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Water pollutions of heavy metal and metalloids (HMMs), typically including As, Cd, Cu, Cr, Mn, Ni, Pb, and Zn, are becoming a severe environmental problem to be controlled. Constructed wetlands (CWs) have been intensively investigated and applied for the removal of HMMs. By analyzing a mass of data from the existing literatures, this review found that the HMM removals in CWs varied from 12.35 % to 91.01 %, depending upon the HMM species and CW conditions. Nonetheless, 88.50 % of the influent HMMs were eventually immobilized in the CW sediments, while the common wetland plants are inefficient (i.e., accounting for 4.64 %) to uptake and accumulate the HMMs. It was also found that the concentrations of certain HMMs in the CW sediments have already exceeded up to 100 % of various environmental standards, indicating the urgency of introducing HMM hyperaccumulators in the systems. Through comparison, both the aboveground and belowground HMM accumulating capacities of reported hyperaccumulators were higher by magnitudes than common wetland plants. Following this, the efficacies and mechanisms of candidate hyperaccumulators were provided for the various scenarios of HMM control in CWs. Further, the selection principals, culture methods, and harvest strategies of hyperaccumulator in CWs were discussed. Finally, several perspectives were suggested for the future research. Overall, this review provided guiding information for the utilization of hyperaccumulators in CWs, which can improve the efficiency and sustainability of HMM removal in the CW systems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Heavy metals and metalloids in the environment are recognised as a threat to the health of organism. Terrestrial birds are ideal subjects for the examination of these pollutants because of their high mobility and high intra- and interspecific variation in trophic levels. We examined the contents of 6 trace metals (Cd, Pb, Cr, Sb and V) and metalloids (As) in the liver, kidney, muscle, and feathers of woodcocks (Scolopax rusticola) from Southern Italy by a validated ICP-MS method. Significant differences in trace elements were found in all the tissues examined (p < 0.05). The highest Sb and Cr levels were found in feathers samples with mean values of 0.019 mg/Kg and 0.085 mg/Kg, respectively. High Pb levels were found in muscle, with 23 % of the samples exceeding the limits set by the European Union. Cd was predominantly found in the kidney samples (0.76 mg/Kg). Vanadium was the less abundant trace metal, showing the highest concentrations in the liver (0.028 ± 0.011 mg/Kg). Higher As levels were found in muscle (0.02 ± 0.015 mg/Kg). No significant differences between sex and age classes (juveniles vs. adults) were found, nor were there correlations between morphometric parameters and trace metal/metalloid contents. Principal Component Analysis determined differences in metal accumulation between tissues. Feathers were confirmed as useful indicators of metal contamination. The results of this work confirmed that the accumulation of toxic elements in the tissues of woodcocks is primarily influenced by ecological traits such as feeding habits and migration status. Statistical analysis of the tissues would seem to exclude important accumulation phenomena of Pb. The high levels found in the muscle could be due to lead ammunition. This work provides the first data on the accumulation of As, Cr, Sb, and V in woodcocks tissue, providing a more comprehensive insight into the potential impact of these pollutants on birds., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The mammalian retina contains high amounts of metals/metalloid-selenium. Their dyshomeostases are associated with certain retinal diseases. We carried out this bioinformatics study to identify the relationships between putative retinal metal/selenium binding proteins, their molecular functions, and biological processes. Identification of putative mouse metal/selenium binding proteins was based on known binding motifs, domains, patterns, and profiles. Annotations were obtained from Uniprot keywords 'metal binding', 'metal ion co-factors', 'selenium proteins'. Protein functions were estimated by associative frequency with key words in UniProt annotations. The raw data of five mouse proteomics PRIDE datasets (available to date) were downloaded and processed with Mascot against the mouse taxa of Uniprot (SwissProt/Trembl) and MaxQuant (version 1.6.10.43) for qualitative and quantitative datasets, respectively. Clinically relevant variants were evaluated using archives and aggregated information in ClinVar. The 438 proteins common to all the retina proteomics datasets were used to identify over-represented Gene Ontology categories. The putative mouse retinal metal/metalloid binding proteins identified are mainly involved in: (1) metabolic processes (enzymes), (2) homeostasis, (3) transport (vesicle mediated, transmembrane, along microtubules), (4) cellular localization, (5) regulation of signalling and exocytosis, (6) organelle organization, (7) (de)phosphorylation, and (8) complex assembly. Twenty-one proteins were identified as involved in response to light stimulus and/or visual system development. An association of metal ion binding proteins rhodopsin, photoreceptor specific nuclear receptor, calcium binding protein 4 with disease-related mutations in inherited retinal conditions was identified, where the mutations affected an area within or in close proximity to the metal binding site or domain. These findings suggest a functional role for the putative metal/metalloid binding site in retinal proteins in certain retinal disorders., (© The Author(s) 2024. Published by Oxford University Press.)

Globally, metal/metalloid(s) soil contamination is a persistent issue that affects the atmosphere, soil, water and plant health in today's industrialised world. However, an overabundance of these transition ions promotes the excessive buildup of reactive oxygen species (ROS) and ion imbalance, which harms agricultural productivity. Plants employ several strategies to overcome their negative effects, including hyperaccumulation, tolerance, exclusion, and chelation with organic molecules. Polyamines (PAs) are the organic compounds that act as chelating agents and modulate various physiological, biochemical, and molecular processes under metal/metalloid(s) stress. Their catabolic products, including H 2 O 2 and gamma amino butyric acid (GABA), are also crucial signalling molecules in abiotic stress situations, particularly under metal/metalloid(s) stress. In this review, we explained how PAs regulate genes and enzymes, particularly under metal/metalloid(s) stress with a specific focus on arsenic (As), boron (B), cadmium (Cd), chromium (Cr), and zinc (Zn). The PAs regulate various plant stress responses by crosstalking with other plant hormones, upregulating phytochelatin, and metallothionein synthesis, modulating stomatal closure and antioxidant capacity. This review presents valuable insights into how PAs use a variety of tactics to reduce the harmful effects of metal/metalloid(s) through multifaceted strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Masson SAS. All rights reserved.)

Arsenic is highly toxic and a significant threat to human health, but certain bacteria have developed defense mechanisms initiated by As III binding to As III -sensing proteins of the ArsR family. The transcriptional regulator AfArsR responds to As III and Sb III by coordinating the metalloids with three cysteines, located in a short sequence of the same monomer chain. Here, we characterize the binding of As III and Hg II to a model peptide encompassing this fragment of the protein via solution equilibrium and spectroscopic/spectrometric techniques (pH potentiometry, UV, CD, NMR, PAC, EXAFS, and ESI-MS) combined with DFT calculations and MD simulations. Coordination of As III changes the peptide structure from a random-coil to a well-defined structure of the complex. A trigonal pyramidal AsS 3 binding site is formed with almost exactly the same structure as observed in the crystal structure of the native protein, implying that the peptide possesses all of the features required to mimic the As III recognition and response selectivity of AfArsR. Contrary to this, binding of Hg II to the peptide does not lead to a well-defined structure of the peptide, and the atoms near the metal binding site are displaced and reoriented in the Hg II model. Our model study suggests that structural organization of the metal site by the inducer ion is a key element in the mechanism of the metalloid-selective recognition of this protein.

Soil pollution by metals and metalloids as a consequence of anthropogenic industrialisation exerts a seriously damaging impact on ecosystems. However, certain plant species, termed hyperaccumulators, are able to accumulate extraordinarily high concentrations of these metal(loid)s in their aboveground tissues. Such hyperaccumulation of metal(loid)s is known to act as a defence against various antagonists, such as herbivores and pathogens. We investigated the influences of metal(loid)s on potential defence traits, such as foliar elemental, organic and mechanical defences, in the hyperaccumulator plant species Arabidopsis halleri (Brassicaceae) by artificially amending the soil with common metallic pollutants, namely cadmium (Cd) and zinc (Zn). Additionally, unamended and metal-amended soils were supplemented with the metalloid silicon (Si) to study whether Si could alleviate metal excess. Individuals originating from one non-/low- and two moderately to highly metal-contaminated sites with different metal concentrations (hereafter called accessions) were grown for eight weeks in a full-factorial design under standardised conditions. There were significant interactive effects of metal amendment and Si supplementation on foliar concentrations of certain elements (Zn, Si, aluminium (Al), iron (Fe), potassium (K) and sulfur (S), but these were accession-specific. Profiles of glucosinolates, characteristic organic defences of Brassicaceae, were distinct among accessions, and the composition was affected by soil metal amendment. Moreover, plants grown on metal-amended soil contained lower concentrations of total glucosinolates in one of the accessions, which suggests a potential trade-off between inorganic defence acquisition and biosynthesis of organic defence. The density of foliar trichomes, as a proxy for the first layer of mechanical defence, was also influenced by metal amendment and/or Si supplementation in an accession-dependent manner. Our study highlights the importance of examining the effects of co-occurring metal(loid)s in soil on various foliar defence traits in different accessions of a hyperaccumulating species., (© 2023. The Author(s).)

Metals and metalloids are used as weapons for predatory feeding by unicellular eukaryotes on prokaryotes. This review emphasizes the role of metal(loid) bioavailability over the course of Earth's history, coupled with eukaryogenesis and the evolution of the mitochondrion to trace the emergence and use of the metal(loid) prey-killing phagosome as a feeding strategy. Members of the genera Acanthamoeba and Dictyostelium use metals such as zinc (Zn) and copper (Cu), and possibly metalloids, to kill their bacterial prey after phagocytosis. We provide a potential timeline on when these capacities first evolved and how they correlate with perceived changes in metal(loid) bioavailability through Earth's history. The origin of phagotrophic eukaryotes must have postdated the Great Oxidation Event (GOE) in agreement with redox-dependent modification of metal(loid) bioavailability for phagotrophic poisoning. However, this predatory mechanism is predicted to have evolved much later - closer to the origin of the multicellular metazoans and the evolutionary development of the immune systems., Competing Interests: Declaration of interests The authors have no interests to declare., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Arsenic (As) remediation is challenging due to the complex nature and the persistence of these metalloid compounds. While it may seem that differences between As forms influence have been extensively described, new findings challenge the previously accepted knowledge, particularly for woody plants. Therefore, this study focused on 2-year-old Tilia cordata Mill. seedlings early (0, 2, 4, 12, 24 h) and late (3, 7, 12, 18, 25, 33 days) responses during growth under: As(III), As(V) or dimethylarsinic acid (DMA) (0.3 mM). Time-dependent transformations of As forms, distribution in plants, and microbiological characteristics (actinobacteria, bacteria, fungi, enzyme activity) were investigated. The highest increase in total As content was observed in plants exposed to As(V) and As(III). Dynamic metalloid form changes in the solution and tree organs were indicated. The most phytotoxic was DMA. This form was the main factor limiting the growth and effective accumulation of As. Despite experimenting in hydroponics, microorganisms played an important role in As form transformations, suggesting the potential for microbial-assisted dendroremediation strategies. The study confirmed that trees can convert more toxic forms into less toxic ones (e.g. As(III) to phytochelatins - As(III)-(PC 3 )), whose presence in roots seedlings exposed to As(III) and As(V) has been identified. The formation of hydrophobic forms (e.g. dimethylarsinoyl lipid) in the roots of seedlings grown under As(V) was confirmed. It is the first discovery for trees, previously observed only in bacteria and algae. The dynamics of metalloid form changes indicated that T. cordata transforms As forms according to their needs, which may give tree species an advantage in phytoremediation techniques. It holds great promise for the potential of dendroremediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In the face of flourishing industrialization and global trade, heavy metal and metalloid contamination of the environment is a growing concern throughout the world. The widespread presence of highly toxic compounds of arsenic, antimony, and cadmium in nature poses a particular threat to human health. Prolonged exposure to these toxins has been associated with severe human diseases, including cancer, diabetes, and neurodegenerative disorders. These toxins are known to induce analogous cellular stresses, such as DNA damage, disturbance of redox homeostasis, and proteotoxicity. To overcome these threats and improve or devise treatment methods, it is crucial to understand the mechanisms of cellular detoxification in metal and metalloid stress. Membrane proteins are key cellular components involved in the uptake, vacuolar/lysosomal sequestration, and efflux of these compounds; thus, deciphering the multilevel regulation of these proteins is of the utmost importance. In this review, we summarize data on the mechanisms of arsenic, antimony, and cadmium detoxification in the context of membrane proteome. We used yeast Saccharomyces cerevisiae as a eukaryotic model to elucidate the complex mechanisms of the production, regulation, and degradation of selected membrane transporters under metal(loid)-induced stress conditions. Additionally, we present data on orthologues membrane proteins involved in metal(loid)-associated diseases in humans.

Introduction: Nodulin-26-like intrinsic proteins (NIPs) are integral membrane proteins belonging to the aquaporin family, that facilitate the transport of neutral solutes across the bilayer. The OsNIP2;1 a member of NIP-III class of aquaporins is permeable to beneficial elements like silicon and hazardous arsenic. However, the atomistic cross-talk of these molecules traversing the OsNIP2;1 channel is not well understood., Objective: Due to the lack of genomic variation but the availability of high confidence crystal structure, this study aims to highlight structural determinants of metalloid permeation through OsNIP2;1., Methods: The molecular simulations, combined with site-directed mutagenesis were used to probe the role of specific residues in the metalloid transport activity of OsNIP2;1., Results: We drew energetic landscape of OsNIP2;1, for silicic and arsenous acid transport. Potential Mean Force (PMF) construction illuminate three prominent energetic barriers for metalloid passage through the pore. One corresponds to the extracellular molecular entry in the channel, the second located on ar/R filter, and the third size constriction in the cytoplasmic half. Comparative PMF for silicic acid and arsenous acid elucidate a higher barrier for silicic acid at the cytoplasmic constrict resulting in longer residence time for silicon. Furthermore, our simulation studies explained the importance of conserved residues in loop-C and loop-D with a direct effect on pore dynamics and metalloid transport. Next we assessed contribution of predicted key residues for arsenic uptake, by functional complementation in yeast. With the aim of reducing arsenic uptake while maintaining beneficial elements uptake, we identified novel OsNIP2;1 mutants with substantial reduction in arsenic uptake in yeast., Conclusion: We provide a comprehensive assessment of pore lining residues of OsNIP2;1 with respect to metalloid uptake. The findings will expand mechanistic understanding of aquaporin's metalloid selectivity and facilitate variant interpretation to develop novel alleles with preference for beneficial metalloid species and reducing hazardous ones., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Production and hosting by Elsevier B.V.)

Due to anthropogenic activities, environmental pollution of heavy metals/metalloids (HMs) has increased and received growing attention in recent decades. Plants growing in HM-contaminated soils have slower growth and development, resulting in lower agricultural yield. Exposure to HMs leads to the generation of free radicals (oxidative stress), which alters plant morpho-physiological and biochemical pathways at the cellular and tissue levels. Plants have evolved complex defense mechanisms to avoid or tolerate the toxic effects of HMs, including HMs absorption and accumulation in cell organelles, immobilization by forming complexes with organic chelates, extraction via numerous transporters, ion channels, signaling cascades, and transcription elements, among others. Nonetheless, these internal defensive mechanisms are insufficient to overcome HMs toxicity. Therefore, unveiling HMs adaptation and tolerance mechanisms is necessary for sustainable agriculture. Recent breakthroughs in cutting-edge approaches such as phytohormone and gasotransmitters application, nanotechnology, omics, and genetic engineering tools have identified molecular regulators linked to HMs tolerance, which may be applied to generate HMs-tolerant future plants. This review summarizes numerous systems that plants have adapted to resist HMs toxicity, such as physiological, biochemical, and molecular responses. Diverse adaptation strategies have also been comprehensively presented to advance plant resilience to HMs toxicity that could enable sustainable agricultural production., (© 2024 The Authors. Physiologia Plantarum published by John Wiley & Sons Ltd on behalf of Scandinavian Plant Physiology Society.)

Anthropogenic activities have dramatically accelerated the release of toxic metal(loid)s into soil and water, which can be subsequently accumulated in plants and animals, threatening biodiversity, human health, and food security. Compared to physical and chemical remediation, bioremediation of metal(loid)-polluted soil using plants and/or plant symbiotic fungi is usually low-cost and environmentally friendly. Mycorrhizal fungi and endophytic fungi are two major plant fungal symbionts. Mycorrhizal fungi can immobilize metal(loid)s via constitutive mechanisms, including intracellular sequestration with vacuoles and vesicles and extracellular immobilization by cell wall components and extracellular polymeric substances such as glomalin. Mycorrhizal fungi can improve the efficacy of phytoremediation by promoting plant symplast and apoplast pathways. Endophytic fungi also use constitutive cellular components to immobilize metal(loid)s and to reduce the accumulation of metal(loid)s in plants by modifying plant physiological status. However, a specific mechanism for the removal of methylmercury pollution was recently discovered in the endophytic fungi Metarhizium, which could be acquired from bacteria via horizontal gene transfer. In contrast to mycorrhizal fungi that are obligate biotrophs, some endophytic fungi, such as Metarhizium and Trichoderma, can be massively and cost-effectively produced, so they seem to be well-placed for remediation of metal(loid)-polluted soil on a large scale., (Copyright © 2024. Published by Elsevier Inc.)

Aquaporins can facilitate the passive movement of water, small polar molecules, and some ions. Here, we examined solute selectivity for the barley Nodulin 26-like Intrinsic Protein (HvNIP2;1) embedded in liposomes and examined through stopped-flow light scattering spectrophotometry and Xenopus laevis oocyte swelling assays. We found that HvNIP2;1 permeates water, boric and germanic acids, sucrose, and lactose but not d-glucose or d-fructose. Other saccharides, such as neutral (d-mannose, d-galactose, d-xylose, d-mannoheptaose) and charged (N-acetyl d-glucosamine, d-glucosamine, d-glucuronic acid) aldoses, disaccharides (cellobiose, gentiobiose, trehalose), trisaccharide raffinose, and urea, glycerol, and acyclic polyols, were permeated to a much lower extent. We observed apparent permeation of hydrated KCl and MgSO 4 ions, while CH 3 COONa and NaNO 3 permeated at significantly lower rates. Our experiments with boric acid and sucrose revealed no apparent interaction between solutes when permeated together, and AgNO 3 or H[AuCl 4 ] blocked the permeation of all solutes. Docking of sucrose in HvNIP2;1 and spinach water-selective SoPIP2;1 aquaporins revealed the structural basis for sucrose permeation in HvNIP2;1 but not in SoPIP2;1, and defined key residues interacting with this permeant. In a biological context, sucrose transport could constitute a novel element of plant saccharide-transporting machinery. Phylogenomic analyses of 164 Viridiplantae and 2993 Archaean, bacterial, fungal, and Metazoan aquaporins rationalized solute poly-selectivity in NIP3 sub-clade entries and suggested that they diversified from other sub-clades to acquire a unique specificity of saccharide transporters. Solute specificity definition in NIP aquaporins could inspire developing plants for food production., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Heavy metals and metalloids (HMs) contamination in the environment has heightened recently due to increasing global concern for food safety and human livability. Zinc (Zn2+ ) is an important nutrient required for the normal development of plants. It is an essential cofactor for the vital enzymes involved in various biological mechanisms of plants. Interestingly, Zn2+ has an additional role in the detoxification of HMs in plants due to its unique biochemical-mediating role in several soil and plant processes. During any exposure to high levels of HMs, the application of Zn2+ would confer greater plant resilience by decreasing oxidative stress, maintaining uptake of nutrients, photosynthesis productivity and optimising osmolytes concentration. Zn2+ also has an important role in ameliorating HMs toxicity by regulating metal uptake through the expression of certain metal transporter genes, targeted chelation and translocation from roots to shoots. This review examined the vital roles of Zn2+ and nano Zn in plants and described their involvement in alleviating HMs toxicity in plants. Moving forward, a broad understanding of uptake, transport, signalling and tolerance mechanisms of Zn2+ /zinc and its nanoparticles in alleviating HMs toxicity of plants will be the first step towards a wider incorporation of Zn2+ into agricultural practices.

The constant, ever-increasing antibiotic resistance crisis leads to the announcement of "urgent, novel antibiotics needed" by the World Health Organization. Our previous works showed a promising synergistic antibacterial activity of silver nitrate with potassium tellurite out of thousands of other metal/metalloid-based antibacterial combinations. The silver-tellurite combined treatment not only is more effective than common antibiotics but also prevents bacterial recovery, decreases the risk of future resistance chance, and decreases the effective concentrations. We demonstrate that the silver-tellurite combination is effective against clinical isolates. Further, this study was conducted to address knowledge gaps in the available data on the antibacterial mechanism of both silver and tellurite, as well as to give insight into how the mixture provides synergism as a combination. Here, we defined the differentially expressed gene profile of Pseudomonas aeruginosa under silver, tellurite, and silver-tellurite combination stress using an RNA sequencing approach to examine the global transcriptional changes in the challenged cultures grown in simulated wound fluid. The study was complemented with metabolomics and biochemistry assays. Both metal ions mainly affected four cellular processes, including sulfur homeostasis, reactive oxygen species response, energy pathways, and the bacterial cell membrane (for silver). Using a Caenorhabditis elegans animal model we showed silver-tellurite has reduced toxicity over individual metal/metalloid salts and provides increased antioxidant properties to the host. This work demonstrates that the addition of tellurite would improve the efficacy of silver in biomedical applications. IMPORTANCE Metals and/or metalloids could represent antimicrobial alternatives for industrial and clinical applications (e.g., surface coatings, livestock, and topical infection control) because of their great properties, such as good stability and long half-life. Silver is the most common antimicrobial metal, but resistance prevalence is high, and it can be toxic to the host above a certain concentration. We found that a silver-tellurite composition has antibacterial synergistic effect and that the combination is beneficial to the host. So, the efficacy and application of silver could increase by adding tellurite in the recommended concentration(s). We used different methods to evaluate the mechanism for how this combination can be so incredibly synergistic, leading to efficacy against antibiotic- and silver-resistant isolates. Our two main findings are that (i) both silver and tellurite mostly target the same pathways and (ii) the coapplication of silver with tellurite tends not to target new pathways but targets the same pathways with an amplified change., Competing Interests: The authors declare no conflict of interest. Pormohammad A, Turner RJ. February 23, 2022. US Patent No. 63/312,861 filed with WIPO international. PCT/IB2023/051621, Metal(loid)-based compositions and uses thereof against bacterial biofilms.

Soil contamination with trace metals and metalloids can cause toxicity to plants and threaten food safety and human health. Plants have evolved sophisticated mechanisms to cope with excess trace metals and metalloids in soils, including chelation and vacuolar sequestration. Sulfur-containing compounds, such as glutathione and phytochelatins, play a crucial role in their detoxification, and sulfur uptake and assimilation are regulated in response to the stress of toxic trace metals and metalloids. This review focuses on the multi-level connections between sulfur homeostasis in plants and responses to such stresses, especially those imposed by arsenic and cadmium. We consider recent progress in understanding the regulation of biosynthesis of glutathione and phytochelatins and of the sensing mechanism of sulfur homeostasis for tolerance of trace metals and metalloids in plants. We also discuss the roles of glutathione and phytochelatins in controlling the accumulation and distribution of arsenic and cadmium in plants, and possible strategies for manipulating sulfur metabolism to limit their accumulation in food crops., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Plants take up a wide range of trace metals/metalloids (hereinafter referred to as trace metals) from the soil, some of which are essential but become toxic at high concentrations (e.g., Cu, Zn, Ni, Co), while others are non-essential and toxic even at relatively low concentrations (e.g., As, Cd, Cr, Pb, and Hg). Soil contamination of trace metals is an increasing problem worldwide due to intensifying human activities. Trace metal contamination can cause toxicity and growth inhibition in plants, as well as accumulation in the edible parts to levels that threatens food safety and human health. Understanding the mechanisms of trace metal toxicity and how plants respond to trace metal stress is important for improving plant growth and food safety in contaminated soils. The accumulation of excess trace metals in plants can cause oxidative stress, genotoxicity, programmed cell death, and disturbance in multiple physiological processes. Plants have evolved various strategies to detoxify trace metals through cell-wall binding, complexation, vacuolar sequestration, efflux, and translocation. Multiple signal transduction pathways and regulatory responses are involved in plants challenged with trace metal stresses. In this review, we discuss the recent progress in understanding the molecular mechanisms involved in trace metal toxicity, detoxification, and regulation, as well as strategies to enhance plant resistance to trace metal stresses and reduce toxic metal accumulation in food crops., (© 2022 Institute of Botany, Chinese Academy of Sciences.)

Methylarsenite [MAs(III)] is a highly toxic arsenical produced by some microbes as an antibiotic. In this study, we demonstrate that a PadR family transcriptional regulator, PadR ars , from Azospirillum halopraeferens strain Au 4 directly binds to the promoter region of the arsenic resistance (ars) operon (consisting of padR ars , arsV, and arsW) and represses transcription of arsV and arsW genes involved in MAs(III) resistance. Quantitative reverse transcriptase PCR and transcriptional reporter assays showed that transcription of the ars operon is induced strongly by MAs(III) and less strongly by arsenite and antimonite. Electrophoretic mobility shift assays with recombinant PadR ars showed that it represses transcription of the ars operon by binding to two inverted-repeat sequences within the ars promoter. PadR ars has two conserved cysteine pairs, Cys56/57 and Cys133/134; mutation of the first pair to serine abolished the transcriptional response of the ars operon to trivalent metalloids, suggesting that Cys56/57 form a binding site for trivalent metalloids. Either C133S or C134S derivative responses to MAs(III) but not As(III) or Sb(III), suggesting that it is a third ligand to trivalent metalloids. PadR ars represents a new type of repressor proteins regulating transcription of an ars operon involved in the resistance to trivalent metalloids, especially MAs(III)., (© 2022 Society for Applied Microbiology and John Wiley & Sons Ltd.)

Heavy metal/metalloids (HMs) are among the primary soil pollutants that limit crop production worldwide. Plants grown in HM contaminated soils exhibit reduced growth and development, resulting in a decrease in crop production. The exposure to HMs induces plant oxidative stress due to the formation of free radicals, which alter plant morphophysiological and biochemical mechanisms at cellular and tissue levels. When exposed to HM toxicity, plants evolve sophisticated physiological and cellular defense strategies, such as sequestration and transportation of metals, to ensure their survival. Plants also have developed efficient strategies by activating signaling pathways, which induce the expression of HM transporters. Plants either avoid the uptake of HMs from the soil or activate the detoxifying mechanism to tolerate HM stress, which involves the production of antioxidants (enzymatic and non-enzymatic) for the scavenging of reactive oxygen species. The metal-binding proteins including phytochelatins and metallothioneins also participate in metal detoxification. Furthermore, phytohormones and their signaling pathways also help to regulate cellular activities to counteract HM stress. The excessive levels of HMs in the soil can contribute to plant morpho-physiological, biochemical, and molecular alterations, which have a detrimental effect on the quality and productivity of crops. To maintain the commercial value of fruits and vegetables, various measures should be considered to remove HMs from the metal-polluted soils. Bioremediation is a promising approach that involves the use of tolerant microorganisms and plants to manage HMs pollution. The understanding of HM toxicity, signaling pathways, and tolerance mechanisms will facilitate the development of new crop varieties that help in improving phytoremediation., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Metalloids in plants have diverse physiological effects. From being essential to beneficial to toxic, they have significant effects on many physiological processes, influencing crop yield and quality. Aquaporins are a group of membrane channels that have several physiological substrates along with water. Metalloids have emerged as one of their important substrates and they are found to have a substantial role in regulating plant metalloid homeostasis. The present review comprehensively details the multiple isoforms of aquaporins having specificity for metalloids and being responsible for their influx, distribution or efflux. In addition, it also highlights the usage of aquaporin-mediated transport as a selection marker in toxic screens and as tracer elements for closely related metalloids. Therefore, aquaporins, with their imperative contribution to the regulation of plant growth, development and physiological processes, need more research to unravel the metalloid trafficking mechanisms and their future applications., (© 2022 Scandinavian Plant Physiology Society.)

Siderophores are small molecular weight iron scavengers that are mainly produced by bacteria, fungi, and plants. Recently, they have attracted increasing attention because of their potential role in environmental bioremediation. Although siderophores are generally considered to exhibit high specificity for iron, they have also been reported to bind to various metal and metalloid ions. This unique ability allows siderophores to solubilise and mobilise heavy metals and metalloids from soil, thereby facilitating their bioremediation. In addition, because of their redox nature, they can mediate the production of reactive oxygen species (ROS), and thus promote the biodegradation of organic contaminants. The aim of this review is to summarise the existing knowledge on the developed strategies of siderophore-assisted bioremediation of metals, metalloids, and organic contaminants. Additionally, this review also includes the biosynthesis and classification of microbial and plant siderophores., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

With the introduction of tandem mass spectrometry to inductively coupled plasma mass spectrometry (ICPMS/MS), the potential for non-targeted elemental metabolomic analysis has been expanded to many non-metals of pivotal biological importance. Arsenic and selenium are trace elements that share chemical similarity with the non-metals phosphorus and sulfur, respectively, and this similarity can be exploited to gain more insight into the incompletely understood biological significance of these metalloids and the evolution of their biochemical pathways. As a proof of concept, we show the applicability of HPLC-ICPMS/MS for non-targeted and parallel speciation analysis of arsenic, selenium, phosphorus, and sulfur in mushrooms-metabolically diverse organisms. Incredibly contrasting levels of diversity were found in the metabolomic profiles of the four investigated elements among the various species along with sharp discrepancies among related elements (e.g. phosphorous vs. arsenic) in certain mushroom species. The present work shows that ICPMS/MS offers a new dimension in non-targeted metabolomic analysis and enables a unique comparative approach in investigating and tracking the biochemistry of related elements in moderately complex organisms., (© The Author(s) 2021. Published by Oxford University Press.)

Metals and metalloids are integral to biological processes and play key roles in physiology and metabolism. Nonetheless, overexposure to some metals or lack of others can lead to serious health consequences. In this study, eight zebrafish facilities collaborated to generate a multielement analysis of their centralized recirculating water systems. We report a first set of average concentrations for 46 elements detected in zebrafish facilities. Our results help to establish an initial baseline for trouble-shooting purposes, and in general for safe ranges of metal concentrations in recirculating water systems, supporting reproducible scientific research outcomes with zebrafish.

Background: Exposure to metals/metalloids, including essential and nonessential elements, has been associated to male reproductive health in animals. However, findings from human studies are inconsistent., Objectives: To investigate the impact of exposure to multiple metals/metalloids at environmental levels on the conventional human semen-quality parameters., Materials and Methods: Men living in rural or industrial areas were recruited by personalized letters. No exclusion criteria were applied. Each man provided one semen sample and one blood sample. We analyzed the semen sample both to determine conventional sperm parameters (concentration, progressive motility and normal forms) and to quantify lead (Pb), cadmium (Cd), mercury (Hg), arsenic (As), nickel (Ni), vanadium (V) and selenium (Se) levels. The levels of these metals/metalloids were also quantified in venous blood and spermatozoa samples. Associations between the blood/seminal plasma metal/metalloid levels and semen quality parameters were assessed using confounder adjusted logistic regression models. Correlation and interactions between blood/seminal plasma and semen metal/metalloid levels were investigated using the Spearman's correlation., Results: We found a positive association of seminal plasma cadmium level with lower Total count (OR = 4.48, 95%CI 0.25-80); whereas lead (OR = 4.51, 95%CI 0.86-23) and cadmium (OR = 3.45, 95%CI 0.77-16) seminal plasma levels had a positive association with progressive sperm motility. Overall, these associations remained suggestive after adjustment, though statistically unstable risks. Finally, we found weak interactions between beneficial effects of Se and detrimental ones only for Cd and Pb blood level on sperm concentration, total sperm count and progressive sperm motility., Conclusions: Our findings suggest that environmental exposure to Pb and Cd contributes to a decline in human semen quality, whereas Se can have beneficial effects. Measurements of metals/metalloids in the seminal fluid may be more predictable of semen quality than conventional blood measurements., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

The intensive shift on land cover by anthropogenic activities have led to changes in natural habitats and environmental contamination, which can ultimately impact and threat biodiversity and ecosystem services, such as pollination. The aim of this study was to evaluate the effect of native forest and human-modified land covers on the concentrations of chemical elements accumulated in the neotropical pollinator bee T. angustula. Eight landscapes, within an Ecological Corridor in the State of São Paulo, Brazil, with gradients of forest cover, spatial heterogeneity and varying land covers were used as sampling unities. Bees collected in traps or through actives searches had the concentration of 21 chemical elements determined by ICP-MS. Results show a beneficial effect of forested areas on the concentrations of some well-known toxic elements accumulated in bees, such as Hg, Cd, and Cr. Multivariate Redundancy Analysis (RDA) suggests road as the most important driver for the levels of Cr, Hg, Sb, Al, U, As, Pb and Pt and bare soil, pasture and urban areas as the landscape covers responsible for the concentrations of Zn, Cd, Mn, Mg, Ba and Sr in bees. The results reinforce the potential use of T. angustula bees as bioindicators of environmental quality and also show that these organisms are being directly affected by human land use, offering potential risks for the Neotropical ecosystem. Our study sheds light on how land covers (native forest and human-modified) can influence the levels of contaminants in insects within human-dominated landscapes. The generation of predictions of the levels of toxic metals and metalloids based on land use can both contribute to friendly farming planning as well as to support public policy development on the surrounding of protected areas and biodiversity conservation hotspots., (Copyright © 2021. Published by Elsevier Inc.)

In San Luis Potosí, Mexico, the exploitation of minerals has historically been carried out as an activity that has left in its path environmental liabilities, with high concentrations of heavy metals. These metals have undergone weathering by rain and wind and have moved closer to inhabited locations as is the case of Cerro de San Pedro (CSP) and Villa de la Paz (VDP). The objective of this study is to show the biological alteration of soils due to the presence of heavy metals and metalloids like Cadmium (Cd), Copper (Cu), Lead (Pb) and Arsenic (As) and to find the relationship between contamination and risk indexes. Soil samples were obtained from sites with historical records of mining activity and their surroundings. Several analyses were performed, such as pH levels, organic matter, electrical conductivity, clays, heavy metals and As. Moreover, Community Level Physiological profiling (CLPP) were conducted. The obtained evidence showed high levels of contamination by As and heavy metals in both sites (CSP: 6485.1 mg/Kg of Pb and pH of 4.4; VDP: 7188.2 mg/Kg of As and pH of 7.8). According to the Metal Pollution Index (MPI), 607.0 in CSP and 1050.5 in VDP, presented a high environmental risk, apart from, risk to human health (SQGQI) 35.8 in CSP and 131.5 in VDP. At the same time, CLPPs showed that microbiological communities were selective in taking up substrate groups, in the following order: Carbohydrates > Polymers > Carboxylic acids > Amino acids > Amines/Amides. However, a positive correlation in CSP was only found between both indexes and Amines/Amides (r = 0.46, p < 0.05), and in VDP the D-Galactonic acid-γ-Lactone with the MPI (r = 0.49, p < 0.05), and with the SQGQI (r = 0.45, p < 0.05). Although this behavior was not homogeneous, it was possible to find negative correlations between both indexes and the AWCD with other substrates, influenced by the physicochemical characteristics presented in each studied site. Consequently, according to our findings, a combined effect between the physicochemical characteristics, As, and heavy metals took place, on the metabolic activity, causing alterations to soil functions., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

The Tablas de Daimiel National Park (TDNP) is a floodplain ecosystem in central Spain with a potential risk of heavy metal and metalloid pollution. The objective of this study was to know the accumulation of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), and selenium (Se) in muscle of six species of freshwater fish from the floodplain of TDNP. We obtained muscle samples of Cyprinus carpio (n = 89); Squalius pyrenaicus (n = 16); Ameiurus melas (n = 9); Lepomis gibbosus (n = 8); Micropterus salmoides (n = 6) and Carassius auratus (n = 5). A. melas, which is a predatory species, had significantly higher Hg concentrations than omnivorous or herbivorous species (i.e. C. carpio). On the contrary, A. melas showed lower concentrations of As, Pb and Se than omnivorous species (i.e. S. pyrenaicus and L. gibbosus ). The concentration of Hg was positively associated with fish size in C. carpio and A. melas. Some individuals of C. carpio (5.7%) and S. pyrenaicus (12.5%) showed Pb muscle concentrations above the maximum residue levels established by the European legislation for human consumers. The observed muscle Se concentrations can be associated with adverse effects on fish such as blood changes, reduced growth, mortality of juveniles and reproductive failure. The accumulation of Se in this floodplain located in a seleniferous area and the contamination produced by spent Pb shot pellets used for hunting in the past are discussed as potential sources of the elevated levels of these two elements in fish from this floodplain wetland., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Metal(loid) pollution of soils has important negative effects on the environment and human health. For the rehabilitation of these soils, some eco-innovative strategies, such as phytoremediation, could be chosen. This practice could establish a plant cover to reduce the toxicity of the pollutants and stabilize the soil, preventing soil erosion and water leaching; this technique is called phytoremediation. For this, plants need to be tolerant to the pollutants present; thus, phytoremediation can have better outcomes if endemic species of the polluted area are used. Finally, to further improve phytoremediation success, amendments can be applied to ameliorate soil conditions. Different amendments can be used, such as biochar, a good metal(loid) immobilizer, compost, a nutrient-rich product and iron sulfate, an efficient arsenic immobilizer. These amendments can either be applied alone or combined for further positive effects. In this context, a mesocosm experiment was performed to study the effects of three amendments, biochar, compost and iron sulfate, applied alone or combined to a former mine technosol, on the soil properties and the phytoremediation potential of two endemic species, Alnus sp. and Betula sp. Results showed that the different amendments reduced soil acidity and decreased metal(loid) mobility, thus improving plant growth. Both species were able to grow on the amended technosols, but alder seedlings had a much higher growth compared to birch seedlings. Finally, the combination of compost with biochar and/or iron sulfate and the establishment of endemic alder plants could be a solution to rehabilitate a former mine technosol.

Covering: up to 2019 Siderophores are natural products which have attracted interest due to their ability to bind metal ions with high affinities. This review considers the complex formation of these natural chelators with all kinds of different metal and metalloid ions and links their chelating properties to potential biotechnological applications and towards environmental context.

Remediation of metal(loid) polluted soils is an important area of research nowadays. In particular, one remediation technique is much studied, phytomanagement. Phytomanagement combines amendment application and plant growth in order to reduce the risk posed by contaminants. Salicaceae plants showed tolerance towards metal(loid)s and the ability to accumulate high amounts of metal(loid)s in their tissue. Amendments are often applied to counterbalance the reduced soil fertility and high metal(loid) concentrations. Two amendments gathered attention over the last decades, biochar (product of biomass pyrolysis), which can be activated for better effects, and redmud (by-product of alumina production). Those two amendments showed ability to improve soil conditions and thus plant growth, although few studied their combined application. Moreover, since metal(loid)s are known to induce the overproduction of reactive oxygen species, it is important to measure the level of oxidative stress in the plant, to which plants respond using enzymatic and non-enzymatic systems. But no studies evaluate the response of Salicaceae plants to metal(loid) stress and amendment application at the biochemical level in a real soil condition. Therefore, a mesocosm study was set up to evaluate the effect of amending a mine soil with redmud combined to diverse biochars on the soil properties and Salix triandra growth, metal(loid) accumulation and stress marker levels. Results showed that all amendment combinations improved the soil fertility, reduced metal(loid) mobility and thus ameliorated Salix triandra growth, which accumulated metal(loid)s mainly in its roots. Moreover, among the different amendment combinations, Salix triandra plants still suffered from oxidative stress when grown on PG soil amended with redmud and chemical activated carbon, showing elevated levels of phenolic compounds and salicinoids and important antioxidant and enzymatic activities. Finally, one treatment showed levels of these stress markers similar or lower than the control, the combination of redmud with steam activated carbon. In conclusion, this treatment seemed a good solution in a phytomanagement strategy using Salix triandra, improving soil conditions and plant growth and reducing oxidative stress level in the plant roots., Competing Interests: Declaration of competing interest ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2020 Elsevier Inc. All rights reserved.)

Nodulin 26-like intrinsic proteins (NIPs) play essential roles in transporting the nutrients silicon and boron in seed plants, but the evolutionary origin of this transport function and the co-permeability to toxic arsenic remains enigmatic. Horizontal gene transfer of a yet uncharacterised bacterial AqpN-aquaporin group was the starting-point for plant NIP evolution. We combined intense sequence, phylogenetic and genetic context analyses and a mutational approach with various transport assays in oocytes and plants to resolve the transorganismal and functional evolution of bacterial and algal and terrestrial plant NIPs and to reveal their molecular transport specificity features. We discovered that aqpN genes are prevalently located in arsenic resistance operons of various prokaryotic phyla. We provided genetic and functional evidence that these proteins contribute to the arsenic detoxification machinery. We identified NIPs with the ancestral bacterial AqpN selectivity filter composition in algae, liverworts, moss, hornworts and ferns and demonstrated that these archetype plant NIPs and their prokaryotic progenitors are almost impermeable to water and silicon but transport arsenic and boron. With a mutational approach, we demonstrated that during evolution, ancestral NIP selectivity shifted to allow subfunctionalisations. Together, our data provided evidence that evolution converted bacterial arsenic efflux channels into essential seed plant nutrient transporters., (© 2019 The Authors. New Phytologist © 2019 New Phytologist Trust.)

There is a growing conservation concern about the possible consequences of environmental contamination in the health of bat communities. Most studies on the effects of contaminants in bats have been focused on organic contaminants, and the consequences of bat exposure to metals and metalloids remain largely unknown. The aim of this study was to evaluate the suitability of external biological matrices (fur and wing membrane) for the assessment of exposure and bioaccumulation of metals in bats. The concentration of arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead, selenium and zinc was measured in internal organs (liver, heart, brain), internal (bone) and external tissues (wing membrane, fur) collected from bat carcasses of four species (Hypsugo savii, Nyctalus leisleri, Pipistrellus pipistrellus, Pipistrellus pygmaeus) obtained in windfarm mortality searches. With the exception of zinc (P = 0.223), the results showed significant differences between the concentrations of metals in the analyzed tissues for all metals (P < 0.05). Significant differences were also found between organs/tissues (P < 0.001), metals (P < 0.001) and a significant interaction between organs/tissues and metals was found (P < 0.001). Despite these results, the patterns in terms of metal accumulation were similar for all samples. Depending on the metal, the organ/tissue that showed the highest concentrations varied, but fur and wing had the highest concentrations for most metals. The variability obtained in terms of metal concentrations in different tissues highlights the need to define standardized methods capable of being applied in monitoring bat populations worldwide. The results indicate that wing membrane and fur, biological matrices that may be collected from living bats, yield reliable results and may be useful for studies on bats ecotoxicology, coupled to a standardized protocol for large-scale investigation of metal accumulation., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Little is known about the effects of applying amendments on soil for immobilizing metal(loid)s on the soil microbial community. Alterations in the microbial community were examined after incubation of treated contaminated soils. One soil was contaminated with Pb and As, a second soil with Cd and Zn. Red pepper stalk (RPS) and biochars produced from RPS in either N 2 atmosphere (RPS N ) or CO 2 atmosphere (RPS C ) were applied at a rate of 2.5% to the two soils and incubated for 30 days. Bacterial communities of control and treated soils were characterized by sequencing 16S rRNA genes using the Illumina MiSeq sequencing. In both soils, bacterial richness increased in the amended soils, though somewhat differently between the treatments. Evenness values decreased significantly, and the final overall diversities were reduced. The neutralization of pH, reduced available concentrations of Pb or Cd, and supplementation of available carbon and surface area could be possible factors affecting the community changes. Biochar amendments caused the soil bacterial communities to become more similar than those in the not amended soils. The bacterial community structures at the phylum and genus levels showed that amendment addition might restore the normal bacterial community of soils, and cause soil bacterial communities in contaminated soils to normalize and stabilize., (Copyright © 2019. Published by Elsevier Ltd.)

The industrialization and growth of human population has increased the release and accumulation of metals and metalloids in the environment. Bioaccumulation and exposure to these elements have been associated with different types of diseases and cancer, thus looking for alternatives that decrease their bioavailability in the environment is crucial. Microbiologically induced carbonates precipitation (MICP) has been proposed as a potential bioremediation method to immobilize contaminating metals and metalloids. Studies published to date have mainly used ureolytic bacteria, reporting metal(loid)s removal percentages up to 100% for some toxic elements, thus demonstrating the effectiveness of this treatment. Various genera of bacteria, particularly Gram-positive, have been reported with MICP abilities. More recently, fungi have also been proposed as a viable alternative for the removal of these toxic elements by carbonate precipitation. This mini-review presents updated information about the main studies carried out to date using different types of microorganisms that perform MICP to decrease the environmental bioavailability of toxic metals and metalloids through the formation of metallic carbonates.

The transfer of metal and metalloid trace elements (MTEs) from contaminated soil to grapevines is a major issue for grape consumption and for the associated health risks. Based on an isotopic approach, we shed light on the concept of MTE bioavailability. The bioavailable fractions are identified by using the Sr-isotope ratio as a proxy for MTEs. This allows us to differentiate three soil reservoirs: the 'current available fraction' in soil water, the 'reserve available fraction' stored in mineral phases of the soil fractions, and the 'non-available fraction'. The reserve available fraction, representing 10 to 60% of bulk soil depending on the MTE, includes the exchangeable, carbonates, humic substance and oxides fractions. The 87 Sr/ 86 Sr isotopic signatures of grape berries and vine leaves show an additional source of MTEs, which is imported by foliar uptake and can contribute up to 10% of the MTEs in leaves. In addition, root-uptake and translocation rates show high accumulation rates of Co, Sn and Cu, and low ones for As, Sb, Zn and Cd. A daily intake between 1 and 3 kg of (dry grapes) would reach the benchmark dose level for a 0.5% (BMDL 0.5 ). While such a daily intake of grapes is unreasonable, consumption of other local vegetables and fruit would contribute to the daily intake. Hence, a chronic arsenic exposure is of great concern for human health in mining areas. We outline the importance of geochemical tracers, such as Sr isotopes, when determining the transfer and translocation of MTEs in plants. Our method presents a high-precision evaluation of the bioavailability and bioaccumulation of MTEs, and a better understanding of these processes in plants, thus leading to a better assessment of the environmental risk on human health., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study assesses the sediment quality of the Guadalquivir River watercourse between the Alcalá del Río dam and the city of Seville. The main objective of this work is to address sediment quality in the area using an integrative approach that links sediment contamination and toxicity using the Asiatic clam (Corbicula fluminea) under field conditions. This is the first study conducted in the area that use of a battery of biomarkers from exposure (GST, GPx) to adverse biological effect (DNA and histopathological damage) to identify the contamination adverse effects in a river area affected by a cocktail of different anthropogenic activities (urban, industrial, agricultural, etc.). The sediment quality characterized in the area shows a significant biological stress related to metal(loid)s at station located in Alcalá del Río in the river upper part of the studied area, being this stress toxic when approaching the city of Seville. The sediments located nearby this city showed toxicity by means of positive values in the biomarkers of effects measured in the caged clams and related to contaminants with an industrial and urban discharge origins. These results have shown the useful and strength of the biomarker approach used in this study that combines biomarker responses from exposure to effects and allows identifying the contamination adverse effects by means of using caging individuals of the Asian clam. It has been proved in the different experiments how once the exposure biomarkers reach a maximum value of their system the detoxification ability of the organisms is collapsed and then the biomarkers of effect are measured significantly in the different tissues. The use of field surveys using tolerant specie such as the Asian clam is recommendable to determine sediment quality under an integrative point of view as here reported., (Copyright © 2018 Elsevier B.V. All rights reserved.)

We addressed the hypothesis that birds in eutrophic wetlands receiving wastewater treatment plant (WWTP) effluents are exposed to high levels of metals and metalloids and this may drive an ecological trap in some species attracted to these highly productive ecosystems. Levels of metals and metalloids were determined in sediment and in blood and feathers of common moorhens (Gallinula chloropus) from two wetlands in Central Spain: Navaseca Pond, which receives directly the effluent of a WWTP; and Tablas de Daimiel National Park, which is a floodplain less affected by urban discharges. Sediment concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb were higher in Navaseca Pond than in Tablas de Daimiel; only Se was higher in Tablas de Daimiel than in Navaseca. Blood levels of Hg and Se were higher in moorhens from Tablas de Daimiel than those from Navaseca. In the case of Hg these levels were below the threshold of adverse effect, but Se levels in 24% of moorhens from Tablas de Daimiel were above the threshold value associated with Se toxicity in birds (1000 ng/mL). In feathers, Hg, Se, Mn, Cu and As levels were higher in Tablas de Daimiel than in Navaseca. Body condition of moorhens was negatively associated with blood Se levels in the moorhens from Tablas de Daimiel. We can reject the hypothesis of a higher accumulation of metals and metalloids in birds associated with the WWTP effluent, but Se levels may need further research considering the nature of the floodplain of Tablas de Daimiel National Park., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Physical systems, such as currents and winds, have traditionally been considered responsible for transporting contaminants. Although evidence is mounting that animals play a role in this process through their movements, we still know little about how such contaminant biotransport occurs and the extent of effects at deposition sites. In the present study, we address this question by studying how rhinoceros auklets (Cerorhinca monocerata), a seabird that occurs in immense colonies (∼300 000 pairs at our study site, Teuri Island), affect contaminant levels at their colony and at nearby sites. More specifically, we hypothesize that contaminants are transported and deposited by seabirds at their colony and that these contaminants are passed on locally to the terrestrial ecosystem. To test this hypothesis, we analyzed the concentration of 9 heavy metal and metalloids, as well as δ 13 C and δ 15 N stable isotopes, in bird tissues, plants, and soil, both within and outside of the colony. The results show that rhinoceros auklets transport marine-derived mercury (Hg), possibly from their wintering location, and deposit Hg via their feces at their breeding site, thereby contaminating plants and soils within the breeding colony. The present study confirms not only that animals can transport contaminants from marine to terrestrial ecosystems, potentially over unexpectedly long distances, but also that bird tissues contribute locally to plant contamination. Environ Toxicol Chem 2019;38:106-114. © 2018 SETAC., (© 2018 SETAC.)

The Actinobacterium Gordonia rubripertincta CWB2 (DSM 46758) produces hydroxamate-type siderophores (188 mg L -1 ) under iron limitation. Analytical reversed-phase HPLC allowed determining a single peak of ferric iron chelating compounds from culture broth which was confirmed by the Fe-CAS assay. Elution profile and its absorbance spectrum were similar to those of commercial (des)ferrioxamine B which was used as reference compound. This confirms previously made assumptions and shows for the first time that the genus Gordonia produces desferrioxamine-like siderophores. The reversed-phase HPLC protocol was optimized to separate metal-free and -loaded oxamines. This allowed to determine siderophore concentrations in solutions as well as metal affinity. The metal loading of oxamines was confirmed by ICP-MS. As a result, it was demonstrated that desferrioxamine prefers trivalent metal ions (Fe 3+  > Ga 3+  > V 3+  > Al 3+ ) over divalent ones. In addition, we aimed to show the applicability of the newly established reversed-phase HPLC protocol and to increase the re-usability of desferrioxamines as metal chelators by immobilization on mesocellular silica foam carriers. The siderophores obtained from strain CWB2 and commercial desferrioxamine B were successfully linked to the carrier with a high yield (up to 95%) which was verified by the HPLC method. Metal binding studies demonstrated that metals can be bound to non-immobilized and to the covalently linked desferrioxamines, but also to the carrier material itself. The latter was found to be unspecific and, therefore, the effect of the carrier material remains a field of future research. By means of a reversed CAS assay for various elements (Nd, Gd, La, Er, Al, Ga, V, Au, Fe, As) it was possible to demonstrate improved Ga 3+ - and Nd 3+ -binding to desferrioxamine loaded mesoporous silica carriers. The combination of the robust reversed-phase HPLC method and various CAS assays provides new avenues to screen for siderophore producing strains, and to control purification and immobilization of siderophores., (Copyright © 2018 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.)

To provide information on reclamation of multi-heavy metal polluted soils with conception of phytostabilization, a field survey on the uptake and accumulation of potentially toxic elements such as antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) in colonized plant species around the world's largest antimony mine area, China, was conducted. Samples including leaves and shoots (including roots and stems) of colonized plants as well as rhizospheric soils were collected from eight sampling zones in the studied area. The results showed that the contents of Cu, Zn, and Pb in rhizospheric soils below plants were comparable to the corresponding background values of Hunan province, otherwise Sb, Cd, and As contents were extremely high (17-106, 17-87, and 3-7 times of the corresponding background values). The highest concentration of Sb was found in Aster subulatus (410 mg kg -1 ); Cd, As, and Zn were in Herba bidentis bipinnatae (10.9, 264, and 265 mg kg -1 , respectively); and Cu was in Artemisia lavandulaefolia (27.1 mg kg -1 ). It also exhibited that all the contents of As in leaves were several times of those in shoots of plants, Cd and other heavy metals showed in a similar pattern in several studied species, implying that the uptake route of these heavy metals via foliar might contribute to the accumulation. With high bioconcentration factors of heavy metals (more than 1, except for Zn), together with the growth abundance, Herba bidentis bipinnatae was considered as the most suitable colonized species for phytostabilization of the multi-heavy metal pollution in soils on this antimony mine area.

In the last 15 years, the exploitation of biological systems (i.e. plants, bacteria, mycelial fungi, yeasts, and algae) to produce metal(loid) (Me)-based nanomaterials has been evaluated as eco-friendly and a cost-effective alternative to the chemical synthesis processes. Although the biological mechanisms of biogenic Me-nanomaterial (Bio-Me-nanomaterials) production are not yet completely elucidated, a key advantage of such bio-nanostructures over those chemically synthesized is related to their natural thermodynamic stability, with several studies ascribed to the presence of an organic layer surrounding these Bio-Me-nanostructures. Different macromolecules (e.g. proteins, peptides, lipids, DNA, and polysaccharides) or secondary metabolites (e.g. flavonoids, terpenoids, glycosides, organic acids, and alkaloids) naturally produced by organisms have been indicated as main contributors to the stabilization of Bio-Me-nanostructures. Nevertheless, the chemical-physical mechanisms behind the ability of these molecules in providing stability to Bio-Me-nanomaterials are unknown. In this context, transposing the stabilization theory of chemically synthesized Me-nanomaterials (Ch-Me-nanomaterials) to biogenic materials can be used towards a better comprehension of macromolecules and secondary metabolites role as stabilizing agents of Bio-Me-nanomaterials. According to this theory, nanomaterials are generally featured by high thermodynamic instability in suspension, due to their high surface area and surface energy. This feature leads to the necessity to stabilize chemical nanostructures, even during or directly after their synthesis, through the development of (i) electrostatic, (ii) steric, or (iii) electrosteric interactions occurring between molecules and nanomaterials in suspension. Based on these three mechanisms, this review is focused on parallels between the stabilization of biogenic or chemical nanomaterials, suggesting which chemical-physical mechanisms may be involved in the natural stability of Bio-Me-nanomaterials. As a result, macromolecules such as DNA, polyphosphates and proteins may electrostatically interact with Bio-Me-nanomaterials in suspension through their charged moieties, showing the same properties of counterions in Ch-Me-nanostructure suspensions. Since several biomolecules (e.g. neutral lipids, nonionic biosurfactants, polysaccharides, and secondary metabolites) produced by metal(loid)-grown organisms can develop similar steric hindrance as compared to nonionic amphiphilic surfactants and block co-polymers generally used to sterically stabilize Ch-Me-nanomaterials. These biomolecules, most likely, are involved in the development of steric stabilization, because of their bulky structures. Finally, charged lipids and polysaccharides, ionic biosurfactants or proteins with amphiphilic properties can exert a dual effect (i.e. electrostatic and steric repulsion interactions) in the contest of Bio-Me-nanomaterials, leading to the high degree of stability observed.

An integrated approach to the investigation of potentially toxic elements (PTEs) was applied to the soil and grapevine leaf samples collected from vineyard environment through the grapevine season. To investigate mobile and bioavailable concentrations of PTEs, six single extraction procedures and pseudo-total digestion were applied to the samples. The element concentrations in the samples were measured using inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS). To assess atmospheric particle deposition, saturation isothermal remanent magnetisation (SIRM) was applied to the leaf samples. The obtained PTE concentrations in samples were used for calculating various ecological implications in the vineyard environment. The notable environmental pollution implications were estimated for As, B, Cd, Co, Cr, Cu, Mn, Ni and Sr. The environmental risk (RI) of the elements soluble under low-acid conditions influenced soil bioavailability risk. The most bioavailable elements from soil to leaves were Mn, Ni and Sr, followed by Cr and Cu. Cadmium and Co were strongly-bonded in the soil and were not bioavailable. The most suitable extractants for assessing bioavailability in the soil-leaf system were chelating agent Na 2 EDTA, and weak salt solutions CaCl 2 and NH 4 NO 3 . The biological accumulation concentrations (BACs) of B, Ba, Cd, Co, Ni and Zn were decreasing in the leaves through the grapevine growing phases, that is contributed to the decreasing agrochemical application through the season. The BACs of Co, Cr, Sb and Pb, in July (veraison), were higher than in other phases, which indicate anthropogenic activities. According to correlations between biogeochemical index (BGI) and BAC, Cu and Na were mostly bioaccumulated from soil to leaves due to agrochemical applications, while bioaccumulation of B, Cd, Sb and Sr could be influenced by the other anthropogenic sources. Significant correlations between PTE concentrations and SIRM imply that leaves indicate Co, Cr and Ni air pollution in the vineyard environment., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Metal/metalloid accumulation in fish organs elicits biochemical responses indicating the overall fish and environmental health status. This study evaluated the bioaccumulation of metals and metalloid in relation to a suite of biochemical biomarkers (superoxide dismutase, catalase, glutathione-S-transferase, Na+/K+-ATPase, H+-ATPase, acetylcholinesterase activities and the levels of glutathione, metallothionein, lipid peroxidation and oxidized protein) in different organs of fish, Centropomus parallelus, in Vitória Bay and Santa Cruz estuaries (State of Espírito Santo, Brazil) with distinct contamination levels. Metal and metalloid concentrations differ in each organ and were significantly higher in winter than in summer. Chemometric evaluation performed between metal/metalloid accumulation and the biomarkers revealed a complex scenario in which the biomarker responses depend on both metal accumulation and organ/tissue sensitivity. The metal levels in gills indicate fish contamination mainly via water and the low sensitivity of this organ to most metals. Biomarker responses suggested that the metal elimination pathway is through the gills and kidney. The hepatopancreas and kidneys were the most important detoxification organs while muscle was the less reactive tissue. In general, the finding suggested that, C. parallelus is partly able to tolerate such metal contamination. However, it is emphasized that the biomarker responses imply an energetic cost and may affect the growth rate and reproduction. Given the ecological and economic importance of C. parallelus, the level of toxic metals/metalloids in juvenile fish is an important early-warning for the maintenance, conservation and commercial use of this species., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The genetic engineering of plants to facilitate the reclamation of soils and waters contaminated with inorganic pollutants is a relatively new and evolving field, benefiting from the heterologous expression of genes that increase the capacity of plants to mobilize, stabilize and/or accumulate metals. The efficiency of phytoremediation relies on the mechanisms underlying metal accumulation and tolerance, such as metal uptake, translocation and detoxification. The transfer of genes involved in any of these processes into fast-growing, high-biomass crops may improve their reclamation potential. The successful phytoextraction of metals/metalloids and their accumulation in aerial organs have been achieved by expressing metal ligands or transporters, enzymes involved in sulfur metabolism, enzymes that alter the chemical form or redox state of metals/metalloids and even the components of primary metabolism. This review article considers the potential of genetic engineering as a strategy to improve the phytoremediation capacity of plants in the context of heavy metals and metalloids, using recent case studies to demonstrate the practical application of this approach in the field., (© 2017 John Wiley & Sons Ltd.)

This chapter focuses on bioimaging in metallomics, which involves metal and metalloids distribution in animal tissues. It starts with laser ablation-inductively coupled plasma-mass spectrometry followed by secondary ion mass spectrometry, synchrotron-based X-ray fluorescence, and electron microscopy, including transmission electron microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The basic principles of these techniques and their application for qualitative and quantitative imaging of elements are presented. Sample preparation for bioimaging is briefly discussed. The usefulness of element bioimaging is demonstrated for cells and several animal tissues, including the brain, liver, hair, eye, teeth, and bone. As such, this chapter addresses the state of the art in bioimaging metallomics.

Metallomics, a discipline integrating sciences that address the biometals and biometalloids, provides new opportunities for discoveries. As part of a systems biology approach, it draws attention to the importance of many chemical elements in biochemistry. Traditionally, biochemistry has treated life as organic chemistry, separating it from inorganic chemistry, considered a field reserved for investigating the inanimate world. However, inorganic chemistry is part of the chemistry of life, and metallomics contributes by showing the importance of a neglected fifth branch of building blocks in biochemistry. Metallomics adds chemical elements/metals to the four building blocks of biomolecules and the fields of their studies: carbohydrates (glycome), lipids (lipidome), proteins (proteome), and nucleotides (genome). The realization that non-essential elements are present in organisms in addition to essential elements represents a certain paradigm shift in our thinking, as it stipulates inquiries into the functional implications of virtually all the natural elements. This article discusses opportunities arising from metallomics for a better understanding of human biology and health. It looks at a biological periodic system of the elements as a sum of metallomes and focuses on the major roles of metals in about 30-40% of all proteins, the metalloproteomes. It emphasizes the importance of zinc and iron biology and discusses why it is important to investigate non-essential metal ions, what bioinformatics approaches can contribute to understanding metalloproteins, and why metallomics has a bright future in the many dimensions it covers.

Metallomics allows the integration of traditionally analytical studies with inorganic and biochemical studies. The study of metallomics in living organisms allows us to obtain information about how the metal ion is distributed and coordinated with proteins, the essentiality and/or toxicity, and the individual concentrations of metal species, thus contributing to elucidation of the physiological and functional aspects of these biomolecules. In this context, several lines of research have appeared in the literature with different terms and approaches. For example, metallomic, which deals with the characterization of the total metal/metalloid species present in an organism; metalloprotein, which deals with the characterization of the total elements present in a specific site of an organism (cellular behavior, protein, metalloprotein); and metallomic, which deals with a more in-depth study of metallome. In this area, information is sought on the interactions and functional connections of metal/metalloid species with genes, proteins, metabolites and other biomolecules of the organism and, therefore, the elucidation of the biological role exerted by the metal ions bound to the biomolecules. In this chapter, we will describe techniques used in animal studies.

Chemical speciation approaches is an inherent part of metallomics, once metals/metalloids and organic structures need to be currently evaluated for attaining metallomics studies. Then, this chapter focuses on the applications of the chemical speciation applied to the human health risk, food and human diet, drugs, forensic, nanoscience, and geological metallomics, also pointing out the advances in such area. Some aspects regarding sample preparation is commented along this chapter, and some strategies for maintaining the integrity of the metallomics information are also emphasized.