Mercury mobility, colloid formation and methylation in a polluted Fluvisol as affected by manure application and flooding–draining cycle

Floodplain soils polluted with high levels of mercury (Hg) are potential point sources to downstream ecosystems. Repeated flooding (e.g., redox cycling) and agricultural activities (e.g., organic matter addition) may influence the fate and speciation of Hg in these soil systems. The formation and aggregation of colloids and particles influence both Hg mobility and its bioavailability to microbes that form methylmercury (MeHg). In this study, we conducted a microcosm flooding–draining experiment on Hg-polluted floodplain soils originating from an agriculturally used area situated in the Rhone Valley (Valais, Switzerland). The experiment comprised two 14 d flooding periods separated by one 14 d draining period. The effect of freshly added natural organic matter on Hg dynamics was assessed by adding liquid cow manure (+MNR) to two soils characterized by different Hg (47.3±0.5 or 2.38±0.01 mg kg−1) and organic carbon (OC: 1.92 wt % or 3.45 wt %) contents. During the experiment, the release, colloid formation of Hg in soil solution and net MeHg production in the soil were monitored. Upon manure addition in the highly polluted soil (lower OC), an accelerated release of Hg to the soil solution could be linked to a fast reductive dissolution of Mn oxides. The manure treatments showed a fast sequestration of Hg and a higher percentage of Hg bound by particulate (0.02–10 µm). Also, analyses of soil solutions by asymmetrical flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (AF4–ICP–MS) revealed a relative increase in colloidal Hg bound to dissolved organic matter (Hg–DOM) and inorganic colloidal Hg (70 %–100 %) upon manure addition. Our experiment shows a net MeHg production the first flooding and draining period and a subsequent decrease in absolute MeHg concentrations after the second flooding period. Manure addition did not change net MeHg production significantly in the incubated soils. The results of this study suggest that manure addition may promote Hg sequestration by Hg complexation on large organic matter components and the formation and aggregation of inorganic HgS(s) colloids in Hg-polluted Fluvisols with low levels of natural organic matter.</p

Plant secondary metabolite-dependent plant-soil feedbacks can improve crop yield in the field.

Plant secondary metabolites that are released into the rhizosphere alter biotic and abiotic soil properties, which in turn affect the performance of other plants. How this type of plant-soil feedback affects agricultural productivity and food quality in the field in the context of crop rotations is unknown. Here, we assessed the performance, yield and food quality of three winter wheat varieties growing in field plots whose soils had been conditioned by either wild type or benzoxazinoid-deficient bx1 maize mutant plants. Following maize cultivation, we detected benzoxazinoid-dependent chemical and microbial fingerprints in the soil. The benzoxazinoid fingerprint was still visible during wheat growth, but the microbial fingerprint was no longer detected. Wheat emergence, tillering, growth, and biomass increased in wild type conditioned soils compared to bx1 mutant conditioned soils. Weed cover was similar between soil conditioning treatments, but insect herbivore abundance decreased in benzoxazinoid-conditioned soils. Wheat yield was increased by over 4% without a reduction in grain quality in benzoxazinoid-conditioned soils. This improvement was directly associated with increased germination and tillering. Taken together, our experiments provide evidence that soil conditioning by plant secondary metabolite producing plants can increase yield via plant-soil feedbacks under agronomically realistic conditions. If this phenomenon holds true across different soils and environments, optimizing root exudation chemistry could be a powerful, genetically tractable strategy to enhance crop yields without additional inputs

Investigation into mercury bound to biothiols: structural identification using ESI–ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS

Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)2, Hg(GS)2, MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury–amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants

A herbivore tag-and-trace system reveals contact- and density-dependent repellence of a root toxin

Foraging behavior of root feeding organisms strongly affects plant-environment-interactions and ecosystem processes. However, the impact of plant chemistry on root herbivore movement in the soil is poorly understood. Here, we apply a simple technique to trace the movement of soil-dwelling insects in their habitats without disturbing or restricting their interactions with host plants. We tagged the root feeding larvae of Melolontha melolontha with a copper ring and repeatedly located their position in relation to their preferred host plant, Taraxacum officinale, using a commercial metal detector. This method was validated and used to study the influence of the sesquiterpene lactone taraxinic acid β-D-glucopyranosyl ester (TA-G) on the foraging of M. melolontha. TA-G is stored in the latex of T. officinale and protects the roots from herbivory. Using behavioral arenas with TA-G deficient and control plants, we tested the impact of physical root access and plant distance on the effect of TA-G on M. melolontha. The larvae preferred TA-G deficient plants to control plants, but only when physical root contact was possible and the plants were separated by 5 cm. Melolontha melolontha showed no preference for TA-G deficient plants when the plants were grown 15 cm apart, which may indicate a trade-off between the cost of movement and the benefit of consuming less toxic food. We demonstrate that M. melolontha integrates host plant quality and distance into its foraging patterns and suggest that plant chemistry affects root herbivore behavior in a plant-density dependent manner. © 2017, Springer Science+Business Media New York

Antimony release and volatilization from organic-rich and iron-rich submerged soils.

Antimony (Sb) is an poorly understood, increasingly common pollutant, especially in soils susceptible to waterlogging. We investigated the impact of waterlogging on Sb release, methylation, and volatilization from an organic-rich wetland soil and an iron (Fe)-rich floodplain soil in a 27-day microcosm experiment. The release of Sb into the porewaters of the organic-rich soil was environmentally relevant and immediate with waterlogging (3.2 to 3.5 mg L-1), and likely associated with a complex interplay of sulfide precipitation, sorption with organic matter and manganese (Mn) (oxyhydr)oxides in the soil. The release of Sb from the Fe-rich soil was likely associated with Fe-(oxyhydr)oxide reduction and immobilized due to co-precipitation with Fe-sulfides or as Sb-sulfides. Volatile Sb was produced from the soils after waterlogging. The organic-rich soil produced more volatile Sb (409 to 835 ng kgsoil-1), but the Fe-rich soil volatilized Sb more efficiently. The negligible association of Sb volatilization with soil parameters indicates a more complex underlying, potentially microbial, mechanism and that antimony volatilization could be ubiquitous and not dependent on specific soil properties. Future works should investigate the microbial and physiochemical drivers of Sb volatilization in soils as it may be an environmentally relevant part of the biogeochemical cycle

Arsenic and selenium mobilisation from organic matter treated mine spoil with and without inorganic fertilisation

Organic matter amendments are applied to contaminated soil to provide a better habitat for re-vegetation and remediation, and olive mill waste compost (OMWC) has been described as a promising material for this aim. We report here the results of an incubation experiment carried out in flooded conditions to study its influence in As and metal solubility in a trace elements contaminated soil. NPK fertilisation and especially organic amendment application resulted in increased As, Se and Cu concentrations in pore water. Independent of the amendment, dimethylarsenic acid (DMA) was the most abundant As species in solution. The application of OMWC increased pore water dissolved organic-carbon (DOC) concentrations, which may explain the observed mobilisation of As, Cu and Se; phosphate added in NPK could also be in part responsible of the mobilisation caused in As. Therefore, the application of soil amendments in mine soils may be particularly problematic in flooded systems

Soil chemistry determines whether defensive plant secondary metabolites promote or suppress herbivore growth

Plant secondary (or specialized) metabolites mediate important interactions in both the rhizosphere and the phyllosphere. If and how such compartmentalized functions interact to determine plant–environment interactions is not well understood. Here, we investigated how the dual role of maize benzoxazinoids as leaf defenses and root siderophores shapes the interaction between maize and a major global insect pest, the fall armyworm. We find that benzoxazinoids suppress fall armyworm growth when plants are grown in soils with very low available iron but enhance growth in soils with higher available iron. Manipulation experiments confirm that benzoxazinoids suppress herbivore growth under iron-deficient conditions and in the presence of chelated iron but enhance herbivore growth in the presence of free iron in the growth medium. This reversal of the protective effect of benzoxazinoids is not associated with major changes in plant primary metabolism. Plant defense activation is modulated by the interplay between soil iron and benzoxazinoids but does not explain fall armyworm performance. Instead, increased iron supply to the fall armyworm by benzoxazinoids in the presence of free iron enhances larval performance. This work identifies soil chemistry as a decisive factor for the impact of plant secondary metabolites on herbivore growth. It also demonstrates how the multifunctionality of plant secondary metabolites drives interactions between abiotic and biotic factors, with potential consequences for plant resistance in variable environments