Phosphatase-mediated bioprecipitation of lead by soil fungi

Geoactive soil fungi were examined for their ability to release inorganic phosphate (Pi ) and mediate lead bioprecipitation during growth on organic phosphate substrates. Aspergillus niger and Paecilomyces javanicus grew in 5 mM Pb(NO3 )2 -containing media amended with glycerol 2-phosphate (G2P) or phytic acid (PyA) as sole P sources, and liberated Pi into the medium. This resulted in almost complete removal of Pb from solution and extensive precipitation of lead-containing minerals around the biomass, confirming the importance of the mycelium as a reactive network for biomineralization. The minerals were identified as pyromorphite (Pb5 (PO4 )3 Cl), only produced by P. javanicus, and lead oxalate (PbC2 O4 ), produced by A. niger and P. javanicus. Geochemical modelling of lead and lead mineral speciation as a function of pH and oxalate closely correlated with experimental conditions and data. Two main lead biomineralization mechanisms were therefore distinguished: pyromorphite formation depending on organic phosphate hydrolysis and lead oxalate formation depending on oxalate excretion. This also indicated species specificity in biomineralization depending on nutrition and physiology. Our findings provide further understanding of lead geomycology and organic phosphates as a biomineralization substrate, and are also relevant to metal immobilization biotechnologies for bioremediation, metal and P biorecovery, and utilization of waste organic phosphates

Fractionation of lead in soil by isotopic dilution and sequential extraction

‘Reactivity’ or ‘lability’ of lead is difficult to measure using traditional methods. We investigated the use of isotopic dilution with 204Pb to determine metal reactivity in four soils historically contaminated with contrasting sources of Pb, including (i) petrol-derived Pb, (ii) Pb/Zn minespoil, (iii) long-term sewage sludge application and (iv) 19th century urban waste disposal; total soil Pb concentrations ranged from 217 to 13 600 mg kg–1. A post-spike equilibration period of 3 days and suspension in 5.0 × 10–4 M ethylenediaminetetraacetic acid provided reasonably robust conditions for measuring isotopically exchangeable Pb. However, in acidic organic soils a dilute Ca(NO3)2 electrolyte may be preferable to avoid mobilisation of ‘non-labile’ Pb. Results showed that the reactive pool of soil Pb can be a large proportion of the total soil lead content but varies with the original Pb source. A comparison of isotopic exchangeability with the results of a sequential extraction procedure showed that (isotopically) ‘non-labile’ Pb may be broadly equated with ‘residual’ Pb in organic soils. However, in mineral soils the ‘carbonate’ and ‘oxide-bound’ Pb fractions included non-labile forms of Pb. The individual isotopic signatures of labile and non-labile Pb pools suggested that, despite prolonged contact with soil, differences between the lability of the original contaminant and the native soil Pb may remain

The Geomycology of Elemental Cycling and Transformations in the Environment

Geomicrobiology addresses the roles of microorganisms in geological and geochemical processes, and geomycology is a part of this topic focusing on the fungi. Geoactive roles of fungi include organic and inorganic transformations important in nutrient and element cycling, rock and mineral bioweathering, mycogenic biomineral formation, and metal-fungal interactions. Lichens and mycorrhizas are significant geoactive agents. Organic matter decomposition is important for cycling of major biomass-associated elements, e.g., C, H, N, O, P, and S, as well as all other elements found in lower concentrations. Transformations of metals and minerals are central to geomicrobiology, and fungi affect changes in metal speciation, as well as mediate mineral formation or dissolution. Such mechanisms are components of biogeochemical cycles for metals as well as associated elements in biomass, soil, rocks, and minerals, e.g., S, P, and metalloids. Fungi may have the greatest geochemical influence within the terrestrial environment. However, they are also important in the aquatic environment and are significant components of the deep subsurface, extreme environments, and habitats polluted by xenobiotics, metals, and radionuclides. Applications of geomycology include metal and radionuclide bioleaching, biorecovery, detoxification, bioremediation, and the production of biominerals or metal(loid) elements with catalytic or other properties. Adverse effects include biodeterioration of natural and synthetic materials, rock and mineral-based building materials (e.g., concrete), cultural heritage, metals, alloys, and related substances and adverse effects on radionuclide mobility and containment. The ubiquity and importance of fungi in the biosphere underline the importance of geomycology as a conceptual framework encompassing the environmental activities of fungi.</p

Synthesis of earthworm trace metal uptake and bioaccumulation data: role of soil concentration, earthworm ecophysiology, and experimental design

Trace metals can be essential for organo-metallic structures and oxidation-reduction in metabolic processes or may cause acute or chronic toxicity at elevated concentrations. The uptake of trace metals by earthworms can cause transfer from immobilized pools in the soil to predators within terrestrial food chains. We report a synthesis and evaluation of uptake and bioaccumulation empirical data across different metals, earthworm genera, ecophysiological groups, soil properties, and experimental conditions (metal source, uptake duration, soil extraction method). Peer-reviewed datasets were extracted from manuscripts published before June 2019. The 56 studies contained 3513 soil-earthworm trace metal concentration paired data sets across 11 trace metals (As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Sb, U, Zn). Across all field and laboratory experiments studied, the median concentrations of Hg, Pb, and Cd in earthworm tissues that were above concentrations known to be hazardous for consumption by small mammals and avian predators but not for Cu, Zn, Cr, Ni, and As. Power regressions show only Hg and Cd earthworm tissue concentrations were well-correlated with soil concentrations with R2 > 0.25. However, generalized linear mixed-effect models reveal that earthworm concentrations were significantly correlated with soil concentrations for log-transformed Hg, Cd, Cu, Zn, As, Sb (p < 0.05). Factors that significantly contributed to these relationships included earthworm genera, ecophysiological group, soil pH, and organic matter content. Moreover, spiking soils with metal salts, shortening the duration of exposure, and measuring exchangeable soil concentrations resulted in significantly higher trace metal uptake or greater bioaccumulation factors. Our results highlight that earthworms are able to consistently bioaccumulate toxic metals (Hg and Cd only) across field and laboratory conditions. However, future experiments should incorporate greater suites of trace metals, broader genera of earthworms, and more diverse laboratory and field settings to generate data to devise universal quantitative relationships between soil and earthworm tissue concentrations

Lead minerals in soils contaminated by mine-waste : implications for human health.

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