Fire-induced effects on the bioavailability of potentially toxic elements in a polluted agricultural soil: implications for Cr uptake by durum wheat plants.

Fire events can modify the distribution and speciation of potentially toxic elements (PTEs) in soil, especially if they are associated to organic matter (OM). In fact, OM can undergo substantial structural modifications at high temperatures, up to the complete mineralization. The present study aims to investigate the changes of PTEs' bioavailability to durum wheat (Triticum durum Desf.) plants after simulating fire events (up to 300 °C and 500 °C) in an agricultural soil polluted by Cr, Zn, Cu, and Pb. The PTEs' uptake and allocation in plant tissues were assessed using the RHIZOtest system. After the fire simulations, no evident risk of accumulation and translocation in plants was observed for Zn, Pb, and Cu. Conversely, a high accumulation in roots and a significant translocation to shoots were observed for Cr, which reached concentrations of 829 mg kg-1 in roots and 52 mg kg-1 in shoots at 500 °C. Additional experimental evidence suggested that Cr was taken up by plants grown on heated soils as Cr(VI). Once acquired by roots, only a small part of Cr (up to 6%) was translocated to shoots where it was likely present as mobile forms, as evidenced by micro X-ray fluorescence (µ-XRF) analyses. Overall, the results obtained provide evidence that the high temperatures occurring during fire events can increase the mobility and bioavailability of certain PTEs transforming apparently safe environments into potentially dangerous sources of pollution. These processes can ultimately affect the human health through the food chain transfer of PTEs or their migration into surface water and groundwater.

Evidence of hexavalent chromium formation and changes of Cr speciation after laboratory-simulated fires of composted tannery sludges long-term amended agricultural soils.

Controlled or accidental fires can impact agricultural soils amended with composted organic materials since high temperatures cause fast organic matter (OM) mineralization and soil properties modifications. During these events, potentially toxic elements (PTEs) associated with OM can be released and change their distribution and speciation thus becoming a threat to the environment and to crops. In this study, we investigated the changes of distribution and speciation of chromium in soils long-term amended with compost obtained from tannery sludges, after simulating fires of different intensity (300, 400 and 500 °C) likely to occur on agricultural soils. A combination of conventional soil chemical analyses and bulk and (sub)micro X-ray analyses allowed the observation of the formation of hexavalent chromium and changes of chromium speciation. Specifically, a strong decrease of Cr-OM associations was found with increasing temperature in favour of Cr-iron (hydr)oxides interactions and CaCrO4 formation. These data provide first evidence that fires can transform OM-stabilized Cr into more mobile, available and toxic Cr-forms potentially accessible for plant uptake, thus posing a risk for the food chain and the environment.

Combined Effect of Laboratory-Simulated Fire and Chromium Pollution on Microbial Communities in an Agricultural Soil.

Fire events in agricultural soils can modify not only soil properties but also the structure of soil microbial communities, especially in soils containing high concentrations of potentially toxic elements (PTEs). The recolonization of burned soils can in fact favor the proliferation of certain microorganisms, more adaptable to post-fire soil conditions and higher PTE availability, over others. In this study, we simulated with laboratory experiments the microbial recolonization of an agricultural soil containing high Cr concentrations after heating at 500 °C for 30 min, to mimic the burning of crop residues. Changes in soil properties and Cr speciation were assessed, as well as soil microbial structure by means of 16S rRNA gene sequencing. Both altered soil conditions and increased Cr availability, especially Cr(VI), appeared to be responsible for the reduction in species diversity in heated soils and the proliferation of Firmicutes. Indeed, already after 3 days from the heat treatment, Firmicutes increased from 14% to 60% relative abundance. In particular, Paenibacillus was the most abundant genus identified after the simulation, with an average relative abundance of 40%. These bacteria are known to be good fire-responders and Cr-tolerant. These results could be useful to identify bacterial strains to be used as bioindicators of altered environments and for the recovery of fire-impacted polluted sites.

Fire effects on the distribution and bioavailability of potentially toxic elements (PTEs) in agricultural soils.

In the last years, uncontrolled fires are frequently occurring in forest and agricultural areas as an indirect effect of the rising aridity and global warming or caused by intentional illegal burnings. In addition, controlled burning is still largely used by farmers as an agricultural practice in many parts of the world. During fire events, soil can reach very high temperatures at the soil surface, causing dramatic changes of soil properties and elements biogeochemistry. Among soil elements, also potentially toxic elements (PTEs) can be affected by fires, becoming more or less mobile and bioavailable, depending on fire severity and soil characteristics. Such transformations could be particularly relevant in agricultural soils used for crop productions since fire events could modify PTEs speciation and uptake by plants and associated (micro)organisms thus endangering the whole food-chain. In this review, after describing the effects of fire on soil minerals and organic matter, the impact of fires on PTEs distribution and speciation in soils is presented, as well as their influence on soil microorganisms and plants uptake. The most common experimental methods used to simulate fires at the laboratory and field scale are briefly illustrated, and finally the impact that traditional and innovative agricultural practices can have on PTEs availability in burned agricultural soils is discussed in a future research perspective.

Assessing chromium pollution and natural stabilization processes in agricultural soils by bulk and micro X-ray analyses.

A combined approach based on multiple X-ray analytical techniques and conventional methods was adopted to investigate the distribution and speciation of Cr in a polluted agricultural soil, from the bulk-scale down to the (sub)micro-level. Soil samples were collected from two different points, together with a control sample taken from a nearby unpolluted site. The bulk characterization revealed that the polluted soils contained much higher concentrations of organic matter (OM) and potentially toxic elements (PTE) than the control. Chromium was the most abundant PTE (up to 5160 g kg-1), and was present only as Cr(III), as its oxidation to Cr(VI) was hindered by the high OM content. According to sequential extractions, Cr was mainly associated to the soil oxidisable fraction (74%) and to the residual fraction (25%). The amount of Cr potentially bioavailable for plant uptake (DTPA-extractable) was negligible. Characterization of soil thin sections by micro X-ray fluorescence (µXRF) and field emission scanning electron microscopy coupled with microanalysis (FEGSEM-EDX) showed that Cr was mainly distributed in aggregates ranging from tens micrometres to few millimetres in size. These aggregates were coated with an aluminosilicate layer and contained, in the inner part, Cr, Ca, Zn, P, S and Fe. Hyperspectral elaboration of µXRF data revealed that polluted soils were characterised by an exogenous organic-rich fraction containing Cr (not present in the control), and an endogenous aluminosilicate fraction (present also in the control), coating the Cr-containing aggregates. Analyses by high-resolution micro X-ray computed tomography (µCT) revealed a different morphology of the soil aggregates in polluted soils compared with the control. The finding of microscopic leather residues, combined with the results of bulk- and micro-characterizations, suggested that Cr pollution was likely ascribable to soil amendment with tannery waste-derived matrices. However, over the years, a natural process of Cr stabilization occurred in the soil thus reducing the environmental risks.