Remediation of Pb-contaminated soil using modified bauxite refinery residue.

This study examines amendment of Pb-contaminated soil with modified bauxite refinery residue (MBRR) to decrease soil Pb mobility and bioaccessibility. Amendment experiments were conducted using four soils contaminated with Pb from various sources, including smelting, shooting-range activities and Pb-based paint waste. Lead L3-edge X-ray absorption spectroscopy (XAS) indicated that Pb speciation in these soils was a mixture of Pb sorbed to Fe (hydr)oxide and clay minerals, along with Pb bound to organic matter. Amendment with MBRR decreased water-soluble Pb and/or Toxicity Characteristic Leachate Procedure (TCLP) Pb concentrations. Lead L3-edge XAS and X-ray diffraction (XRD) indicated that Pb retention by MBRR occurred via sorption to Fe- and Al-(hydr)oxides at low Pb loadings, in addition to formation of hydrocerussite (Pb3(CO3)2(OH)2) at high loadings. Soil amendment with MBRR had relatively little effect on gastric-phase Pb bioaccessibility; as quantified via the Solubility/Bioavailability Research Consortium, SBRC, in vitro assay. In contrast, amendment with MBRR caused substantial decreases in relative intestinal-phase Pb bioaccessibility (Rel-SBRC-I) due to increased Pb sorption by MBRR's Fe- and Al-hydr(oxide) minerals as simulated GI tract conditions shifted from the gastric- to the intestinal-phase. These decreases in Rel-SBRC-I point to the potential efficacy of using amendment with MBRR to decrease soil Pb bioavailability.

Antimony speciation, phytochelatin stimulation and toxicity in plants.

Antimony (Sb) is a toxic metalloid that has been listed as a priority pollutant. The environmental impacts of Sb have recently attracted attention, but its phytotoxicity and biological transformation remain poorly understood. In this study, Sb speciation and transformation in plant roots was quantified by Sb K-edge X-ray absorption spectroscopy. In addition, the phytotoxicity of antimonate (SbV) on six plant species was assessed by measuring plant photosynthesis, growth, and phytochelatin production induced by SbV. Linear combination fitting of the Sb K-edge X-ray absorption near-edge structure (XANES) spectra indicated reduction of SbV was limited to ∼5-33% of Sb. The data confirmed that Sb-polygalacturonic acid was the predominant chemical form in all plant species (up to 95%), indicating Sb was primarily bound to the cell walls of plant roots. Shell fitting of Sb K-edge X-ray absorption fine-structure (EXAFS) spectra confirmed Sb-O and Sb-C were the dominant scattering paths. The fitting indicated that SbV was bound to hydroxyl functional groups of cell walls, via development of a local coordination environment analogous to Sb-polygalacturonic acid. This is the first study to demonstrate the key role of plant cell walls in Sb metabolism.

Arsenic geochemistry and mineralogy as a function of particle-size in naturally arsenic-enriched soils.

Naturally arsenic (As) enriched agricultural soils represent a significant global human health risk. In this study, As fractionation and mineralogy were investigated in naturally As-enriched agricultural soils and their corresponding sand, silt and clay fractions. Median As increased generally in the order (mg/kg)∶ silt (280) < bulk (314) < sand (323)

The influence of long-term ageing on arsenic ecotoxicity in soil.

The ageing of a contaminant in soil influences the bioavailability and toxicity of environmental pollutants. Yet, despite arsenic (As) being an important terrestrial contaminant, the effect of As ageing on phytotoxicity has received relatively little research. Research to date has reported predominantly short term (< 0.5 years) experiments. Here, we studied the influence of ageing over 0.25 and 5 years on the phytotoxicity of As (as arsenate) on Cucumis sativus L. (cucumber). The study showed that increasing ageing time of As from 0.25 to 5 years increased the EC10 and EC50 values by 4.0 and 1.76 fold, respectively. The dependence of ageing on soil properties was also examined, although only Freundlich sorption parameters were correlated to the ageing factor (r = 0.68, P = 0.028). Soils with high adsorption capacity also showed the greatest change in toxicity over 5 years. In addition, data was compiled from relevant literature to develop a model for As ecotoxicity. The combined model (n = 54) showed no relationship with pH but was correlated to the oxalate extractable iron content and %clay. Arsenate ecotoxicity (EC50, mg/kg) in the multivariate model was related to oxalate iron content, %clay and ageing time. Thus, the results of this study have significant implications for risk assessment of long-term As contaminated soils.

Copper interactions on arsenic bioavailability and phytotoxicity in soil.

Arsenic (As) and copper (Cu) are co-contaminants in the environment but little is known about their ecological impact as mixtures in soil. In this study, we investigated the combined As-Cu interactions on toxicity and uptake as binary mixtures in 5 contrasting soils. The study included solubility, contaminant uptake and toxicity in cucumber (Cucumis sativus L.) as a model plant species. Soils were spiked individually and as a mixtures at 10 different As levels (2, 4, 8 up to 1024mgkg-1). Copper was added with As at two effective concentration levels (EC10Cu and EC50Cu). Arsenic uptake was significantly reduced in the presence of Cu and a higher effect was demonstrated with increasing pore-water pH. Copper accumulation was not significantly influenced by As. An additive response on plant growth was predominant overall when expressed from pore-water parameters with root mean square errors of 12.6 and 13.2 for EC10Cu and EC50Cu treatments, respectively.

Zinc-arsenic interactions in soil: Solubility, toxicity and uptake.

Arsenic (As) and zinc (Zn) are common co-contaminants in mining impacted soils. Their interaction on solubility and toxicity when present concurrently is not well understood in natural systems. The aim of this study was to observe their interaction in solubility (soil-solution), bioaccumulation (shoot uptake) and toxicity to cucumber (Cucumis sativa L) conducting 4 weeks pot study in 5 different soils spiked with As (0, 2, 4, 8 to 1024 mg kg-1) individually and with Zn at two phytotoxic doses. The As pore-water concentration was significantly reduced (df = 289, Adjusted R2 = 0.84, p < 0.01) in the presence of Zn in the whole dataset, whereas Zn and Zn2+ activity in pore-water was reduced significantly only in the two alkaline soils. This outcome may be due to adsorption/surface precipitation or tertiary bridging complexation. No homogenous precipitation of zinc arsenate could be established using electron microscopy, XRD or even equilibrium calculations. For bioaccumulation phase, no significant effect of Zn on As uptake was observed except acidic MG soil whereas, Zn uptake was significantly reduced (p < 0.05) by As in whole dataset. However, an additive response was observed mostly except acidic MG soil. The synergistic response (more than additive) was predominant in this soil for a wide range of inhibition concentration (0-80%) at both Zn EC10 and EC50 levels. Since additive response is mostly considered in risk assessment for mixtures, precautions should be implemented for assessment of toxicity for As-Zn mixture in acidic soil due to their synergistic response in some soils.

Pore-Water Carbonate and Phosphate As Predictors of Arsenate Toxicity in Soil.

Phytotoxicity of inorganic contaminants is influenced by the presence of competing ions at the site of uptake. In this study, interaction of soil pore-water constituents with arsenate toxicity was investigated in cucumber (Cucumis sativa L) using 10 contrasting soils. Arsenate phytotoxicity was shown to be related to soluble carbonate and phosphate. The data indicated that dissolved phosphate and carbonate had an antagonistic impact on arsenate toxicity to cucumber. To predict arsenate phytotoxicity in soils with a diverse range of soil solution properties, both carbonate and phosphate were required. The relationship between arsenic and pore-water toxicity parameters was established initially using multiple regression. In addition, based on the relationship with carbonate and phosphate we successively applied a terrestrial biotic ligand-like model (BLM) including carbonate and phosphate. Estimated effective concentrations from the BLM-like parametrization were strongly correlated to measured arsenate values in pore-water (R2 = 0.76, P < 0.001). The data indicates that an ion interaction model similar to the BLM for arsenate is possible, potentially improving current risk assessments at arsenic and co-contaminated soils.

Predicting plant uptake of cadmium: validated with long-term contaminated soils.

Cadmium accumulates in plant tissues at low soil loadings and is a concern for human health. Yet at higher levels it is also of concern for ecological receptors. We determined Cd partitioning constants for 41 soils to examine the role of soil properties controlling Cd partitioning and plant uptake. From a series of sorption and dose response studies, transfer functions were developed for predicting Cd uptake in Cucumis sativa L. (cucumber). The parameter log Kf was predicted with soil pHca, logCEC and log OC. Transfer of soil pore-water Cd2+ to shoots was described with a power function (R 2 = 0.73). The dataset was validated with 13 long-term contaminated soils (plus 2 control soils) ranging in Cd concentration from 0.2 to 300 mg kg-1. The series of equations predicting Cdshoot from pore-water Cd2+ were able to predict the measured data in the independent dataset (root mean square error = 2.2). The good relationship indicated that Cd uptake to cucumber shoots could be predicted with Cdpore and Cd2+ without other pore-water parameters such as pH or Ca2+. The approach may be adapted to a range of plant species.

Predicting plant uptake and toxicity of lead (Pb) in long-term contaminated soils from derived transfer functions.

Regulatory assessment of lead (Pb) in contaminated soils is still expressed primarily as total Pb concentrations in soil. In this study, we estimated effective concentrations (ECx) of Pb to Cucumis sativa L. (cucumber) focusing primarily on pore-water Pb data from 10 different soils after 12 weeks ageing. Phytotoxicity expressed in terms of Pb(2+) was observed to occur in the nanomolar range in neutral to alkaline soils (EC50 values 90 to 853 nM) and micromolar levels for acidic soils (EC50 values 7.35 to 9.66 µM). Internal Pb concentrations relating to toxicity (PT50) in roots and shoots also decreased with increasing pore-water pH (R (2) = 0.52 to 0.53). From a series of dose-response studies, we developed transfer functions predicting Pb uptake in C. sativa and we validated these functions with long-term Pb contaminated soils. The significant independent parameters were pore-water Pb(2+) and dissolved Pb plus dissolved organic carbon (DOC). The observed RMSE for the Pb-DOC model and Pb(2+) were 2.6 and 8.8, respectively. The Pb-DOC model tended to under-predict Pb, whilst Pb(2+) tended to over-predict accumulation despite reasonable RMSE values. Further validation is needed in soils with higher pore-water Pb solubility.

Predicting copper phytotoxicity based on pore-water pCu.

The free ion activity and "biotic ligand" models predict that the free metal ion and other pore-water parameters describe terrestrial phytotoxicity. In this study, pore-water chemistry and measured Cu(2+) was used to describe phytotoxicity of cucumber (Cucumis sativa L) in 10 contrasting soils at different soil Cu loadings. Both soil solution Cu (Cu(pw)) and Cu(2+) successfully described the response variable for all ten soils with R(2) values of 0.73 and 0.66, respectively. Separation of soils as acid and alkaline and fitting separately showed that there was a strongly significant fit for both log Cu(2+) and log Cu(pw) in acidic soils (R(2) = 0.92 and 0.86, respectively) but weakly significant fit for alkaline soils. The pCu EC50 and EC10 values in all acidic soils for cucumber were 5.83 (6.03-5.63) and 7.53 (8.27-7.00), respectively. In our dataset alkaline soils need to be treated individually. In addition, pCu could be predicted based on pH and total concentration alone. Despite only 12 weeks 'ageing' there was quantitative agreement between pCu model from this study and predicted pCu from Sauvé et al. This agreement from studies performed independently indicates that, at least in the case of Cu(2+), the difference in an ageing period of ≥10 years appears minimal.

Bioaccessibility of barium from barite contaminated soils based on gastric phase in vitro data and plant uptake.

Barite contamination of soil commonly occurs from either barite mining or explorative drilling operations. This work reported in vitro data for barite contaminated soils using the physiologically based extraction test (PBET) methodology. The existence of barite in plant tissue and the possibility of 'biomineralised' zones was also investigated using Scanning Electron Microscopy. Soils with low barium (Ba) concentrations showed a higher proportion of Ba extractability than barite rich samples. Barium uptake to spinach from soil was different between short term spiking studies and field weathered soils. Furthermore, Ba crystals were not evident in spinach tissue or acid digest solutions grown in barium nitrate spiked soils despite high accumulation. Barite was found in the plant digest solutions from barite contaminated soils only. Results indicate that under the conservative assumptions made, a child would need to consume extreme quantities of soil over an extended period to cause chronic health problems.

Pore-water chemistry explains zinc phytotoxicity in soil.

Zinc (Zn) is a widespread soil contaminant arising from a numerous anthropogenic sources. However, adequately predicting toxicity of Zn to ecological receptors remains difficult due to the complexity of soil characteristics. In this study, we examined solid-solution partitioning using pore-water data and toxicity of Zn to cucumber (Cucumis sativus L.) in spiked soils. Pore-water effective concentration (ECx, x=10%, 20% and 50% reduction) values were negatively related to pH, indicating lower Zn pore water concentration were needed to cause phytotoxicity at high pH soils. Total dissolved zinc (Znpw) and free zinc (Zn(2+)) in soil-pore water successfully described 78% and 80.3% of the variation in relative growth (%) in the full dataset. When the complete data set was used (10 soils), the estimated EC50pw was 450 and 79.2 µM for Znpw and Zn(2+), respectively. Total added Zn, soil pore water pH (pHpw) and dissolve organic carbon (DOC) were the best predictors of Znpw and Zn(2+) in pore-water. The EC10 (total loading) values ranged from 179 to 5214 mg/kg, depending on soil type. Only pH measurements in soil were related to ECx total Zn data. The strongest relationship to ECx overall was pHca, although pHw and pHpw were in general related to Zn ECx. Similarly, when a solution-only model was used to predict Zn in shoot, DOC was negatively related to Zn in shoot, indicating a reduction in uptake/ translocation of Zn from solution with increasing DOC.

Bioavailability of barium to plants and invertebrates in soils contaminated by barite.

Barium (Ba) is a nonessential element to terrestrial organisms and is known to be toxic at elevated concentrations. In this study, the bioavailability and toxicity of Ba in barite (BaSO4) contaminated soils was studied using standard test organisms (Lactuca sativa L. "Great Lakes", Eisenia fetida). Contamination resulted from barite mining activities. Barium concentrations in contaminated soils determined by X-ray fluorescence were in the range 0.13-29.2%. Barite contaminated soils were shown to negatively impact both E. fetida and L. sativa relative to control soil. For E. fetida, pore-water concentrations and acid extractable Ba were linearly related to % body weight loss. In L. sativa, pore-water Ba and exchangeable Ba were both strongly related to shoot Ba and shoot biomass production. A negative linear relationship was observed between shoot Ba content and shoot weight (P < 0.0004, R(2) = 0.39), indicating that Ba accumulation is likely to have induced phytotoxicity. Plant weights were correlated to % weight loss in earthworm (r = -0.568, P = 0.028). Barium concentrations in pore-water were lower than predicted from barite solubility estimates but strongly related to exchangeable Ba, indicating an influence of ion exchange on Ba solubility and toxicity to E. fetida and L. sativa.

Copper phytotoxicity in native and agronomical plant species.

Copper (Cu) is a widespread soil contaminant that is known to be highly toxic to soil biota. Limited information is available on the response of wild endemic species to Cu in the literature, which hinders ecological risk assessments and revegetation. In the present study, the phytotoxicity of Cu in nutrient solution was studied in five Australian endemic plant species (Acacia decurrens, Austrodanthonia richardsonii (Wallaby Grass), Bothriochloa macra (Redgrass), Eucalyptus camaldulensis var. camaldulensis (River Red-Gum) and Dichanthium sericeum (Bluegrass) and two vegetable plants species (Lactuca sativa L. 'Great lakes' and Raphanus sativa L.). Vegetable species were grown in a more concentrated nutrient solution. The response of B. macra was also compared between the two nutrient solutions (dilute and concentrated nutrient solution). In the first experiment, D. sericeum and E. camaldulensis were found to be highly sensitive to Cu exposure in nutrient culture. Critical exogenous Cu concentrations (50 percent reduction in roots) for E. camaldulensis, D. sericeum, A. richardsonii, B. macra (dilute), L. sativa, B. macra (concentrated), R. sativa and A. decurrens were, respectively, (µg/L) 16, 35, 83, 88, 97, 105, 128 and 186. Copper tolerance in B. macra was observed to be higher in the more concentrated nutrient solution despite the estimated Cu(2+) concentration being very similar in treatment solutions. Additional short-term rhizo-accumulation studies showed that neither Ca(2+) not K(+) was responsible for reduced uptake at the roots. However, the estimated maximum shoot Cu was reduced from 41 to 24mg/kg in the more concentrated solution.

Bioavailability of lead in contaminated soil depends on the nature of bioreceptor.

Long-term lead (Pb) contaminated soils from two lead-zinc smelters and a shooting range, along with freshly spiked control soil, were studied by means of chemical, biological or a physiological method to examine the effect of ageing on Pb bioavailability. The freshly Pb spiked control soil was subjected to an earthworm toxicity test to observe the avoidance and mortality response of the earthworms. Meanwhile, an extractable fraction of Pb on the spiked soil as a result of ageing was examined and further compared with physiologically based in vitro bioaccessibility extraction tests. Their differences in lethal concentration, LC(50), to the earthworm population from spiked soils varied substantially as a function of soil pH. The strong effect of ageing on toxicity was also reflected in the extractability of Pb which was far greater in acidic soil, labelled AC, compared to the alkaline soil, labelled BC. This demonstrates that the bioavailable fraction causing toxicity to earthworms was achieved at a much lower total Pb content for acidic soils relative to alkaline soils. Moreover, the effect of ageing also exhibits that a marked decline in bioavailable Pb results in lowering toxicity. Significant amounts of weight loss in earthworms during an acute toxicity test in long-term contaminated soils at a relatively low Pb concentration suggested that other metal or combined metal toxicity may also play a significant role. This study demonstrates that the soil characteristics and ageing period greatly influence the bioavailable fraction of Pb which is related to the bioreceptor.

Relative tolerance of a range of Australian native plant species and lettuce to copper, zinc, cadmium, and lead.

The tolerance of wild flora to heavy-metal exposure has received very little research. In this study, the tolerance of four native tree species, four native grass species, and lettuce to copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb) was investigated in a root-elongation study using Petri dishes. The results of these studies show a diverse range of responses to Cu, Zn, Cd, and Pb amongst the tested plant species. Toxicity among metals decreased in the following order: Cd ~ Cu > Pb > Zn. Metal concentrations resulting in a 50% reduction in growth (EC(50)) varied considerably, ranging from (microM) 30 (Dichanthium sericeum) to >2000 (Acacia spp.) for Cu; from 260 (Lactuca sativa) to 2000 (Acacia spp.) for Zn; from 27 (L. sativa) to 940 (Acacia holosericea) for Cd; and from 180 (L. sativa) to >1000 (Acacia spp.) for Pb. Sensitive native plant species identified included D. sericeum, Casuarina cunninghamiana, and Austrodanthonia caespitosa. However, L. sativa (lettuce) was also among the most sensitive to all four metals. Acacia species showed a high tolerance to metal exposure, suggesting that the Acacia genus shows potential for use in contaminated-site revegetation.

Phytotoxicity and accumulation of lead in Australian native vegetation.

Lead (Pb) is a wide spread contaminant in the terrestrial landscape. It is highly detrimental to plant and animal life and possesses no known biologic function. Yet there is a paucity of reliable information available on the response of Australian and other plant species to Pb exposure at phytotoxic doses. In this study, the response of three Australian native grass species and two tree species to Pb in nutrient solution culture was investigated. Plants were exposed to average Pb concentrations ranging from 0.020 to 15.2 microM. The plant species included Acacia decurrens, Austrodanthonia richardsonii, Bothriochloa macra, Eucalyptus camaldulensis, and Dichanthium sericeum. Few foliar symptoms were evident in any plant species, although some discolouration in young leaves of E. camaldulensis was evident from 1 microM, and B. macra showed pronounced reddening at the highest treatments. The most tolerant plant species studied based on solution EC(50, roots) (microM) results was B. macra (7.0 +/- 0.2), followed by A. decurrens (3.9 +/- 0.2), D. sericeum (2.9 +/- 0.3), E. camaldulensis (1.1 +/- 0.3), and A. richardsonii (0.4). A hazardous concentration value (HC(5)) (n = 9) for soil solution was estimated to be 0.16 microM. A. richardsonii was highly sensitive to Pb and possessed little ability to restrict Pb translocation to its shoots. B. macra was able to tolerate high root (3924 mg kg(-1)) and shoot (743.0 mg kg(-1)) Pb concentrations. A. decurrens excluded Pb from it shoots. The high tolerance of A. decurrens to Pb and limited translocation to shoots indicates it may be useful in revegetation of Pb-contaminated soils.

Heavy metal (Cu, Zn, Cd and Pb) partitioning and bioaccessibility in uncontaminated and long-term contaminated soils.

We investigated the pore-water content and speciation of copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb) in a range of uncontaminated and long-term contaminated soils in order to establish their potential bioaccessibility to soil biota, plants and humans. Among the samples, soil pH (0.01 M CaCl(2)) ranged from 4.9 to 8.2. The total metal content of the uncontaminated soils ranged from 3.8 to 93.8 mg Cu kg(-1), 10.3 to 95 mg kg(-1) Zn, 0.1 to 1.8 mg Cd kg(-1) and 5.2 to 183 mg kg(-1) Pb, while metal content in the contaminated soils ranged from 104 to 6841 mg Cu kg(-1), 312 to 39,000 mg kg(-1) Zn, 6 to 302 mg Cd kg(-1) and 609 to 12,000 mg kg(-1) Pb. Our analysis of pore-water found the Cu concentrations to be much higher in contaminated soils than in uncontaminated soils, with the distribution coefficients (K(d)) correlating significantly with the log of dissolved organic carbon concentrations. Despite the high total metal content of the contaminated soil, Zn, Cd and Pb were not generally found at elevated levels in the pore-water with the exception of a single contaminated soil. A long period of ageing and soil weathering may have led to a substantial reduction in heavy metal concentrations in the pore-water of contaminated soils. On the other hand, Pb bioaccessibility was found to be comparatively high in Pb contaminated soils, where it tended to exceed the total Pb values by more than 80%. We conclude that, despite the extensive ageing of some contaminated soils, the bioaccessibility of Pb remains relatively high.