Distribution of soil arsenic species, lead and arsenic bound to humic acid molar mass fractions in a contaminated apple orchard

Excessive application of lead arsenate pesticides in apple orchards during the early 1900s has led to the accumulation of lead and arsenic in these soils. Lead and arsenic bound to soil humic acids (HA) and soil arsenic species in a western Massachusetts apple orchard was investigated. The metal-humate binding profiles of Pb and As were analyzed with size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). It was observed that both Pb and As bind "tightly" to soil HA molar mass fractions. The surface soils of the apple orchard contained a ratio of about 14:1 of water soluble As (V) to As (III), while mono-methyl (MMA) and di-methyl arsenic (DMA) were not detectable. The control soil contained comparatively very low levels of As (III) and As (V). The analysis of soil core samples demonstrated that As (III) and As (V) species are confined to the top 20 cm of the soil.     

Preliminary evidence that copper inhibits the degradation of DDT to DDE in pip and stonefruit orchard soils in the Auckland region,New Zealand

Orchards (n=13) were sampled as part of a larger survey investigating agrichemical residues (pesticides and trace elements) in cropping soils in the Auckland region, New Zealand. SigmaDDT concentrations in orchard soils ranged from <0.03 to 24.41 mg kg(-1). DDT (o,p'- and p,p'-) comprised at least 40% of the SigmaDDT residues in 67% of orchards in which DDT residues were detected. There was a highly significant negative correlation (-0.924, P<0.001) between copper concentration (21-490 mg kg-1) and the ratio of DDE:DDT (0.4-5.2) in pip and stonefruit orchard soils. In further investigations involving five pip and stone fruit orchard sites and one grazing paddock it was found that soil respiration and the ratio of soil microbial carbon to soil carbon (%Cmic/Org-C) in orchard soils decreased with increasing copper concentration. These findings are consistent with the conclusion that elevated soil copper concentrations in pip and stone fruit orchard soils in the Auckland region may have reduced the ability of the indigenous soil microbial community to degrade DDT to DDE     

An investigation of inorganic antimony species and antimony associated with soil humic acid molar mass fractions in contaminated soils

The presence of antimony compounds is often suspected in the soil of apple orchards contaminated with lead arsenate pesticide and in the soil of shooting ranges. Nitric acid (1M) extractable Sb from the shooting range (8300 microg kg(-1)) and the apple orchard (69 microg kg(-1)) had considerably higher surface Sb levels than the control site (<1.5 microg kg(-1)), and Sb was confined to the top approximately 30 cm soil layer. Sb(V) was the principal species in the shooting range and the apple orchard surface soils. Size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) analysis of humic acids isolated from the two contaminated soils demonstrated that Sb has complexed to humic acid molar mass fractions. The results also indicate that humic acids have the ability to arrest the mobility of Sb through soils and would be beneficial in converting Sb(III) to a less toxic species, Sb(V), in contaminated areas.     

Particulate copper in soils and surface runoff from contaminated sandy soils under citrus production

Soil contamination by copper (Cu) is a worldwide concern. Laboratory incubation and soil Cu characterization were conducted to examine the effects of external Cu loading and liming on Cu speciation in both bulk soil and particulates of an Alfisol and Spodosol under citrus production. Also, drainage water from the sites was evaluated for dissolved and particulate forms of Cu. Soil available Cu estimated by CaCl₂, NH₄OAc, or Mehlich-3 extraction significantly increased with external Cu loads and decreased with soil pH. Most increases in soil Cu occurred in the exchangeable and oxide-bound fractions. Organically bound Cu was the dominant fraction in both bulk soil and particulates, but more in particulates than bulk soil (P?≤?0.001). Organically bound Cu was highly correlated with total recoverable Cu (P?≤?0.01), increased significantly with external Cu loads (P?≤?0.001), and decreased with soil pH (P?≤?0.05). Lime addition converted part of Cu from available pools to more stable forms. Organically bound Cu complexes were found to dominate in soil solution or surface runoff. These results indicate that most Cu accumulated in the contaminated soils is highly mobile, and thus may impact citrus production and the environment.     

Fractionation and bioavailability of metals and their impacts on microbial properties in sewage irrigated soil

A study was conducted to evaluate the effect of long-term irrigation of sewage contaminated with heavy metals like Cd, Cr, Cu and Pb on microbial and biochemical parameters of soils of West Bengal, India. The microbial parameters included microbial biomass carbon (MBC), microbial metabolic quotient; the biochemical parameters included fluorescein diacetate hydrolyzing activity, beta-glucosidase, urease, phosphatase, and aryl sulphatase activities. A sequential extraction technique was used to quantify water soluble, exchangeable, carbonate bound, Fe/Mn-oxide bound, organically bound, and residual metal fractions. Metal concentrations in the two most labile fractions (i.e., water soluble and exchangeable fractions) were generally low. Total metal concentrations at each site seemed to be associated with soil amorphous Fe and Al minerals. The MBC and the enzymes studied were significantly and negatively correlated with water soluble and exchangeable metals but not significantly correlated with other forms, indicating that water soluble and exchangeable forms exerted a strong inhibitory effect on the soil microbial and biochemical parameters. It was concluded that irrigating soils with metal contaminated sewage seemed to damage soil quality in the long term.     

Speciation of scandium and gallium in soil

A method for the speciation of scandium and gallium in soil has been developed. The sequential extraction scheme of Tessier et al. for heavy metals was examined for the scandium and gallium separation. The regents proposed by Tessier were used for the extraction, and only for the residual fraction the HClO(4) was replaced with H(2)SO(4). The optimum conditions for leaching scandium and gallium from the soil were chosen for each fraction. Very sensitive, spectrophotometric methods based on the mixed complexes of Sc(III) and Ga(III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide were applied for the scandium and gallium determination after their separation by solvent extraction. 100% mesityl oxide and a 0.5M solution of 2-thenoyltrifluoroacetone in xylene were chosen for the extraction of scandium and butyl acetate was selected for gallium. Soil samples from two different regions of Poland were the object of this research. The content of scandium and gallium found in the individual fractions of Upper Silesia soil (industrial region) was [in mugg(-1)] Sc: I, 1.52; II, 0.53; III, 7.78; IV, 1.79; V, 0.20; Ga: I, 24.7; III, 29.2; IV, 35.4; V, 6.9. In Podlasie soil (agricultural region), the content of both elements was clearly lower. The total content of scandium and gallium in the five soil fractions was in good correlation with the total content of these elements in the soils found after HF-H(2)SO(4) digestion. Analysis using the ICP-OES method gave comparable results.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Potentially toxic element fractionation in technosoils using two sequential extraction schemes

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier’s scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe–Mn oxide bound fraction of Tessier’s scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier’s scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier’s scheme. The order of mobility of PTE was as follows: Cd?>?Zn?>?Pb in MDN site and As?>?Sb?>?Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.     

Cadmium contamination in orchard soils and fruit trees and its potential health risk in Guangzhou, China

This study examines cadmium (Cd) contamination in orchard soils and fruit trees in Guangzhou, China, and assesses its potential health risk. Soils and tissues samples of three species of fruit trees were collected from three orchards. The average soil Cd concentration was 1.27, 1.84 and 0.68 mg/kg in orchards I, II, and III, respectively. The carambola (Averrhoa carambola) accumulated exceptionally high concentrations of Cd (7.57, 10.84, 9.01 and 2.15 mg/kg dw in root, twig, leaf and fruit, respectively), being 6.0-24 times and 4.0-10 times the corresponding tissue Cd in the longan (Dimocarpus longan) and wampee (Clausena lansium), respectively. Furthermore, all Cd concentrations (0.04-0.25 mg Cd/kg fw) of the fruits exceeded the tolerance limit of cadmium in foods of PR China (0.03 mg/kg fw). Our results indicate that the carambola tree has high Cd accumulation capacity and might be a Cd accumulator; and its fruit, among the three species of fruits studied, also poses the highest potential health risk to local residents.     

Distribution and fractionation of phosphorus, cadmium, nickel, and lead in calcareous soils amended with composts

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0-22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P > Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0-22 cm soil depths except for Cd in the 10-22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe-Mn oxides form in the 0-10 and 10-22 cm soil layers. Cadmium was predominantly in the Fe-Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0-10 cm soil layer.     

Bacterial diversity in paclobutrazol applied agricultural soils

The aim of this study was to investigate the bacterial communities on paclobutrazol [(2RS, 3RS)-1-(4-Chlorophenyl)-4, 4-dimethyl-2-(1H-1,2,4-triazol-1-yl) pentan-3-ol]–applied agricultural soils by denaturing gradient gel electrophoresis (DGGE) of polymerase chain reaction (PCR) amplified 16S rDNA gene fragments. Three different agricultural soil samples were collected from paclobutrazol applied mango and waxapple orchards, peanut fields and untreated rice fields as a control for DGGE analysis. The DGGE pattern of PCR- generated 16S rDNA gene fragments indicated that the bacterial populations from four paclobutrazol–applied soils of peanut fields were closely related to each other and two paclobutrazol–applied soils of mango and waxapple orchards harbored closely related bacterial communities. But, paclobutrazol–free agricultural soils comprised relatively a different bacterial group. However, the bacterial populations of mango and waxapple orchard are completely different from the bacterial communities of peanut field. Further purification and sequence analysis of 40 DGGE bands followed by phylogenetic tree assay showed similar results that soil bacteria from paclobutrazol applied mango and waxapple orchard are phylogenetically related. Based on the phylogenetic analysis, the clone M-4 was clad 100 % (bootstrap value) with Mycobacterium sp. The Mycobacterium sp. has been proved to degrade the phenolic compounds such as phenol, 4-chlorphenol, 2,4-dichlorophenol and paclobutrazol molecule containing chlorobenzene ring.     

Long-term effects of liquid swine manure land surface application in an apple orchard field on soil bacterial community and heavy metal contents in apple (Malus pumila Mill.)

Environmental Science and Pollution Research - This study investigated the impact of liquid swine manure (LSM) land surface application in an apple orchard on soil health and copper (Cu) and zinc...     

Acetylcholinesterase activity in the terrestrial snail Xeropicta derbentina transplanted in apple orchards with different pesticide management strategies

Apple orchards are highly manipulated crops in which large amounts of pesticides are used. Some of these pesticides lack target specificity and can cause adverse effects in non-target organisms. In order to evaluate the environmental risk of these products, the use of transplanted sentinel organisms avoids side-effects from past events and facilitate comparison of multiple sites in a short time. We released specimens of the terrestrial snail Xeropicta derbentina in each 5 of two kinds of apple orchards with either conventional or organic management strategies plus in a single abandoned orchard. After one month, individuals were retrieved in order to measure acetylcholinesterase (AChE) activity. Mean values of AChE activity were significantly reduced in all conventional apple orchards compared to the others. Results show that the measurement of biomarkers such as AChE inhibition in transplated X. derbentina could be useful in the environmental risk assessment of post-authorized pesticides.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

2种分步浸提方法对土壤中Cr形态提取效果的比较

实验模拟了受铬渣污染的土壤环境,比较在不同活性炭加入量下2种典型分步浸提方法:Tessier 5步法和改进的7步分离方法得到的不同结果,探究适合于铬渣污染对土壤环境的铬形态浸提方法。实验结果表明,2种方法的浸提数据虽有较大差异,但能得到相对一致的变化趋势;七步法形态分类更为细致,99%以上的铬都分布在2~3个结合形态,Tessier五步法的物料衡算结果更为准确(96%~103%),相比七步法形态分类更具包容性,数据更具重现性;随着活性炭的加入,土壤环境中游离铬离子明显减少,转化为有机结合态等更稳定的结合形态,说明活性炭能有效固定土壤环境中游离的铬离子,增加其迁移稳定性。     

Application of 16S rDNA-PCR amplification and DGGE fingerprinting for detection of shift in microbial community diversity in Cu-, Zn-, and Cd-contaminated paddy soils

Seven soils were sampled from farmland at different distances (0.01-5 km) from a copper and zinc smelter. The total contents of heavy metals in these soils ranged from 46 to 4895 mg Cu kg-1, 96 to 1133 mg Zn kg-1, and 6.9 to 28.8 mg Cd kg-1, respectively. The available fractions were highly correlated with total contents of the metals. In order to assess the impact of combined contamination of heavy metals on soil bacterial communities, denaturing gradient gel electrophoresis (DGGE) of polymerase chain reaction (PCR) amplicons of 16S rDNA sequence of bacteria in soil was used. Bacterial community structure was affected to some extent by heavy metals. The number of DGGE bands in soils increased with increasing distance from the copper and zinc smelter. Clustering analysis of the DGGE profiles showed that bacteria in the seven soils belonged to three clusters. Bacterial communities in three soils sampled at 0.01-0.60 km from the smelter belonged to one cluster, and those in three soils sampled at 0.8-1.2 km from the smelter belong to another cluster. Bacterial community in soil farthest from the smelter belonged to a single cluster. This study demonstrated that heavy metal contamination decreased both biomass and diversity of bacterial community in the soil.     

Retention and distribution of heavy metals in mangrove soils receiving wastewater

The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.     

Food (miles) for Thought - Energy Balance for Locally-grown versus Imported Apple Fruit (3 pp)

- This commentary compares the primary energy requirement for apples (cultivar ‘Braeburn’), which were either imported or locally-grown in Meckenheim, Germany. Imported apples of the same cultivar were grown in a Southern hemisphere winter in Nelson, Southland, New Zealand, and were picked at the end of March with subsequent 28 d transport by sea for sale in April in Germany. Locally-grown apples (cultivar ‘Braeburn’) were picked in mid-October and required a primary energy of nearly 6 MJ/kg of fruit including 0.8 MJoule/kg for five months CA storage at 1°C during a Northern hemisphere winter until mid-March. This compared favourably with 7.5 MJoule/kg for overseas shipment from New Zealand, i.e. a ca. 27% greater energy requirement for these imported fruits. Overall, the primary energy requirement of regional produce, stored several months on-site, partially compensated for the larger energy required to import fresh fruit from overseas. This result is in marked contrast to reported overestimates of a reported up to 8-fold energy requirement for domestic versus imported apple juice concentrate [7]. Our own findings of less primary energy required for domestic apple fruit is discussed with respect to providing local employment, fruit orchards preserving the countryside, quality assurance systems for local fruit such as QS and EUREP-GAP, networking and other factors favouring regional production.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

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.