Remediation options to reduce bioaccessible and bioavailable lead and arsenic at a smelter impacted site - consideration of treatment efficacy.

In this study, smelter contaminated soil was treated with various soil amendments (ferric sulfate [Fe2(SO4)3], triple superphosphate [TSP] and biochar) to determine their efficacy in immobilizing soil lead (Pb) and arsenic (As). In soils incubated with ferric sulfate (0.6M), gastric phase Pb bioaccessibility was reduced from 1939 ± 17 mg kg-1 to 245 ± 4.7 mg kg-1, while intestinal phase bioaccessibility was reduced from 194 ± 25 mg kg-1 to 11.9 ± 3.5 mg kg-1, driven by the formation of plumbojarosite. In TSP treated soils, there were minor reductions in gastric phase Pb bioaccessibility (to 1631 ± 14 mg kg-1) at the highest TSP concentration (6000 mg kg-1) although greater reductions were observed in the intestinal phase, with bioaccessibility reduced to 9.3 ± 2.2 mg kg-1. Speciation analysis showed that this was primarily driven by the formation of chloropyromorphite in the intestinal phase following Pb and phosphate solubilization in the low pH gastric fluid. At the highest concentration (10% w/w), biochar treated soils showed negligible decreases in Pb bioaccessibility in both gastric and intestinal phases. Validation of bioaccessibility outcomes using an in vivo mouse assay led to similar results, with treatment effect ratios (TER) of 0.20 ± 0.01, 0.76 ± 0.11 and 1.03 ± 0.10 for ferric sulfate (0.6M), TSP (6000 mg kg-1) and biochar (10% w/w) treatments. Results of in vitro and in vivo assays showed that only ferric sulfate treatments were able to significantly reduce As bioaccessibility and bioavailability with TER at the highest application of 0.06 ± 0.00 and 0.14 ± 0.04 respectively. This study highlights the potential application of ferric sulfate treatment for the immobilization of Pb and As in co-contaminated soils.

Effects of various Fe compounds on the bioavailability of Pb contained in orally ingested soils in mice: Mechanistic insights and health implications.

Reducing lead (Pb) exposure via oral ingestion of contaminated soils is highly relevant for child health. Elevating dietary micronutrient iron (Fe) intake can reduce Pb oral bioavailability while being beneficial for child nutritional health. However, the practical performance of various Fe compounds was not assessed. Here, based on mouse bioassays, ten Fe compounds applied to diets (100-800 mg Fe kg-1) reduced Pb oral relative bioavailability (RBA) in two soils variedly depending on Fe forms. EDTA-FeNa was most efficient, which reduced Pb-RBA in a soil from 79.5 ± 14.7 % to 23.1 ± 2.72 % (71 % lower) at 100 mg Fe kg-1 in diet, more effective than other 9 compounds at equivalent or higher doses (3.6-68 % lower). When EDTA-FeNa, ferrous gluconate, ferric citrate, and ferrous bisglycinate were supplemented, Fe-Pb co-precipitation was not observed in the intestinal tract. EDTA-FeNa, ferrous gluconate, ferric citrate, and ferrous sulfate suppressed duodenal divalent metal transporter 1 (DMT1)mRNA relative expression similarly (27-68 % lower). In comparison, among ten compounds, EDTA-FeNa elevated Fe concentrations in mouse liver, kidney, and blood (1.50-2.69-fold higher) most efficiently, suggesting the most efficient Fe absorption that competed with Pb. In addition, EDTA was unique from other organic ligands, ingestion of which caused 12.0-fold higher Pb urinary excretion, decreasing Pb concentrations in mouse liver, kidney, and blood by 68-88 %. The two processes (Fe-Pb absorption competition and Pb urinary excretion with EDTA) interacted synergistically, leading to the lowest Pb absorption with EDTA-FeNa. The results provide evidence of a better inhibition of Pb absorption by EDTA-FeNa, highlighting that EDTA-FeNa may be the most appropriate supplement for intervention on human Pb exposure. Future researches are needed to assess the effectiveness of EDTA-FeNa for intervention on human Pb exposure.

Mineral Dietary Supplement To Decrease Cadmium Relative Bioavailability in Rice Based on a Mouse Bioassay.

To determine the effectiveness of mineral dietary supplements to modulate cadmium (Cd) exposure, an in vivo mouse bioassay was conducted to determine Cd relative bioavailability (Cd-RBA) in Cd-contaminated rice (0.80 mg Cd kg-1) with and without Zn, Fe, or Ca supplements as nitrate or chloride salts. Without mineral supplements, Cd-RBA was 43 ± 5.3% based on average Cd accumulation in the liver plus kidneys as the end point. Among Ca(NO3)2, Zn(NO3)2, and Fe(NO3)2 supplements, 150-5000 mg kg-1 Ca was the most effective in reducing rice Cd-RBA by 31-80% to 8.5-29%, while 30-200 mg kg-1 Zn supplements was ineffective, with Cd-RBA being 33-57%. Low Fe at <40 mg kg-1 had little impact on rice Cd-RBA (39-47%), while high Fe at 80-200 mg kg-1 decreased Cd-RBA by 37% to 26-27%. The ineffectiveness of Zn supplements in reducing Cd-RBA was probably due to coinciding 8.3- and 3.1-fold increases in Zn accumulation in mouse kidneys and liver with Zn supplements, while Ca and Fe supplements led to much-smaller increases in Ca and Fe accumulation in mouse tissues (1.3-1.6 fold). In addition, compared to Ca(NO3)2 supplements, Cd-RBA values determined with CaCl2 supplements were significantly higher (25-67% versus 8.5-29%), suggesting that chloride enhanced Cd-RBA. Results of this study have important implications for developing effective dietary strategies to reduce dietary Cd exposure and the associated health risks in humans.

The application of a carrier-based bioremediation strategy for marine oil spills.

The application of recycled marine materials to develop sustainable remediation technologies in marine environment was assessed. The remediation strategy consisted of a shell carrier mounted bacterial consortium composed of hydrocarbonoclastic strains enriched with nutrients (Bioaug SC). Pilot scale studies (5000 l) were used to examine the ability of Bioaug-SC to degrade weathered crude oil (10 g l(-1); initially 315,000±44,000 mg l(-1)) and assess the impacts of the introduction and biodegradation of oil. Total petroleum hydrocarbon mass was effectively reduced by 53.3 (±5.75)% to 147,000 (±21,000) mg l(-1) within 27 weeks. 16S rDNA bacterial community profiling using Denaturant Gradient Gel Electrophoresis revealed that cyanobacteria and Proteobacteria dominated the microbial community. Aquatic toxicity assessment was conducted by ecotoxicity assays using brine shrimp hatchability, Microtox and Phaeodactylum tricornutum. This study revealed the importance of combining ecotoxicity assays with oil chemistry analysis to ensure safe remediation methods are developed.

Potential impact of soil microbial heterogeneity on the persistence of hydrocarbons in contaminated subsurface soils.

In situ bioremediation is potentially a cost effective treatment strategy for subsurface soils contaminated with petroleum hydrocarbons, however, limited information is available regarding the impact of soil spatial heterogeneity on bioremediation efficacy. In this study, we assessed issues associated with hydrocarbon biodegradation and soil spatial heterogeneity (samples designated as FTF 1, 5 and 8) from a site in which in situ bioremediation was proposed for hydrocarbon removal. Test pit activities showed similarities in FTF soil profiles with elevated hydrocarbon concentrations detected in all soils at 2 m below ground surface. However, PCR-DGGE-based cluster analysis showed that the bacterial community in FTF 5 (at 2 m) was substantially different (53% dissimilar) and 2-3 fold more diverse than communities in FTF 1 and 8 (with 80% similarity). When hydrocarbon degrading potential was assessed, differences were observed in the extent of (14)C-benzene mineralisation under aerobic conditions with FTF 5 exhibiting the highest hydrocarbon removal potential compared to FTF 1 and 8. Further analysis indicated that the FTF 5 microbial community was substantially different from other FTF samples and dominated by putative hydrocarbon degraders belonging to Pseudomonads, Xanthomonads and Enterobacteria. However, hydrocarbon removal in FTF 5 under anaerobic conditions with nitrate and sulphate electron acceptors was limited suggesting that aerobic conditions were crucial for hydrocarbon removal. This study highlights the importance of assessing available microbial capacity prior to bioremediation and shows that the site's spatial heterogeneity can adversely affect the success of in situ bioremediation unless area-specific optimizations are performed.

Impact of bacterial and fungal processes on 14C-hexadecane mineralisation in weathered hydrocarbon contaminated soil.

In this study, the impact of bacterial and fungal processes on (14)C-hexadecane mineralisation was investigated in weathered hydrocarbon contaminated soil. The extent of (14)C-hexadecane mineralisation varied depending on the bioremediation strategy employed. Under enhanced natural attenuation conditions, (14)C-hexadecane mineralisation after 98 days was 8.5 ± 3.7% compared to <1.2% without nitrogen and phosphorus additions. (14)C-hexadecane mineralisation was further enhanced through Tween 80 amendments (28.9 ± 2.4%) which also promoted the growth of a Phanerochaete chyrsosporium fungal mat. Although fungal growth in weathered hydrocarbon contaminated soil could be promoted through supplementing additional carbon sources (Tween 80, sawdust, compost, pea straw), fungal (14)C-hexadecane mineralisation was negligible when sodium azide was added to soil microcosms to inhibit bacterial activity. In contrast, when fungal activity was inhibited through nystatin additions, (14)C-hexadecane mineralisation ranged from 6.5 ± 0.2 to 35.8 ± 3.8% after 98 days depending on the supplied amendment. Bacteria inhibition with sodium azide resulted in a reduction in bacterial diversity (33-37%) compared to microcosms supplemented with nystatin or microcosms without inhibitory supplements. However, alkB bacterial groups were undetected in sodium azide supplemented microcosms, highlighting the important role of this bacterial group in (14)C-hexadecane mineralisation.

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils.

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-ß-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.

Bioavailability of residual polycyclic aromatic hydrocarbons following enhanced natural attenuation of creosote-contaminated soil.

The impact of residual PAHs (2250 +/- 71 microg total PAHs g(-1)) following enhanced natural attenuation (ENA) of creosote-contaminated soil (7767 +/- 1286 microg total PAHs g(-1)) was assessed using a variety of ecological assays. Microtox results for aqueous soil extracts indicated that there was no significant difference in EC(50) values for uncontaminated, pre- and post-remediated soil. However, in studies conducted with Eisenia fetida, PAH bioaccumulation was reduced by up to 6.5-fold as a result of ENA. Similarly, Beta vulgaris L. biomass yields were increased 2.1-fold following ENA of creosote-contaminated soil. While earthworm and plant assays indicated that PAH bioavailability was reduced following ENA, the residual PAH fraction still exerted toxicological impacts on both receptors. Results from this study highlight that residual PAHs following ENA (presumably non-bioavailable to bioremediation) may still be bioavailable to important receptor organisms such as earthworms and plants.

Chromium-microorganism interactions in soils: remediation implications.

Discharge of Cr waste from many industrial applications such as leather tanning, textile production, electroplating, metallurgy, and petroleum refinery has led to large-scale contamination of land and water. Generally, Cr exists in two stable states: Cr(III) and Cr(VI). Cr(III) is not very soluble and is immobilized by precipitation as hydroxides. Cr(VI) is toxic, soluble, and easily transported to water resources. Cr(VI) undergoes rapid reduction to Cr(III), in the presence of organic sources or other reducing compounds as electron donors, to become precipitated as hydroxides. Cr(VI)-reducing microorganisms are ubiquitous in soil and water. A wide range of microorganisms, including bacteria, yeasts; and algae, with exceptional ability to reduce Cr(VI) to Cr(III) anaerobically and/or aerobically, have been isolated from Cr-contaminated and noncontaminated soils and water. Bioremediation approaches using the Cr(VI)-reducing ability of introduced (in bioreactors) or indigenous (augmented by supplements with organic amendments) microorganisms has been more successful for remediation of Cr-contaminated water than soils. Apart from enzymatic reduction, nonenzymatic reduction of Cr(VI) can also be common and widespread in the environment. For instance, biotic-abiotic coupling reactions involving the microbially formed products, H2S (the end product of sulfate reduction), Fe(II) [formed by Fe(III) reduction], and sulfite (formed during oxidation of elemental sulfur), can mediate the dissimilatory reduction of Cr(VI). Despite the dominant occurrence of enzymatic and nonenzymatic reduction of Cr(VI), natural attenuation of Cr(VI) is not taking place at a long-term contaminated site in South Australia, even 225 years after the last disposal of tannery waste. Evidence suggests that excess moisture conditions leading to saturation or flooded conditions promote the complete removal of Cr(VI) in soil samples from this contaminated site; but Cr(VI) reappears, probably because of oxidation of the Cr(III) by Mn oxides, with a subsequent shift to drying conditions in the soil. In such environments with low natural attenuation capacity resulting from reversible oxidation of Cr(III), bioeremediation of Cr(VI) can be a challenging task.