Co, Fe, Mn, Ni, Se, Ag, and Ti – were lower than their collective minimum benchmarks in soils for the jurisdictions surveyed, indicating their concentrations in soils could not be reasonably expected to exceed any soil benchmarks. Nine metals (As, Ba, Cd, Cr, Cu, Pb, Sn, V and Zn), but particularly arsenic, cadmium, lead, tin, and zinc, were identified as potential contaminants of concern (PCOC) for soils from locations impacted with used engine oils, owing to their higher median concentrations (i.e., 2.5, 1.4, 1038, 5.0, and 922 mg/kg in oil, respectively) relative to most soil benchmarks. Site-specific benchmarks and metal concentrations at reasonable oil in soil concentrations require consideration when developing the suite of PCOC metal analytes for conducting site assessments of soils impacted by used engine oil.     

Phosphorus leaching in soils amended with piggery effluent or lime residues from effluent treatment

Phosphorus (P) in wastes from piggeries may contribute to the eutrophication of waterways if not disposed of appropriately. Phosphorus leaching, from three soils with different P sorption characteristics (two with low P retention and one with moderate P retention) when treated with piggery effluent (with or without struvite), was investigated using batch and leaching experiments. The leaching of P retained in soil from the application of struvite effluent was determined. In addition, P leaching from lime residues (resulting from the treatment of piggery effluent with lime to remove P) was determined in comparison to superphosphate when applied to the same three soils. Most P was leached from sandy soils with low P retention when effluent with or without struvite was applied. More than 100% of the filterable P applied in struvite effluent was leached in sandy soils with low P retention. Solid, inorganic forms of P (struvite) became soluble and potentially leachable at pH<7 or were sorbed after dissolution if there were sufficient sorption sites. In sandy soils with low P retention, more than 39% of the total filterable P applied in recycled effluent (without struvite) was leached. Soil P increased mainly in surface layers after treatment with effluent. Sandy soils pre-treated with struvite effluent leached 40% of the P retained in the previous application. Phosphorus decreased in surface layers and increased at depth in the soil with moderate P retention after leaching the struvite effluent pre-treated soil with water. The soils capacity to adsorb P and the soil pH were the major soil properties that affected the rate and amount of P leaching, whereas the important characteristics of the effluent were pH, P concentration and the forms of P in the effluent. Phosphorus losses from soils amended with hydrated lime and lime kiln dust residues were much lower than losses from soils amended with superphosphate. Up to 92% of the P applied as superphosphate was leached from sandy soils with low P retention, whereas only up to 60% of the P applied in lime residues was leached. The P source contributing least to P leaching was the lime kiln dust residue. The amount of P leached depended on the water-soluble P content, neutralising value and application rate of the P source, and the pH and P sorption capacity of the soil.     

Sorption of 2,4-d on natural and organic amended soils of different characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unammended soils. In contrast, the ST soil showed the largest adsorption for unammended soil.     

The use of a sequential leaching procedure for assessing the heavy metal leachability in lime waste from the lime kiln at a caustizicing process of a pulp mill

A five-stage sequential leaching procedure was used to fractionate 13 heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Al, Ni, Co, As, V, Ba) and sulphur (S) in lime waste from the lime kiln at the causticizing plant of Stora Enso Oyj Veitsiluoto Pulp Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction (H₂O), (2) exchangeable fraction (CH₃COOH), (3) easily reduced fraction (HONH₃Cl), (4) oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) residual fraction (HF + HNO₃ + HCl). Although metals were leachable in all fractions, the highest concentrations for most of the metals were observed in the residual fraction (stage 5). It was also notable that the total heavy metal concentrations in lime waste did not exceed the maximal allowable heavy metal concentrations for soil conditioner agents set by the ministry of the Agricultural and Forestry in Finland. The heavy metals concentrations in lime waste were also lower than the maximal allowable heavy metals concentrations of the European Union Directive 86/278/EEC on the protection of environment, and in particular of the soil, when sewage sludge is used in agriculture. The Ca concentration (420 g kg⁻¹; d.w.) was about 262 times higher than the typical value of 1.6 g kg⁻¹ (d.w.) in arable land in Central Finland. However, the concentration Mg (0.2 g kg⁻¹; d.w.) in lime waste was equal to the Mg concentration in arable land in the Central Finland. The lime waste has strongly alkaline pH (12.8) and a neutralizing value (i.e. liming effect) of 47.9% expressed as Ca equivalents (d.w.). This indicates lime waste to be a potential soil conditioner and improvement as well as a pH buffer.     

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.     

Heavy metals incidence in the application of inorganic fertilizers and pesticides to rice farming soils

The concentrations of Cd, Co, Cu, Ni, Pb, Zn, Fe and Mn in different inorganic fertilizers (urea, calcium superphosphate, iron sulphate and copper sulphate) and in pesticides (two herbicides and one fungicide) are evaluated together with the contribution of these metals in soils from their use. The study was made in rice farming areas to the north of Albufera Natural Park (Valencia, Spain). The results obtained show that superphosphate is the fertilizer that contains the highest concentrations of Cd, Co, Cu and Zn as impurities. Copper sulphate and iron sulphate have the most significant concentrations of Pb, and are the only fertilizers in which Ni was detected. The three pesticides analysed show similar Cd contents and the highest levels of Fe, Mn, Zn, Pb and Ni are found in the herbicides. The most significant additions of heavy metals as impurities that soil receives from agricultural practices, are Mn, Zn, Co and Pb. Three contamination indexes have been applied to provide a basis for comparison of potential heavy metal toxicity. These results denote the potential toxicity of heavy metals in the studied soils.     

The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.