Arsenic accumulation in the hyperaccumulator Chinese brake and its utilization potential for phytoremediation

The unique property of arsenic hyperaccumulation by the newly discovered Chinese brake (Pteris vittata L.) fern is of great significance in the phytoremediation of arsenic-contaminated soils. The objectives of this study were to (i) examine arsenic accumulation characterized by its distribution pattern in Chinese brake, and (ii) assess the phytoextraction potential of the plant. Young ferns with five or six fronds were transferred to an arsenic-contaminated soil containing 98 mg As kg-1 and grown for 20 wk in a greenhouse. At harvest, the Chinese brake produced a total dry biomass of 18 g plant-1. Arsenic concentration in the fronds was 6000 mg kg-1 dry mass after 8 wk of transplanting, and it increased to 7230 mg kg-1 after 20 wk with a bioconcentration factor (ratio of plant arsenic concentration to water-soluble arsenic in soil) of 1450 and a translocation factor (ratio of arsenic concentration in shoot to that in root) of 24. The arsenic concentrations increased as the fronds aged, with the old fronds accumulating as much as 13,800 mg As kg-1. Most (approximately 90%) of the arsenic taken up by the Chinese brake was transported to the fronds, with the lowest arsenic concentrations in roots. About 26% of the initial soil arsenic was removed by the plant after 20 wk of transplanting. Our data suggest that the arsenic hyperaccumulating property of the Chinese brake could be exploited on a large scale to remediate arsenic contaminated soils.     

Mycorrhizae increase arsenic uptake by the hyperaccumulator Chinese brake fern (Pteris vittata L.)

Chinese brake fern (Pteris vittata L.) is a hyperaccumulator of arsenic (As) that grows naturally on soils in the southern United States. It is reasonable to expect that mycorrhizal symbiosis may be involved in As uptake by this fern. This is because arbuscular mycorrhizal (AM) fungi have a well-documented role in increasing plant phosphorus (P) uptake, P and As have similar chemical properties, and ferns are known to be colonized by AM fungi. We conducted a factorial greenhouse experiment with three levels of As (0, 50, and 100 mg kg(-1)) and P (0, 25, and 50 mg kg(-1)) and with and without Chinese brake fern colonized by a community of AM fungi from an As-contaminated site. We found that the AM fungi not only tolerated As amendment, but their presence increased frond dry mass at the highest As application rate. Furthermore, the AM fungi increased As uptake across a range of P levels, while P uptake was generally increased only when there was no As amendment. These data indicate that AM fungi have an important role in arsenic accumulation by Chinese brake fern. Therefore, to effectively phytoremediate As-contaminated soils, the mycorrhizal status of ferns needs to be taken into account.     

Role of mycorrhizal fungi and phosphorus in the arsenic tolerance of basin wildrye

Revegetation of arsenic (As)-rich mine spoils is often impeded by the lack of plant species tolerant of high As concentrations and low nutrient availability. Basin wildrye [Leymus cinereus (Scribner & Merr.) A. L?ve] has been observed to establish naturally in soils with elevated As content and thus may be useful for the stabilization of As-contaminated soils. An experiment was conducted to evaluate how variable phosphorus (P) concentrations and inoculation with site-specific arbuscular mycorrhizal fungi influence As tolerance of basin wildrye. Basin wildrye was grown in sterile sand in the greenhouse for 16 weeks. Pots of sterile sand were amended to create one of four rates of As (0, 3, 15, or 50 mg As kg(-1)), two rates of P (3 or 15 mg P kg(-1)), and +/-mycorrhizal inoculation in a 2 x 4 x 2 factorial arrangement. After 16 weeks of growth, plants were harvested, shoots and roots thoroughly washed, and the tissue analyzed for total shoot biomass, total root and shoot As and P concentrations, and degree of mycorrhizal infection. Basin wildrye was found to be tolerant of high As concentrations allowing for vigorous plant growth at application levels of 3 or 15 mg As kg(-1). Arsenic was sequestered in the roots, with 30 to 50 times more As in the roots than shoots under low P conditions. Mycorrhizal infection did not confer As tolerance in basin wildrye nor did mycorrhizal fungi influence biomass production. Phosphorus concentrations of 15 mg kg(-1) effectively inhibited As accumulation in basin wildrye. Basin wildrye has the potential to be used for stabilization of As-rich soils while minimizing exposure to grazing animals following reclamation.     

Antimony impurity in lead arsenate insecticide enhances the antimony content of old orchard soils

Lead arsenate was a commonly used insecticide during the first half of the 20th century, particularly in deciduous tree fruit orchards. Antimony is cotransported with As during the ore refining process and could occur as an impurity in commercial lead arsenate products. The total concentrations of As and Sb in eight soil samples collected from eight orchards located throughout central Washington State were analyzed by neutron activation analysis. Total soil Sb concentrations ranged between 0.4 and 1.5 mg kg(-1), while total soil As concentration ranged from 1 to 170 mg kg(-1). Total soil Sb and As concentrations were positively related. Total Pb and As concentrations in four of the soils were substantially higher than natural background, while the Sb to As concentration ratios in these soils were consistent with values measured in three lead arsenate insecticide products. These results confirm that Sb impurity is present in lead arsenate insecticide and has contributed to Sb enrichment of soils on which lead arsenate-treated plants were grown. Although higher than in uncontaminated soils from the same region, the Sb concentrations in the affected soils fall within the normal range observed worldwide and are substantially lower than values associated with impaired human or environmental health.     

Arsenic distribution in Florida urban soils: comparison between Gainesville and Miami

Arsenic contamination is of concern due to its effect as a carcinogen. Understanding the distribution of arsenic in urban soils is important for establishing baseline concentrations from which anthropogenic effects can be measured. The soil cleanup target level (SCTL) for arsenic in Florida (0.8 and 3.7 mg kg(-1) in residential and commercial areas, respectively) is lower than in most states and is near the arsenic background concentrations in Florida soils. The objective of this study was to characterize the distribution of arsenic in the soils of two Florida cities, Gainesville and Miami. More than 200 soil samples were collected from three land-use classes in each city (residential, commercial, and public land), digested with USEPA Method 3051a, and analyzed with graphite furnace atomic absorption spectrophotometry. Arsenic concentrations varied greatly in Gainesville, ranging from 0.21 to approximately 660 mg kg(-1) with a geometric mean (GM) of 0.40 mg kg(-1) (after discarding outliers), which was significantly lower than the GM of 2.81 mg kg(-1) in Miami, although Miami samples ranged only from 0.32 to approximately 110 mg kg(-1). Arsenic concentrations in 29 and 4% of the Gainesville soil samples and 95 and 33% of the Miami samples exceeded the Florida residential and commercial SCTL, respectively. This study is the first to provide information on arsenic distribution in urban soils of Florida, and the data are useful for assessing arsenic contamination and determining the need for remediation.     

Occurrence of metals in soil and ground water near chromated copper arsenate-treated utility poles

To thoroughly investigate the metal contamination around chromated copper arsenate (CCA)/polyethylene glycol (PEG)-treated utility poles, a total of 189 soil samples obtained from different depths and distances near six treated poles in the Montreal area (Canada) were analyzed for Cu, Cr, and As content. Various soil physicochemical properties were also determined. Ground water samples collected below the poles were analyzed for metals and bioassays with Daphnia magna were conducted. Generally, sandy soils had lower contaminant levels than clayey and organic soils. Copper concentrations in soil were highest followed by As and Cr. The highest Cu (1460 +/- 677 mg kg(-1)), As (410 +/- 150 mg kg(-1)), and Cr (287 +/- 32 mg kg(-1)) concentrations were found at the ground line and immediately adjacent to the pole. Contaminant levels then decreased with distance, approaching background levels within 0.1 m from the pole for Cr and 0.5 m for Cu and As. Chromium and Cu levels generally approached background levels at a depth of 0.5 m. Average As content near the pole on all study sites was three to eight times higher than Quebec's Level C criterion (50 mg kg(-1)), although it dropped to 31 mg kg(-1) at 0.1 m. Results also showed that As persisted up to 1 m in soil depth (17-54 mg kg(-1)). Copper and Cr concentrations in ground water samples were always <1.000 mg L(-1) and <0.05 mg L(-1), respectively and Cr(VI) was <0.02 mg L(-1). One sample contained an As concentration >0.025 mg L(-1) but bioassays showed that, overall, ground water had a low ecotoxic potential.     

Arsenic availability from chromated copper arsenate (CCA)-treated wood

Lumber used to construct raised garden beds is often treated with chromated copper arsenate (CCA). This project aimed to determine (i) how far As, Cu, and Cr had diffused away from CCA-treated wood surfaces in raised garden beds under realistic conditions, (ii) the uptake of these elements by crops, and (iii) the effect of CCA solution on soil bacteria. This study showed that As, Cu, and Cr diffuse into soil from CCA-treated wood used to construct raised garden beds. To determine crop uptake of these elements, contaminated soil 0 to 2 cm from the treated wood was obtained from two different beds (40-50 mg kg(-1) As); control soil was collected 1.5 m away from the treated wood (<3-10 mg kg(-1) As). Four replicates of carrot (Daucus carota var. sativus Hoffm. cv. Thumbelina), spinach (Spinacia oleracea L. cv. Indian Summer), bush bean (Phaseolus vulgaris L. cv. Provider), and buckwheat (Fagopyrum esculentum Moench cv. Common) were grown in pots containing these soils in a greenhouse. After harvest, plant materials were dried, ground, digested, and analyzed for As by inductively coupled plasma-hydride generation (ICP-HG). Concentrations of As in all crops grown in contaminated soils were higher than those from control soils. The levels of As in the crops remained well below the recommended limit for As set by the United States Public Health Service (2.6 mg kg(-1) fresh wt.). To determine if bacteria in soils 0 to 2 cm from the treated wood had higher resistance to Type C chromated copper arsenate (CCA-C) solution than those from reference soils, dilution plates were set up using quarter-strength tryptic soy agar (TSA) media and 0 to 22.94 g L(-1) (0-1.25% v/v) CCA-C working solution. The microorganisms from soils adjacent to treated wood had greater growth on the CCA-amended media than those from reference soils outside the bed.     

Assessment of contamination from arsenical pesticide use on orchards in the Great Valley region, Virginia and West Virginia, USA

Lead arsenate pesticides were widely used in apple orchards from 1925 to 1955. Soils from historic orchards in four counties in Virginia and West Virginia contained elevated concentrations of As and Pb, consistent with an arsenical pesticide source. Arsenic concentrations in approximately 50% of the orchard site soils and approximately 1% of reference site soils exceed the USEPA Preliminary Remediation Goal (PRG) screening guideline of 22 mg kg(-1) for As in residential soil, defined on the basis of combined chronic exposure risk. Approximately 5% of orchard site soils exceed the USEPA PRG for Pb of 400 mg kg(-1) in residential soil; no reference site soils sampled exceed this value. A variety of statistical methods were used to characterize the occurrence, distribution, and dispersion of arsenical pesticide residues in soils, stream sediments, and ground waters relative to landscape features and likely background conditions. Concentrations of Zn, Pb, and Cu were most strongly associated with high developed land density and population density, whereas elevated concentrations of As were weakly correlated with high orchard density, consistent with a pesticide residue source. Arsenic concentrations in ground water wells in the region are generally <0.005 mg L(-1). There was no spatial association between As concentrations in ground water and proximity to orchards. Arsenic had limited mobility into ground water from surface soils contaminated with arsenical pesticide residues at concentrations typically found in orchards.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Chromated copper arsenate-treated fence posts in the agronomic landscape: soil properties controlling arsenic speciation and spatial distribution

Soils adjacent to chromated copper arsenate (CCA)-treated fence posts along a fence line transecting different soil series, parent material, drainage classes, and slope were used to determine which soil properties had the most influence on As spatial distribution and speciation. Metal distribution was evaluated at macroscopic (total metal concentration contour maps) and microscopic scales (micro-synchrotron X-ray fluorescence maps), As speciation was determined using extended X-ray absorption fine structure spectroscopy, and redox status and a myriad of other basic soil properties were elucidated. All geochemical parameters measured point to a condition in which the mobilization of As becomes more favorable moving down the topographic gradient, likely resulting through competition (Meh-P, SOM), neutral or slightly basic pH, and redox conditions that are favorable for As mobilization (higher Fe(II) and total-Fe concentrations in water extracts). On the landscape scale, with hundreds of kilometers of fence, the arsenic loading into the soil can be substantial (～8-12 kg km). Although a significant amount of the As is stable, extended use of CCA-treated wood has resulted in elevated As concentrations in the local environment, increasing the risk of exposure and ecosystem perturbation. Therefore, a move toward arsenic-free alternatives in agricultural applications for which it is currently permitted should be considered.     

Chemistry of inorganic arsenic in soils: II. Effect of phosphorus, sodium, and calcium on arsenic sorption

There are more than 10000 arsenic (As) contaminated sites in Australia. The ability of soils at these contaminated sites to sorb As is highly variable and appreciable amounts of As have been recorded in the subsurface soils. The potential risk of surface and ground water contamination by As at these sites is a major environmental concern. Factors that influence adsorption capacity of soils influence the bioavailability and subsequent mobility of As in soils. In the present study we investigated the effect of PO4(3-) and Na+ and Ca2+ on the sorption of AsV and AsIII by an Oxisol, a Vertisol, and two Alfisols. The presence of P (0.16 mmol L(-1)) greatly decreased AsV sorption by soils containing low amounts of Fe oxides (<100 mmol kg(-1)), indicating competitive adsorption between P and AsV for sorption sites. In contrast, the presence of a similar amount of P had little effect on the amount of AsV adsorbed by soils with high Fe content (>800 mmol kg(-1)). However, AsV sorption substantially decreased from 0.63 to 0.37 mmol kg(-1) as P concentration was increased from 0.16 to 3.2 mmol L(-1) in selected soils. This suggests increased competition between P and AsV for soil sorption sites, through either the higher affinity or the effect of mass action of the increasing concentration of P in solution. A similar effect of P on AsIII sorption was observed in the low sorbing Alfisol and high affinity Oxisol. However, the amount of AsIII sorbed by the Oxisol was much greater than the Alfisol for all treatments. The presence of Ca2+ increased the amount of AsV sorbed compared with that of Na+ and was manifested through changes in the surface charge characteristics of the soils. A similar trend in AsIII sorption was recorded with changes in index cation, although the effect was not as marked as recorded for AsV.     

A comparison of reliability of soil cadmium determination by standard spectrometric methods

Inductively coupled plasma emission spectrometry (ICP-OES) is the most common method for determination of soil Cd, yet spectral and matrix interferences affect measurements at the available analytical wavelengths for this metal. This study evaluated the severity of the interference over a range of total soil Cd by comparing ICP-OES and inductively coupled plasma mass spectrometry (ICP-MS) measurements of Cd in acid digests. Using the emission at 226.5 nm, ICP-OES was generally unable to quantify soil Cd at low (near-background) levels and gave unreliable values compared with ICP-MS. Using the line at 228.8 nm, a marked positive bias in Cd measurement (relative to the 226.5 nm measurement) was attributable to arsenic (As) interference even at soil As concentrations below 10 mg kg. This spectral interference in ICP-OES was severe in As-contaminated orchard soils, giving a false value for soil total Cd near 2 mg kg when soil As was 100 to 150 mg kg. In attempting to avoid these ICP emission-specific interferences, this study evaluated a method to estimate total soil Cd using 1 M HNO extraction followed by determination of Cd by flame atomic absorption (FAA), either with or without preconcentration of Cd using an Aliquat-heptanone extractant. The 1 M HNO extracted an average of 82% of total soil Cd. The FAA method had no significant interferences and estimated the total Cd concentrations in all soils tested with acceptable accuracy. For Cd-contaminated soils, the Aliquat-heptanone preconcentration step was not necessary, as FAA sensitivity was adequate for quantification of extractable soil Cd and reliable estimation of total soil Cd.     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

Competitive mobilization of phosphate and arsenate associated with goethite by root activity

Arsenate (As V) is the predominant form of arsenic in soils under aerobic conditions and competes with the major plant nutrient phosphorus (P) in the form of phosphate (PV) not only for sorption sites on mineral surfaces in soil but also for root membrane transporters. Plants have evolved several mechanisms for the mobilization of PV in soils in response to P deficiency, such as the release of organic anions and protons. The aim of the present study was to test whether these mechanisms result in a simultaneous mobilization of arsenate and what would be the consequences for As transfer from soil to plant. The compartment system approach with Zea mays as model crop was chosen as an experimental setup. The system is equipped with micro suction cups and allowed us to investigate processes occurring in the vicinity of roots. As a case study, an artificial quartz substrate with well defined soil physical properties was fertilized, spiked with As V, and amended with increasing amounts of goethite (0, 1, and 4 g kg(-1) in treatments G-0, G-1, and G-4, respectively). The addition of goethite alleviated the As V-induced growth reduction and reduced As V transfer from the substrate to the plant but induced P deficiency at the same time. When low amounts of goethite (1 g kg(-1)) were added, plants mobilized PV but not As V, which might be related to differences in surface complexation reported for PV and As V. No mobilization of PV or As V was observed with the addition of higher amounts of goethite, probably because of decreasing competition between organic anions, PV, and As V for binding sites.     

Effects of particle size on chemical speciation and bioavailability of copper to earthworms (Eisenia fetida) exposed to copper nanoparticles

To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia ferida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or < 100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg(-1) caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg(-1) of Cu NPs and concentrations exceeding 10 mg kg(-1) of CuSO4. Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (> 65 mg Cu kg(-1) soil).     

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4, was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.     

Potential anthropogenic mobilisation of mercury and arsenic from soils on mineralised rocks, Northland, New Zealand

Eroded roots of hot spring systems in Northland, New Zealand consist of mineralised rocks containing sulfide minerals. Marcasite and cinnabar are the dominant sulfides with subordinate pyrite. Deep weathering and leached soil formation has occurred in a warm temperate to subtropical climate with up to 3 m/year rainfall. Decomposition of the iron sulfides in natural and anthropogenic rock exposures yields acid rock drainage with pH typically between 2 and 4, and locally down to pH 1. Soils and weathered rocks developed on basement greywacke have negligible acid neutralisation capacity. Natural rainforest soils have pH between 4 and 5 on unmineralised greywacke, and pH is as low as 3.5 in soils on mineralised rocks. Roads with aggregate made from mineralised rocks have pH near 3, and quarries from which the rock was extracted can have pH down to 1. Mineralised rocks are enriched in arsenic and mercury, both of which are environmentally available as solid solution impurities in iron sulfides and phosphate minerals. Base metals (Cu, Pb, Zn) are present at low levels in soils, at or below typical basement rock background. Decomposition of the iron sulfides releases the solid solution arsenic and mercury into the acid rock drainage solutions. Phosphate minerals release their impurities only under strongly acid conditions (pH<1). Arsenic and mercury are adsorbed on to iron oxyhydroxides in soils, concentrated in the C horizon, with up to 4000 ppm arsenic and 100 ppm mercury. Waters emanating from acid rock drainage areas have arsenic and mercury below drinking water limits. Leaching experiments and theoretical predictions indicate that both arsenic and mercury are least mobile in acid soils, at pH of c. 3-4. This optimum pH range for fixation of arsenic and mercury on iron oxyhydroxides in soils is similar to natural pH at the field site of this study. However, neutralisation of acid soils developed on mineralised rocks is likely to decrease adsorption and enhance mobility of arsenic and mercury. Hence, development of farmland by clearing forest and adding agricultural lime may mobilise arsenic and mercury from underlying soils on mineralised rocks. In addition, arsenic and mercury release into runoff water will be enhanced where sediment is washed off mineralised road aggregate (pH 3) on to farm land (pH>6). The naturally acid forest soils, or even lower pH of natural acid rock drainage, are the most desirable environmental conditions to restrict dissolution of arsenic and mercury from soils. This approach is only valid where mineralised soils have low base metal concentrations.     

Sorption of arsenic from soil-washing leachate by surfactant-modified zeolite

Post-treatment of leachate from soil-washing remedial actions may be necessary depending on the amounts of dissolved contaminants present. Uptake of arsenic species by surfactant-modified zeolite (SMZ) from a synthetic soil leachate (pH of approximately 12 [NaOH]) was measured as a test of SMZ as a post-treatment sorbent. Batch sorption isotherms were prepared using leachate to SMZ ratios from 40:1 to 4:1, and temperatures of 25 and 15 degrees C. Equilibrium levels of dissolved and total solution arsenic were similar. At each temperature, sorption appeared to reach a plateau or maximum, then decreased at the highest solution concentration, corresponding to the lowest amount of zeolite added (2.5 g). A maximum sorption value of 72.0 mmol of arsenic per kg of SMZ (5400 mg/kg) was observed at 25 degrees C, and 42.1 mmol/kg (3150 mg/kg) at 15 degrees C. Total arsenic recoveries varied from 74 to 125%. Surfactant-modified zeolite removed up to 97% of dissolved organic carbon and decolorized the leachate solutions. Excluding the points for the highest arsenic to SMZ ratio, the sorption isotherms were well described by the linearized form of the Langmuir equation, with coefficients of determination greater than 0.90 at both temperatures. Sorption of arsenic by SMZ is attributed to anion exchange with counterions on the surfactant head groups, and/or partitioning of organic carbon-complexed arsenic into the surfactant bilayer.     

Partitioning species variability from soil property effects on phytotoxicity: ECx normalization using a plant contaminant sensitivity index

Soil properties mitigate hazardous effects of contaminants through soil chemical sequestration and should be considered when evaluating ecological risk from terrestrial contamination. Empirical models that quantify relationships between soil properties and toxicity to ecological receptors are necessary for site-specific adjustments to ecological risk assessments. However, differential sensitivities of test organisms in dose-response studies may limit the utility of such models. We present a novel approach to toxicity estimation that partitions the effect of differential sensitivities of test organisms from that of soil chemical/physical properties. Five soils that ranged in selected properties were spiked with five concentrations of sodium arsenate. Bioassays were conducted where above ground dry matter growth and the corresponding tissue arsenic concentrations were evaluated for three terrestrial plants (Alfalfa, Medicago sativa L.; Perennial ryegrass, Lolium perrene L.; and Japanese millet, Echinochloa crusgalli L.). Estimates were combined into a plant contaminant sensitivity index (PCSI) and used to normalize phytotoxicity parameters to the most sensitive species (i.e., alfalfa) where necessary. Simple linear regression and ANCOVA indicated a 36.5% increase in the explanatory power of the modifying effects of soil properties on phytotoxicity when differential arsenate sensitivities were accounted for by PCSI (r(2) = 0.477-0.833). Normalization of ecotoxicity parameters by PCSI is a seemingly effective approach to quantify the modifying effects of soil properties on phytotoxicity endpoints when it is of interest to consider multiple plant species (or varieties within a species) with differential sensitivities to experimental contaminants.     

Cadmium content of wheat grain from a long-term field experiment with sewage sludge

Grain Cd concentrations were determined in the wheat (Triticum aestivum L.) cultivars Soissons, Brigadier, and Hereward grown in 1994,1996, and 1999, respectively, in soils of a long-term field experiment to which sewage sludges contaminated with Zn, Cu, Ni, or Cr had previously been added. Soil pore water soluble Cd and free Cd2+ increased linearly with increasing total soil Cd (R2=0.82 and 0.84, respectively; P<0.001). Similarly, soil pore water free Cd2+ increased linearly with increasing soil pore water soluble Cd (R2=0.98; P<0.001). There was no evidence of a plateau in soil pore water Cd concentrations with increasing soil Cd concentrations. Grain Cd concentrations were significantly correlated with total soil Cd (P<0.001), soil pore water Cd (P<0.001), and free Cd2+ (P<0.001). A slight curvilinear relationship between grain Cd and soil Cd was apparent, but there was no plateau, even at the maximum soil Cd concentration of about 2.7 mg kg(-1). The relationship between soil pore water Cd and grain Cd was linear for all three cultivars. The slopes were in the order 1994 > 1996 > 1999, with more Cd being taken up into the grain by Soissons grown in 1994, and least by Hereward grown in 1999. For Soissons, Cd concentration in the grain greater than the EU limit (0.24 mg kg(-1) dry wt.) occurred at soil Cd less than the current UK limit of 3 mg kg(-1) for soils receiving sewage sludge. In contrast, for Brigadier and Hereward, grain Cd concentrations were near to and less than the EU limit, respectively, at soil Cd concentrations of 3 mg kg(-1).