Heavy metal binding by the polymeric organic fractions of sewage sludges

Organic complexes in sewage sludge play an important role in the speciation and transformation of metals into potentially more toxic and bioavailable forms. Two organic fractions, bacterial extracellular polymer and fulvic acid, were extracted from mixed liquor and digested sewage sludge by methods established as the most appropriate. The homogeneity of the extracts was verified using gel permeation chromatography. Conditional stability constants and complexation capacities of the organic fractions from the sludges with copper, cadmium, nickel and zinc have been determined using equilibrium dialysis titration. Organic fractions extracted from digested sludge demonstrated a greater capacity to complex metals over mixed liquor extracts. Copper formed stronger complexes than nickel with the mixed liquor biomass and cadmium exhibited the greatest affinity for digested sludge organic matter.     

中国部分城市污泥中矿质元素形态与生物可利用性研究

近年来随着城市污水处理厂数目迅速增加,低成本、高效率的污泥农用受到越来越多的关注。研究从北到南的五家污水处理厂消化污泥中矿质元素的含量和形态分布,为污泥资源化的合理利用提供科学参考。结果表明：消化污泥总体呈高有机质、高氮磷、低K、高矿质元素营养的相似性,但其理化性质如阳离子交换容量(CEC)、pH等差异较大,对矿质元素的形态分布与生物可利用性有明显的影响。同种元素在不同污泥中含量的差异较大,相差数倍,甚至十倍以上。污泥中不同元素含量明显不同,Fe的浓度最高,次之是Mg、Zn、B的浓度最低。连续提取研究表明,污泥pH对污泥中矿质元素的形态分布有明显影响,酸性污泥(厦门污水处理厂)中各矿质元素酸溶／交换态百分率明显高于其他污泥。Cu主要分布在氧化态;Zn的三态分布百分率均在10％以上;Mg、Mn的酸溶／交换态含量较高;Fe主要分布在残渣态;B氧化态和还原态的百分率较高。建议在全国范围内进行一次污水处理厂污泥品质调查,为污泥合理农用提供科学依据。     

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.     

Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils

Heavy metals are potentially toxic to human life and the environment. Their contaminating effect in soils depends on chemical associations. Hence, determining the chemical form of a metal in soils is important to evaluate its mobility and bioavailability. We utilized a sequential extraction procedure and sorption isotherms (monometal and competitive) to evaluate the mobility and distribution of Cd, Cu, Ni, Pb, and Zn in four soils differing in their physicochemical properties: Calcixerollic Xerochrepts (Cx1 and Cx2), Paralithic Xerorthent (Px) and Lithic Haplumbrept (Lh). Most of the metals retained under point B conditions of sorption isotherms were extracted from the more mobile fractions: exchangeable and carbonates, in contrast with the profiles of the original soils where metals were preferently associated with the residual fraction. In soils having carbonate concentration under 6% (Cx1 and Lh), the exchangeable fraction was predominant, whereas in calcareous soils (Cx2 and Px) metals extracted from carbonates predominated. Partitioning profiles were in accordance with the affinity sequences deduced from the initial slope of isotherms and showed that the soils had a greater number of surface sites and higher affinity for Pb and Cu than for Cd, Ni, or Zn. In general, the simultaneous presence of the cations under study increased the percentages of metals released in the exchangeable fraction. The tendency towards less specific forms was more noticeable in Cx2 and Px soils and for Ni, Zn, and Cd. The affinity of inorganic surfaces was larger for Zn than for Cd or Ni, but the affinity of organic surfaces was larger for Cd or Ni than for Zn.     

Simple and sequential extractions of heavy metals from different sewage sludges

The presence of heavy metals in the sludges produced in waste-water treatment plants restricts their use for agricultural purposes. This study looks at different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) and compares the distribution of the heavy metals they contain according to the treatment that they have undergone. Some agronomic parameters necessary for characterising a sludge as suitable for use as amendment were determined. The aim of this study is to compare the availability and the localisation of heavy metals in different sewage sludges using simple (water and DTPA) extraction and the BCR (Community Bureau of Reference) sequential extraction procedure. It was confirmed that the total concentration of heavy metals did not exceed the limits set out by European legislation and that the stabilisation treatment undergone by the sludges strongly influenced the heavy metal distribution and the phases to which they were associated and their bioavailability level. The DTPA extraction procedure is cheap and easy to perform and the obtained results are similar to those obtained with the sequential procedure.     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

Copper and trace element fractionation in electrokinetically treated methanogenic anaerobic granular sludge

The effect of electrokinetic treatment (0.15 mA cm(-2)) on the metal fractionation in anaerobic granular sludge artificially contaminated with copper (initial copper concentration 1000 mg kg(-1) wet sludge) was studied. Acidification of the sludge (final pH 4.2 in the sludge bed) with the intention to desorb the copper species bound to the organic/sulfides and residual fractions did not result in an increased mobility, despite the fact that a higher quantity of copper was measured in the more mobile (i.e. exchangeable/carbonate) fractions at final pH 4.2 compared to circum-neutral pH conditions. Also addition of the chelating agent EDTA (Cu2+:EDTA4- ratio 1.2:1) did not enhance the mobility of copper from the organic/sulfides and residual fractions, despite the fact that it induced a reduction of the total copper content of the sludge. The presence of sulfide precipitates likely influences the copper mobilisation from these less mobile fractions, and thus makes EDTA addition ineffective to solubilise copper from the granules.     

Role of extractable and residual organic matter fractions on sorption of phenanthrene in sediments

Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents were much higher than reported values. Phen sorption for the extracted fractions was almost linear, whereas that for the residual fractions was nonlinear, especially for LGF with n 0.56–0.63. As the different organic fractions were removed sequentially, sorption energy distribution on the residual sediment organic matter (SOM) became more heterogeneous. In addition, increasing sorption capacity for the residual fractions, except for BLF with its high polarity, suggested that more sorption sites on the SOM matrix became accessible to Phen. The sorption capacity for LGF was comparable to that of condensed SOM. The residual fraction LGF generally controlled the overall sorption at low Phen concentration, but the extractable fraction FL surpassed the former fraction at high Phen concentration, demonstrating the importance of condensed SOM in the sorption of hydrophobic organic compounds (HOCs) in sediments.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Persistent organic pollutants in soil density fractions: distribution and sorption strength

The sorption strength of persistent organic pollutants in soils may vary among different soil organic matter (SOM) pools. We hypothesized that polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were unevenly distributed and had different soil organic carbon (SOC)-water partition coefficients (K(OC)) among soil density fractions. We determined the concentrations and K(OC) values of 20 PAHs and 12 PCBs in bulk samples and three density fractions (light, <2.0, medium, 2.0-2.4, and heavy, >2.4 g cm(-3)) of 11 urban topsoils (0-5 cm) from Bayreuth, Germany. The K(OC) values were determined using sequential extraction with methanol-water mixtures (35% and 65% methanol) at 60 degrees C. The sum of 20 PAH concentrations in bulk soil ranged 0.4-186 mg kg(-1), and that of 12 PCB concentrations 1.2-158 microg kg(-1). The concentrations of all PAHs and PCBs decreased in the order light>medium>heavy fraction. When normalized to the SOC concentrations, PAH concentrations were significantly higher in the heavy than in the other density fractions. The K(OC) values of the PAHs in density fractions were 3-20 times higher than those of the PCBs with similar octanol-water partition coefficients (K(OW)). The K(OC) values of individual PAHs and PCBs varied up to a factor of 1000 among the studied soils and density fractions. The K(OC) values of 5- and 6-ring PAHs tended to be highest in the heavy fraction, coinciding with their enrichment in this fraction. For the other PAHs and all PCBs, the K(OC) values did not differ among the density fractions. Thus, there is no relationship between sorption strength and distribution among density fractions, indicating that density fractionation is not a suitable tool to distinguish among differently reactive PAH and PCB pools in soils.     

Heavy metal speciation and mobility assessment of arid soils in the vicinity of Al Ain landfill, United Arab Emirates

Sixty-four surface soil samples taken in the vicinity of Al Ain landfill were analysed for cadmium, chromium, copper, nickel, lead and zinc by inductively coupled plasma spectroscopy. Extraction techniques were used to establish the association of the total concentrations of the six metals in the soil samples with their contents in the exchangeable, carbonate, iron/manganese oxides, and residual fractions. In the investigated soils, the recorded concentrations were as follows: 0.043 mg kg^-1 for cadmium, 19.1 mg kg^-1 for chromium, 53.3 mg kg^-1 for copper, 60 mg kg^-1 for nickel, 13.7 mg kg^-1 for lead, and 117 mg kg^-1 for zinc. Cadmium, chromium, nickel, lead and zinc concentrations in the investigated soil samples reflect the natural background values in shale, whereas copper is slightly enriched. I-geo (geoaccumulation index) values of the metals in the soils under study indicate that they are uncontaminated with cadmium, chromium, nickel, lead and zinc, but contaminated to moderately contaminated with copper. Heavy metal contents in the sediments were found to be significantly influenced by different physico-chemical parameters. The effect of these parameters can be arranged in the following order: clay fraction > carbonate fraction > silt fraction > organic matter fractions. A sequential extraction procedure showed that the total concentrations of the heavy metals are largely bound to the residual phase (retained 71.4% of cadmium, 77.8% of chromium, 75% of copper, 47% of nickel, 62.8% of lead, and 75.8% of zinc). A likely sequence of mobility in the investigated soils is as follows: chromium > lead > nickel > cadmium > zinc > copper.     

Sorption-desorption behavior of polycyclic aromatic hydrocarbons in upstream and downstream river sediments

Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.     

Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials

Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects.     

Mobility of heavy metals associated with the natural weathering of coal mine spoils

Knowledge of chemical mobility of heavy metals is fundamental to understanding their toxicity, bioavailability, and geochemical behavior. In this paper, two different methods, i.e. mineralogical means and sequential extractions, were employed to analyze the total contents, existing states, and chemical forms of heavy metals in coal mine spoils. The results demonstrate that the mobility of heavy metals in coal mine spoils depends not only on their existing states and the stability of their host minerals but also on the properties of the coal mine spoils. In the process of coal mine spoils-water interaction, sulfides that contain heavy metals first break down and release metals, which are then adsorbed and complexed by the iron oxyhydroxide colloid resulting from pyrite oxidization and organic matter. During the natural weathering of coal mine spoils, only a small fraction of these metals are released to the environment, and most of them still remains in the residual material.     

Impact of sewage sludge spreading on heavy metal speciation in tropical soils (Réunion, Indian Ocean)

This study was designed to evaluate the impact of sewage sludge spreading on tropical soilborne heavy metal speciation. Sludgeborne heavy metal speciation was also assessed, and the potential mobility of the elements was classified as follows: Zn>Ni>Cu approximately Cr. Two sequential extraction procedures were applied to study Cr, Cu, Ni and Zn speciation in control soils and sludge-amended soils. We demonstrated that sewage sludge spreading over a 2-year period did not have an impact on soilborne heavy metal concentrations but affected speciation of the most mobile fractions of Ni and Zn. Both protocols were consistent for the organic matter fractions, with an increase in Cu, Zn and Cr concentrations in the amended soil as compared to the control soil. In addition, we highlighted that the two protocols characterized different pools of organic matter and that organic compounds remained in the solid matrix after extraction. With respect to the reducible fraction, completely opposite results were obtained with the two protocols and the solid residue study revealed that the two schemes were ineffective in characterizing iron and manganese fractions.     

Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK _a1 (4–5) corresponding to the carboxyl groups; pK _a2 (6–7) corresponding to the phosphoric groups; pK _a3 (8–10) and pK _a4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

北运河沉积物/水界面上重金属迁移转化规律

分析测定了6种元素(Cr、Co、Mn、Cu、Pb、Zn)在北运河水系10个采样点水体和表层沉积物中的含量和形态分布,利用SPSS 19.0统计软件对重金属在不同形态中的含量进行相关性分析。结果显示,北运河下游重金属污染程度高于上游;Cr、Cu、Pb、Zn在底泥可提取态中所占比例相当高,多数采样点都超过10.0%。所研究的重金属多数在底泥Fe-Mn结合态与悬浮物、可交换态、硫化物和有机质结合态均存在相关性;Mn是北运河地化循环中最为活跃的元素。     

Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption

The transport and fate of arsenate in carbonate-rich soil under alkaline conditions was investigated with multiple approaches combining batch, sequential extraction and column experiments as well as transport modeling studies. Batch experiments indicated that sorption isotherm was nonlinear over a wide range of concentration (0.1-200 mg L(-1)) examined. As(V) adsorption to the calcareous soil was initially fast but then continued at a slower rate, indicating the potential effect of rate-limited sorption on transport. Column experiments illustrated that transport of As(V) was significantly retarded compared to a non-reactive tracer. The degree of retardation decreased with increasing As(V) concentration. As(V) breakthrough curves exhibited nonideal transport behavior due to the coupled effects of nonlinear and rate-limited sorption on arsenate transport, which is consistent with the results of modeling studies. The contribution of nonlinear sorption to the arsenate retardation was negligible at low concentration but increased with increasing As(V) concentration. Sequential extraction results showed that nonspecifically sorbed (easily exchangeable, outer sphere complexes) fraction of arsenate is dominant with respect to the inner-sphere surface bound complexes of arsenate in the carbonate soil fraction, indicating high bioavailability and transport for arsenate in the carbonate-rich soils of which Fe and Al oxyhydroxide fractions are limited.