Metallic micronutrients are associated with the structure and function of the soil microbiome.

The relationship between metallic micronutrients and soil microorganisms, and thereby soil functioning, has been little explored. Here, we investigate the relationship between metallic micronutrients (Fe, Mn, Cu, Zn, Mo and Ni) and the abundance, diversity and function of soil microbiomes. In a survey across 180 sites in China, covering a wide range of soil conditions the structure and function of the soil microbiome are highly correlated with metallic micronutrients, especially Fe, followed by Mn, Cu and Zn. These results are robust to controlling for soil pH, which is often reported as the most important predictor of the soil microbiome. An incubation experiment with Fe and Zn additions for five different soil types also shows that increased micronutrient concentration affects microbial community composition and functional genes. In addition, structural equation models indicate that micronutrients positively contribute to the ecosystem productivity, both directly (micronutrient availability to plants) and, to a lesser extent, indirectly (via affecting the microbiome). Our findings highlight the importance of micronutrients in explaining soil microbiome structure and ecosystem functioning.

The potential of arbuscular mycorrhizal fungi to enhance metallic micronutrient uptake and mitigate food contamination in agriculture: prospects and challenges.

Optimizing agroecosystems and crops for micronutrient uptake while reducing issues with inorganic contaminants (metal(loid)s) is a challenging task. One promising approach is to use arbuscular mycorrhizal fungi (AMF) and investigate the physiological, molecular and epigenetic changes that occur in their presence and that lead to changes in plant metal(loid) concentration (biofortification of micronutrients or mitigation of contaminants). Moreover, it is important to understand these mechanisms in the context of the soil microbiome, particularly those interactions of AMF with other soil microbes that can further shape crop nutrition. To address these challenges, a two-pronged approach is recommended: exploring molecular mechanisms and investigating microbiome management and engineering. Combining both approaches can lead to benefits in human health by balancing nutrition and contamination caused by metal(loid)s in the agro-ecosystem.

Increasing the number of stressors reduces soil ecosystem services worldwide.

Increasing the number of environmental stressors could decrease ecosystem functioning in soils. Yet this relationship has never been globally assessed outside laboratory experiments. Here, using two independent global standardized field surveys, and a range of natural and human factors, we test the relationship between the number of environmental stressors exceeding different critical thresholds and the maintenance of multiple ecosystem services across biomes. Our analysis shows that, multiple stressors, from medium levels (>50%), negatively and significantly correlates with impacts on ecosystem services, and that multiple stressors crossing a high-level critical threshold (over 75% of maximum observed levels), reduces soil biodiversity and functioning globally. The number of environmental stressors >75% threshold was consistently seen as an important predictor of multiple ecosystem services, therefore improving prediction of ecosystem functioning. Our findings highlight the need to reduce the dimensionality of the human footprint on ecosystems to conserve biodiversity and function.

Soil contamination in nearby natural areas mirrors that in urban greenspaces worldwide.

Soil contamination is one of the main threats to ecosystem health and sustainability. Yet little is known about the extent to which soil contaminants differ between urban greenspaces and natural ecosystems. Here we show that urban greenspaces and adjacent natural areas (i.e., natural/semi-natural ecosystems) shared similar levels of multiple soil contaminants (metal(loid)s, pesticides, microplastics, and antibiotic resistance genes) across the globe. We reveal that human influence explained many forms of soil contamination worldwide. Socio-economic factors were integral to explaining the occurrence of soil contaminants worldwide. We further show that increased levels of multiple soil contaminants were linked with changes in microbial traits including genes associated with environmental stress resistance, nutrient cycling, and pathogenesis. Taken together, our work demonstrates that human-driven soil contamination in nearby natural areas mirrors that in urban greenspaces globally, and highlights that soil contaminants have the potential to cause dire consequences for ecosystem sustainability and human wellbeing.

Soils in warmer and less developed countries have less micronutrients globally.

Soil micronutrients are capital for the delivery of ecosystem functioning and food provision worldwide. Yet, despite their importance, the global biogeography and ecological drivers of soil micronutrients remain virtually unknown, limiting our capacity to anticipate abrupt unexpected changes in soil micronutrients in the face of climate change. Here, we analyzed >1300 topsoil samples to examine the global distribution of six metallic micronutrients (Cu, Fe, Mn, Zn, Co and Ni) across all continents, climates and vegetation types. We found that warmer arid and tropical ecosystems, present in the least developed countries, sustain the lowest contents of multiple soil micronutrients. We further provide evidence that temperature increases may potentially result in abrupt and simultaneous reductions in the content of multiple soil micronutrients when a temperature threshold of 12-14°C is crossed, which may be occurring on 3% of the planet over the next century. Altogether, our findings provide fundamental understanding of the global distribution of soil micronutrients, with direct implications for the maintenance of ecosystem functioning, rangeland management and food production in the warmest and poorest regions of the planet.

Grazing and ecosystem service delivery in global drylands.

Grazing represents the most extensive use of land worldwide. Yet its impacts on ecosystem services remain uncertain because pervasive interactions between grazing pressure, climate, soil properties, and biodiversity may occur but have never been addressed simultaneously. Using a standardized survey at 98 sites across six continents, we show that interactions between grazing pressure, climate, soil, and biodiversity are critical to explain the delivery of fundamental ecosystem services across drylands worldwide. Increasing grazing pressure reduced ecosystem service delivery in warmer and species-poor drylands, whereas positive effects of grazing were observed in colder and species-rich areas. Considering interactions between grazing and local abiotic and biotic factors is key for understanding the fate of dryland ecosystems under climate change and increasing human pressure.

Review on the interactions of arsenic, iron (oxy)(hydr)oxides, and dissolved organic matter in soils, sediments, and groundwater in a ternary system.

High concentrations of arsenic (As) in groundwater threaten the environment and public health. Geogenically, groundwater As contamination predominantly occurs via its mobilization from underground As-rich sediments. In an aquatic ecosystem, As is typically driven by several underlying processes, such as redox transitions, microbially driven reduction of iron (Fe) oxide minerals, and release of associated As. Notably, dissolved As mobilized from soils and sediments exhibits high affinity for dissolved organic matter (DOM). Thus, high DOM concentrations can increase As mobility. Therefore, it is crucial to understand the complex interactions and biogeochemical cycling of As, DOM, and Fe oxides. This review collates knowledge regarding the fate of As in multicomponent As-DOM-Fe systems, including ternary complexes involving both Fe and DOM. Additionally, the release mechanisms of As from sediments into groundwater in the presence of both Fe and DOM have been discussed. The mechanisms of As mobilization/sorption at the solid-water interface can be affected by negatively charged DOM competing for sorption sites with As on Fe (oxy)(hydr)oxides and may be further modified by other anionic ubiquitous species such as phosphate, silicic acid, or sulfur. This review emphasizes the need for a comprehensive understanding of the impact of DOM, Fe oxides, and related biogeochemical processes on As mobilization to aquifers. The review identifies important knowledge gaps that may aid in developing applicable practices for preventing the spread of As contamination in aquatic resources and traditional soil management practices.

Synergistic effects of biochar and biostimulants on nutrient and toxic element uptake by pepper in contaminated soils.

BACKGROUND: Nowadays a significant amount of land contaminated with toxic elements is being used for agriculture, posing a serious risk of crop contamination and toxicity. Several methodologies are being used to remediate soil contamination, including the use of amendments such as biochar. This work evaluated the effects of biochar combined with different fertirrigations (water, a conventional fertilizer solution, or a fertilizer solution with a commercial biostimulant derived from leonardite) on the availability of toxic elements and nutrients for pepper cultivated in a soil contaminated with As, Cd, Pb, and Zn. RESULTS: Irrigation with fertilizer solutions improved plant growth regardless of the biochar amendment. Biochar decreased the bioavailability of Cu and Pb in soil and the Cu content in pepper leaves. Combined with fertilization, biochar also decreased plant As and Pb content. Biochar combined with biostimulant decreased the bioavailable content of Cd in soil and its uptake by pepper plants. CONCLUSION: The use of biochar and biostimulant presented advantages for plant production in a non-suitable scenario of nutrient scarcity and contamination. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

(Im)mobilization of arsenic, chromium, and nickel in soils via biochar: A meta-analysis.

Biochar is a promising immobilizing agent of trace elements (TEs) in contaminated soils. However, several contradictory results have been reported regarding the potential of biochar to immobilize arsenic (As), chromium (Cr), and nickel (Ni) in contaminated soils. We conducted a meta-analysis on the published papers since 2006 until 2019 to examine the effects of biochar on the chemical (im)mobilization of As, Cr, and Ni in contaminated soils and to elucidate the major factors that control their interactions with biochar in soil. We synthesized 48 individual papers comprised of a total of 9351 pairwise comparisons and used the statistical tool of Cohen's d as an appropriate effect size for the comparison between means. We found that the application of biochar often increased the As mobilization in soils. Important variables that modulated the biochar effects on As mobilization in soil were pyrolysis temperature and time (ranging between 8 and 16 times when T > 450 °C and t > 1hr), organic matter (7-16 times when SOM<3%) and further site conditions. In contrast to As, biochar efficiently immobilized Cr and Ni in contaminated soils. The extent of the Cr and Ni immobilization was determined by the feedstock (Cr: 7-18 times for agricultural residue-derived biochar; Ni: 13-32 times for woody biomass-derived biochar). Our meta-analysis provides a compilation on the potential of different types of biochar to reduce/increase the mobilization of As, Cr, and Ni in various soils and under different experimental conditions. This study provides important insights on factors that affect biochar's efficiency for the (im)mobilization of As, Cr, and Ni in contaminated soils. While biochar effectively immobilizes Cr and Ni, a proper management of As-polluted soils with pristine biochar is still challenging. This limitation might be overcome by modification of biochar surfaces to exhibit higher surface area and functionality and active sites for surface complexation with TEs.

Soil element coupling is driven by ecological context and atomic mass.

The biogeochemical cycling of multiple soil elements is fundamental for life on Earth. Here, we conducted a global field survey across 16 chronosequences from contrasting biomes with soil ages ranging from centuries to millions of years. For this, we collected and analysed 435 topsoil samples (0-10 cm) from 87 locations. We showed that high levels of topsoil element coupling, defined as the average correlation among nineteen soil elements, are maintained over geological timescales globally. Cross-biome changes in plant biodiversity, soil microbial structure, weathering, soil pH and texture, and mineral-free unprotected organic matter content largely controlled multi-element coupling. Moreover, elements with heavier atomic mass were naturally more decoupled and unpredictable in space than those with lighter mass. Only the coupling of carbon, nitrogen and phosphorus, which are essential to life on Earth, deviated from this predictable pattern, suggesting that this anomaly may be an undeniable fingerprint of life in terrestrial soils.

Biocrusts buffer against the accumulation of soil metallic nutrients induced by warming and rainfall reduction.

The availability of metallic nutrients in dryland soils, many of which are essential for the metabolism of soil organisms and vascular plants, may be altered due to climate change-driven increases in aridity. Biocrusts, soil surface communities dominated by lichens, bryophytes and cyanobacteria, are ecosystem engineers known to exert critical functions in dryland ecosystems. However, their role in regulating metallic nutrient availability under climate change is uncertain. Here, we evaluated whether well-developed biocrusts modulate metallic nutrient availability in response to 7 years of experimental warming and rainfall reduction in a Mediterranean dryland located in southeastern Spain. We found increases in the availability of K, Mg, Zn and Na under warming and rainfall exclusion. However, the presence of a well-developed biocrust cover buffered these effects, most likely because its constituents can uptake significant quantities of available metallic nutrients. Our findings suggest that biocrusts, a biotic community prevalent in drylands, exert an important role in preserving and protecting metallic nutrients in dryland soils from leaching and erosion. Therefore, we highlight the need to protect them to mitigate undesired effects of soil degradation driven by climate change in this globally expanding biome.

Mobility of arsenic, chromium and copper arising from soil application of stabilised aggregates made from contaminated wood ash.

Stabilized cementitious aggregates AG were produced from wood ashes containing ∼10,000 mg kg-1 As, Cr and Cu, then amended to two agricultural pasture soils. Metal(loid) leaching (column tests), mobility (pore water extracts) and uptake to ryegrass was determined, comparing raw ashes with aggregates. Risk modeling was applied to selected data to inform wider discussion of the experimental results. Under rapid leaching (7 h) AG 2 (pre-strengthened with CO2) outperformed AG 1 in suppressing soluble metal(loid) removal. During prolonged leaching (12d) both aggregates were susceptible to mild dissolution/release of metal(loid)s upon acidification. Pore water sampled from the pot test indicated that Cr was generally most mobile, As least so, reduced furthest by AG 2. Risk modelling, based on pot experimental data, demonstrated soil specific accumulation of As in beef muscle and milk, being furthest reduced (compared to the raw ash addition) by AG 2 in soil A, but increased in soil B by the same treatment. The results of this study indicate that a reduction in soluble As, Cr and Cu can be achieved through cementitious aggregation of wood ashes, though the extent is metal(loid) specific when amended to soils. Pre-testing under local soil conditions before field application would be required to ensure that metal(loid) mobility remained suppressed.

Localized Intensification of Arsenic Release within the Emergent Rice Rhizosphere.

Behavior of trace elements in flooded/lowland rice soils is controlled by root-zone iron oxidation. Insoluble iron species bind/capture toxic elements, i.e., arsenic. However, it was recently observed that within this territory of arsenic immobilization lies a zone of prolific iron release, accompanied by a significant flux of arsenic in close proximity to rice root apices. Questions still remain on how common this phenomenon is and whether the chemical imaging approaches or soils/cultivars used influence this event. Here, three types of ultrathin/high-resolution diffusive gradient in thin films (DGT) substrates were integrated with oxygen planar optodes in a multilayer system, providing two-dimensional mapping of solute fluxes. The three DGT approaches revealed a consistent/overlapping spatial distribution with localized flux maxima for arsenic, which occurred in all experiments, concomitant with iron mobilization. Soil/porewater microsampling within the rhizosphere revealed no significant elevation in the solid phase's total iron and arsenic concentrations between aerobic and anaerobic zones. Contrary to arsenic, phosphorus bioavailability was shown to decrease in the arsenic/iron flux maxima. Rice roots, in addition to their role in nutrient acquisition, also perform a key sensory function. Flux maxima represent a significant departure from the chemical conditions of the bulk/field environment, but our observations of a complete rhizosphere reveal a mixed mode of root-soil interactions.

Engineered Pyrogenic Materials as Tools to Affect Arsenic Mobility in Old Mine Site Soil of Mediterranean Region.

The application of pyrogenic materials in immobilization processes of metalloids represents a burning issue in environmental and waste applications and management. The main objective of this study was to characterize the effect of biomass pretreatment by Cu, Fe and Mg blending and pyrolysis temperature on As sorption efficiency as a model of anionic metalloids from model solutions and As immobilization in old mine soil by pyrogenic materials. The physico-chemical characterization of engineered materials produced in slow pyrolysis process at 400 and 700°C from metal-blended hard wood chips (30% w/w) showed increasing of surface areas (1.4-1.8-fold), changes in pH, and more than 50% decrease in total C content. The batch sorption processes of As ions by Cu-modified pyrogenic materials (CuPM), Fe-modified pyrogenic materials (FePM), and Mg-modified pyrogenic materials (MgPM) showed increasing uptake in order CuPM700 (Qmax 2.56 mg g-1) < CuPM400 (Qmax 3.88 mg g-1) < FePM700 (Qmax 5.90 mg g-1) < MgPM700 (Qmax 7.42 mg g-1) < MgPM400 (Qmax 9.59 mg g-1) < FePM400 (Qmax 10.55 mg g-1). Engineered pyrogenic materials produced at 400°C showed higher immobilization effect on soluble As in soil pore water of old mine site soil from Mediterranean area. FePM400 reduced mobility of arsenic > 3.2 times and MgPM400 > 5 times compared to control. Promising pyrogenic material MgPM400 showed immobilization effect also on additional heavy metals (Cd, Cu, Fe, Mn, Pb, Sr, Zn) present in studied soil.

Aided phytostabilisation over two years using iron sulphate and organic amendments: Effects on soil quality and rye production.

An outdoor macrocosm experiment using Fe-based and organic amendments over 2 years was set up to evaluate the effectiveness of aided-phytostabilisation. For that, a soil contaminated with As- and Cu-rich waste material (∼13000 mg As kg-1 and ∼500 mg Cu kg-1) was treated with combinations of iron sulphate (Fe) with lime, paper mill sludge (PS), holm-oak biochar (BC), olive mill waste compost (OMWC) or green waste compost (GWC). Rye (Secale cereale L.) was grown in the treated and non-treated soils 16 months after addition of the amendments. Arsenic and Cu dynamics in soil were assessed throughout the experiment and soil quality parameters (soil nutrients, organic matter and soil biology) were measured almost two years after addition of the amendments. All treatments resulted in a reduction of soluble and extractable Cu during the experiment and, despite the increase in soil pH (from 5 to 68) and DOC (from 10 up to 50 mg DOC L-1) provoked by the amendments, As was not significantly mobilised in the treated soils. Treatments combining Fe sulphate with the organic materials, especially biochar and both composts, resulted in an increase in soil available nutrients and enhanced rye growth. In this semi-field scale experiment, the combination of Fe sulphate with holm-oak biochar showed the most promising results in terms of soil fertility (nutrient availability), plant As and Cu uptake and soil C sequestration. Further research should focus on monitoring long-term effects of the soil amendments on crops, following repeated applications.

Complementary assessment of As, Cu and Zn environmental availability in a stabilised contaminated soil using large-bore column leaching, automatic microcolumn extraction and DGT analysis.

Soil pollution with trace elements is a concerning issue worldwide. Monitoring of soil pollution and remediation protocols need still from valid complementary analytical approaches able to detect changes in speciation and lability of metals in soils (e.g. stabilization or mobility). In this work, we compare three different analytical approaches to assess potential changes in environmental availability of Cu, As and Zn in a Mediterranean polluted soil that was amended with different combinations of iron sulphate and alkaline paper sludge waste. The studied methods were: (i) a standard large-bore flow-through column system (macrocolumn), (ii) an automatic dynamic flow-through microcolumn extraction system, and (iii) the diffusive gradients in thin gels technique (DGT). The three analytical approaches tested showed immobilization of Zn and Cu in contaminated mine soils after co-application of paper sludge and iron sulphate, but they differ quantitatively in terms of As mobility. Interconversion between oxidation states of inorganic As is observed to occur to a larger extent in macrocolumn. Because this may only occur in very specific Mediterranean scenarios (i.e. organic matter application to intermittently flooded mine soils), macrocolumn extraction procedures might not appropriately mimic the environmental availability of As in soils with organic amendments (e.g., paper sludge waste). Microcolumn leaching is the fastest screening tool to ascertain the efficiency of chemical amendments, but DGT is a good alternative with less technical demands.

Aridity and reduced soil micronutrient availability in global drylands.

Drylands cover more than 40% of terrestrial surface, and their global extent and socio-ecological importance will increase in the future due to the forecasted increases in aridity driven by climate change. Despite the essential role of metallic micronutrients in life chemistry and ecosystem functioning, it is virtually unknown how their bioavailability changes along aridity gradients at the global scale. Here we analysed soil total and available Cu, Fe, Mn, and Zn in 143 drylands from all continents, except Antarctica, covering a broad range of aridity and soil conditions. We found that total and available micronutrient concentrations in dryland soils were low compared to averages commonly found in soils of natural and agricultural ecosystems globally. Aridity negatively affected the availability of all micronutrients evaluated, mainly indirectly by increasing soil pH and decreasing soil organic matter. Remarkably, the available Fe:Zn ratio decreased exponentially as aridity increased, pointing to stoichiometric alterations. Our findings suggest that increased aridity conditions due to climate change will limit the availability of essential micronutrients for organisms, particularly that of Fe and Zn, which together with other adverse effects (e.g., reduced water availability) may pose serious threats to key ecological processes and services, such as food production, in drylands worldwide.

Designing biochar properties through the blending of biomass feedstock with metals: Impact on oxyanions adsorption behavior.

Metal-blending of biomass prior to pyrolysis is investigated in this work as a tool to modify biochar physico-chemical properties and its behavior as adsorbent. Six different compounds were used for metal-blending: AlCl3, Cu(OH)2, FeSO4, KCl, MgCl2 and Mg(OH)2. Pyrolysis experiments were performed at 400 and 700 °C and the characterization of biochar properties included: elemental composition, thermal stability, surface area and pore size distribution, Zeta potential, redox potential, chemical structure (with nuclear magnetic resonance) and adsorption behavior of arsenate, phosphate and nitrate. Metalblending strongly affected biochars' surface charge and redox potential. Moreover, it increased biochars' microporosity (per mass of organic carbon). For most biochars, mesoporosity was also increased. The adsorption behavior was enhanced for all metal-blended biochars, although with significant differences across species: Mg(OH)2-blended biochar produced at 400 °C showed the highest phosphate adsorption capacity (Langmuir Qmax approx. 250 mg g-1), while AlCl3-blended biochar produced also at 400 °C showed the highest arsenate adsorption (Langmuir Qmax approx. 14 mg g-1). Significant differences were present, even for the same biochar, with respect to the investigated oxyanions. This indicates that biochar properties need to be optimized for each application, but also that this optimization can be achieved with tools such as metal-blending. These results constitute a significant contribution towards the production of designer biochars.

The effect of biochar amendments on phenanthrene sorption, desorption and mineralisation in different soils.

The contamination of soils and waters with organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), affect a large number of sites worldwide that need remediation. In this context soils amendments can be used to immobilise PAHs while maintaining soil functioning, with biochar being a promising amendment. In this experiment, phenantrene (Phe) was used as a frequent PAH contaminating soils and we studied the effect of three biochars at 1% applications to three different substrates, two agricultural topsoils and pure sand. We evaluated the changes in soil properties, sorption-desorption of Phe, and mineralisation of Phe in all treatments. Phe in pure sand was effectively sorbed to olive pruning (OBC) and rice husk (RBC) biochars, but pine biochar (PBC) was not as effective. In the soils, OBC and RBC only increased sorption of Phe in the silty soil. Desorption was affected by biochar application, RBC and OBC decreased water soluble Phe independently of the soil, which may be useful in preventing leaching of Phe into natural waters. Contrastingly, OBC and RBC slightly decreased the mineralisation of Phe in the soils, thus indicating lower bioavailability of the contaminant. Overall, biochar effects in the two tested soils were low, most likely due to the rather high soil organic C (SOC) contents of 2.2 and 2.8% with Koc values in the same range as those of the biochars. However, OBC and RBC additions can substantially increase adsorption of Phe in soils poor in SOC.