Antimicrobial Activity of Metals and Metalloids.

Competition shapes evolution. Toxic metals and metalloids have exerted selective pressure on life since the rise of the first organisms on the Earth, which has led to the evolution and acquisition of resistance mechanisms against them, as well as mechanisms to weaponize them. Microorganisms exploit antimicrobial metals and metalloids to gain competitive advantage over other members of microbial communities. This exerts a strong selective pressure that drives evolution of resistance. This review describes, with a focus on arsenic and copper, how microorganisms exploit metals and metalloids for predation and how metal- and metalloid-dependent predation may have been a driving force for evolution of microbial resistance against metals and metalloids.

Barley Nodulin 26-like intrinsic protein permeates water, metalloids, saccharides, and ion pairs due to structural plasticity and diversification.

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 MgSO4 ions, while CH3COONa and NaNO3 permeated at significantly lower rates. Our experiments with boric acid and sucrose revealed no apparent interaction between solutes when permeated together, and AgNO3 or H[AuCl4] 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.

AsIII Selectively Induces a Disorder-to-Order Transition in the Metalloid Binding Region of the AfArsR Protein.

Arsenic is highly toxic and a significant threat to human health, but certain bacteria have developed defense mechanisms initiated by AsIII binding to AsIII-sensing proteins of the ArsR family. The transcriptional regulator AfArsR responds to AsIII and SbIII by coordinating the metalloids with three cysteines, located in a short sequence of the same monomer chain. Here, we characterize the binding of AsIII and HgII 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 AsIII changes the peptide structure from a random-coil to a well-defined structure of the complex. A trigonal pyramidal AsS3 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 AsIII recognition and response selectivity of AfArsR. Contrary to this, binding of HgII 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 HgII 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.

Unveiling Innovative Approaches to Mitigate Metals/Metalloids Toxicity for Sustainable Agriculture.

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.

Inorganometallics (Transition Metal-Metalloid Complexes) and Catalysis.

While the formation and breaking of transition metal (TM)-carbon bonds plays a pivotal role in the catalysis of organic compounds, the reactivity of inorganometallic species, that is, those involving the transition metal (TM)-metalloid (E) bond, is of key importance in most conversions of metalloid derivatives catalyzed by TM complexes. This Review presents the background of inorganometallic catalysis and its development over the last 15 years. The results of mechanistic studies presented in the Review are related to the occurrence of TM-E and TM-H compounds as reactive intermediates in the catalytic transformations of selected metalloids (E = B, Si, Ge, Sn, As, Sb, or Te). The Review illustrates the significance of inorganometallics in catalysis of the following processes: addition of metalloid-hydrogen and metalloid-metalloid bonds to unsaturated compounds; activation and functionalization of C-H bonds and C-X bonds with hydrometalloids and bismetalloids; activation and functionalization of C-H bonds with vinylmetalloids, metalloid halides, and sulfonates; and dehydrocoupling of hydrometalloids. This first Review on inorganometallic catalysis sums up the developments in the catalytic methods for the synthesis of organometalloid compounds and their applications in advanced organic synthesis as a part of tandem reactions.

Evaluation of essential and trace metals/metalloids distribution and probable human health risk implications from branded liquid and powder milks available in Dhaka City, Bangladesh.

The processed forms of milk, branded liquid, and power milk available in Dhaka city, the capital of Bangladesh, were investigated for essential and trace metal/metalloids regarding nutritional and human health risk aspects. For this, the potential nutritional contribution, estimated daily intake (EDI) and non-carcinogenic risk for six different life stages with male and female categories, as well as the carcinogenic risk for children and adults of both genders, were addressed. In total, 46 branded liquid and powder milk samples were considered for this analysis employing atomic absorption spectroscopy. The concentration of essential elements showed the trends of K > Ca > Na > Mg > Fe > Zn > Mn > Cu and K > Ca > Na > Mg > Fe > Cu > Mn > Zn for liquid and powder milk samples, respectively, but the potentially hazardous one showed the same trends (Cr > Pb > Hg > As > Cd) for both items. Except for Cr, Hg, and Fe, the elemental compositions of both milk categories differed considerably (< 0.05). Compared to the threshold values for milk samples (liquid and powder), Fe (19% and 27%), Mn (100% and 63%), Cu (0% and 23%), Zn (94% and 0%), Pb (25% and 13%), and Cr (0% and 3%) showed above the permissible limits. The nutrient input was the highest for Ca (27.2% and 18.7%), followed by Mg, K, and Na. The EDI of studied elements was within the daily permissible limit in both the milk category (except age group (≤ 3) and the female category). The non-carcinogenic risk assessment showed that the age groups ≤ 3 for liquid milk and ≤ 3 and 3 < X ≤ 14 with female categories for powder milk exceeded the threshold level (> 1) in the case of Cr, Cd, As, Zn, and Mn. The probable carcinogenic risks indicated an unacceptable risk level (< 1.00E-04) for the ingestion of Cr through powder milk samples for children in male and female categories. Finally, it believes that green cow farming practices and green milk processing technology, as well as continuous monitoring of toxic metals, can limit the ultimate risk worldwide.

Elucidating the synergistic effect of acidity and metalloid poisoning on the microbiome through metagenomics and machine learning approaches.

The abundance and diversity of the microflora in a complex environment such as soil is everchanging. Mica mining has led to metalloid poisoning and changes in soil biogeochemistry affecting the overall produce and leading to toxic dietary exposure. The study focuses on two prominent stressors acidity and arsenic, in mining-contaminated agricultural locations. Soil samples were collected from agricultural fields at a distance of 50 m (zone 1) and 500 m (zone 2) from active mines. Mean arsenic concentration was higher in zone 1 and pH was lower. Geostatistical and self-organizing maps were employed to report that the pattern of localization of soil acidity and arsenic content is similar indicating a causal relationship. Cluster and principal component analysis were further used to materialize a negative effect of soil acidity fractions and arsenic labile pool on soil enzymatic activity (fluorescein diacetate, dehydrogenase, ß-1,4-glucosidase, phosphatase, and urease), respiration and Microbial biomass carbon. Soil metagenomic analysis revealed significant differences in the abundance of microbial populations with zone 1 (contaminated zone) having lower alpha and beta diversity. Finally, the efficacy of several machine-learning tools was tested using Taylor diagrams and an effort was made to select a potent algorithm to predict the causal stressors responsible for depreciating soil microbial health. Random Forrest had superior predictive power based on numerical evidence and was therefore chosen as the best-fitted model. The aforementioned insights into soil microbial health and sustenance in stressed conditions can be beneficial for predicting remedial strategies and practicing sustainable agriculture.

Black Vulture (Coragyps atratus) feathers as bioindicators of exposure to metals and metalloids contamination in urban, semi-urban, and rural areas from Campeche state, Mexico.

Landfills are sources of soil, water, and air pollution due to the release of toxic compounds such as metals and metalloids. In both tropical and temperate environments, scavenger birds such as the Black Vulture (Coragyps atratus) that have learned to use these sites as a feeding area are probably exposed to metals, metalloids and other "persistent bioaccumulative toxic substances (PBTs)" released in open dumpsite (OD) and sanitary landfill (SL). The objective of this study is to evaluate the presence and distribution of toxic metals (Al, Sn, Hg, Cu, Pb, Cd, Cr) and As in OD and SL from urban, semi-urban and rural localities in Campeche, México, using molting feathers of C. atratus as bioindicators. A total of 125 Black Vulture primary and secondary wing feathers were collected from OD and SL. Metals were determined by voltammetry through acid digestion. The highest levels of metals occurred in landfills in urban, semi-urban, and rural localities. The elements with the highest concentrations were Al, with an average of 35.67 ± 33.51 µg g-1 from rural environments, and As, with 16.20 ± 30.06 µg g-1 from the urban localities. Mercury was the only element that had a very homogeneous distribution between the three environments we studied. In general, Pb, Hg, Cu and Cd were the elements that presented the lowest concentrations with 0.32 ± 0.35, 0.16 ± 0.22, 0.14 ± 0.31 and 0.06 ± 0.10 µg g-1, respectively regardless of any particular location or environment. Black Vultures from dumpsites are good bioindicators of what humans consume in urban, semi-urban, and rural environments. However, the conservation of vultures is of great importance since these scavenger birds perform ecosystem services by feeding on decomposing organic material.

Heavy metals and metalloids exposure and liver function in Chinese adults - A nationally representative cross-sectional study.

BACKGROUND: In China, the effects of heavy metals and metalloids (HMMs) on liver health are not consistently documented, despite their prevalent environmental presence. OBJECTIVE: Our research assessed the association between HMMs and liver function biomarkers in a comprehensive sample of Chinese adults. METHODS: We analyzed data from 9445 participants in the China National Human Biomonitoring survey. Blood and urine were evaluated for HMM concentrations, and liver health was gauged using serum albumin (ALB), alanine aminotransferase (ALT), and aspartate aminotransferase (AST) metrics. Various statistical methods were employed to understand the relationship between 11 HMMs and liver function, adjusting for multiple factors. We also explored interactions with alcohol intake, gender, and age. RESULTS: Among HMMs, selenium in blood [weighted geometric mean (GM) = 95.56 µg/L] and molybdenum in urine (GM = 46.44 µg/L) showed the highest concentrations, while lead in blood (GM = 21.92 µg/L) and arsenic in urine (GM = 19.80 µg/L) had the highest levels among risk HMMs. Manganese and thallium consistently indicated potential risk factor to liver in both sample types, while selenium displayed potential liver protection. Blood HMM mixtures were negatively associated with ALB (ß = -0.614, 95% CI: -0.809, -0.418) and positively with AST (ß = 0.701, 95% CI: 0.290, 1.111). No significant associations were found in urine HMM mixtures. Manganese, tin, nickel, and selenium were notable in blood mixture associations, with selenium and cobalt being significant in urine. The relationship of certain HMMs varied based on alcohol consumption. CONCLUSION: This research highlights the complex relationship between HMM exposure and liver health in Chinese adults, particularly emphasizing metals like manganese, thallium, and selenium. The results suggest a need for public health attention to low dose HMM exposure and underscore the potential benefits of selenium for liver health. Further studies are essential to establish causality.

Effects of heavy metals and metalloids on the biodegradation of organic contaminants.

Heavy metals and metalloids (HMMs) inhibit the biodegradation of organic pollutants. The degree of inhibition depends not only on the concentration and bioavailability of HMMs but also on additional factors, such as environmental variables (e.g., inorganic components, organic matter, pH, and redox potential), the nature of the metals, and microbial species. Based on the degradation pattern and metal concentrations causing half biodegradation rate reductions (RC50s), the inhibition of biodegradation was: Hg2+, As2O3 > Cu2+, Cd2+, Pb2+, Cr3+ > Ni2+, Co2+ > Mn2+, Zn2+ > Fe3+. Four patterns were observed: inhibition increases with increasing metal concentration; low concentrations stimulate, while high concentrations inhibit; high concentrations inhibit less; and mild inhibition remains constant. In addition, metal ion mixtures have more complex inhibitory effects on the degradation of organic pollutants, which may be greater than, similar to, or less than that of individual HMMs. Finally, the inhibitory mechanism of HMMs on biodegradation is reviewed. HMMs generally have little impact on the biodegradation pathway of organic pollutants for bacterial strains. However, when pollutants are biodegraded by the community, HMMs may activate microbial populations harbouring different transformation pathways. HMMs can affect the biodegradation efficiency of organic pollutants by changing the surface properties of microbes, interfering with degradative enzymes, and interacting with general metabolism.

Exposure of the general French population to metals and metalloids in 2014-2016: Results from the Esteban study.

BACKGROUND: The purpose of the Esteban study was to describe levels of various biomarkers of exposure to several environmental pollutants, including metals and metalloids, among the French population. This paper describes the distribution of concentrations of 28 metals and metalloids in two different populations, and estimates the main determinants of exposure to total arsenic, the sum of inorganic arsenic (iAs) and its two metabolites monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), cadmium, chromium, copper, mercury and nickel. METHODS: Esteban is a cross-sectional study conducted between 2014 and 2016 on a random sample of 2503 adults (18-74 years old) and 1104 children (6-17 years old) from the general population. The data collected included biological samples (blood, hair, and urines), socio-demographic characteristics, environmental and occupational exposure, and information on dietary factors and lifestyle. The geometric mean and percentiles of the distribution were estimated for each metal. Multivariate analyses were performed to identify the determinants of exposure using a generalized linear model. RESULTS: Only four metals had a quantification rate below 90% in adults (beryllium, iridium, palladium, and platinum), and three metals in children (beryllium, iridium, and platinum). The concentrations of total arsenic, cadmium, chromium and mercury were higher than those found in most international studies. The determinants significantly associated with exposure were mainly diet and smoking. CONCLUSIONS: Esteban provided a nationwide description of 28 metal and metalloid exposure levels for adults (some never measured before) and for the first time in children. The study results highlighted widespread exposure to several metals and metalloids. These results could be used to advocate public health decisions for continued efforts to reduce harmful exposure to toxic metals. The Reference values (RV95) built from Esteban could also be used to support future government strategies.

Mechanisms of genotoxicity and proteotoxicity induced by the metalloids arsenic and antimony.

Arsenic and antimony are metalloids with profound effects on biological systems and human health. Both elements are toxic to cells and organisms, and exposure is associated with several pathological conditions including cancer and neurodegenerative disorders. At the same time, arsenic- and antimony-containing compounds are used in the treatment of multiple diseases. Although these metalloids can both cause and cure disease, their modes of molecular action are incompletely understood. The past decades have seen major advances in our understanding of arsenic and antimony toxicity, emphasizing genotoxicity and proteotoxicity as key contributors to pathogenesis. In this review, we highlight mechanisms by which arsenic and antimony cause toxicity, focusing on their genotoxic and proteotoxic effects. The mechanisms used by cells to maintain proteostasis during metalloid exposure are also described. Furthermore, we address how metalloid-induced proteotoxicity may promote neurodegenerative disease and how genotoxicity and proteotoxicity may be interrelated and together contribute to proteinopathies. A deeper understanding of cellular toxicity and response mechanisms and their links to pathogenesis may promote the development of strategies for both disease prevention and treatment.

Associations between plasma metal/metalloid mixtures and the risk of central obesity: A prospective cohort study of Chinese adults.

Central obesity has increased rapidly over the past decade and posed a substantial disease burden worldwide. Exposure to metals/metalloids has been acknowledged to be involved in the development of central obesity through regulation of cortisol, insulin resistance, and glucocorticoid receptor reduction. Despite the importance, it is lack of prospective study which comprehensively evaluate the relations between multiple metals exposure and central obesity. We explored the prospective associations of plasma metal concentrations with central obesity in a prospective study of the Dongfeng-Tongji cohort. The present study included 2127 participants with a 6.87-year mean follow-up duration. We measured 23 plasma metal/metalloid concentrations at baseline. The associations between metals and incident central obesity were examined utilizing the Cox proportional hazard regression in single and multiple metals models. Additionally, we applied elastic net (ENET), Bayesian kernel machine regression (BKMR), plasma metal score (PMS), and quantile-based g-computation (Qgcomp) models to explore the joint associations of metal mixtures with central obesity. After adjusting potential confounders, we found significant associations of plasma manganese (Mn) and thallium (Tl) concentrations with a higher risk of central obesity, whereas plasma rubidium (Rb) concentration was associated with a lower risk of central obesity both in single and multiple metals models (all FDR <0.05). The ENET and Qqcomp models verified similar metals (Mn, Rb, and Tl) as important predictors for central obesity. The results of both BKMR model and PMS suggested cumulative exposure to metal mixtures was associated with a higher risk of central obesity. Our findings suggested that co-exposure to metals was associated with a higher risk of central obesity. This study expands our knowledge that the management of metals/metalloids exposure may be beneficial for the prevention of new-onset central obesity, which may subsequently alleviate the disease burden of late-life health outcomes.

Associations between seminal plasma metals/metalloids and semen quality: A cross-sectional study.

Exposure to metals/metalloids is reported to potentially influence semen quality. While most studies have focused on single metal impacts, the link between exposure to multiple metals and semen quality has remained less explored. The study aimed to investigate the effects of both individual and mixed metal/metalloid exposure on semen quality. A total of 330 men were recruited from three reproductive centers in eastern China. Seminal plasma levels of 25 metals/metalloids and sperm parameters were determined. We used the Generalized Linear Model (GLM) and Restricted Cubic Spline (RCS) to assess the relationships between single metals/metalloids and semen quality. The weighted quantile sum (WQS) models were then applied to evaluate the combined effect of all these metals/metalloids. We observed positive associations of exposure to lithium (Li), zinc (Zn), and magnesium (Mg) with an increased risk of below reference values for progressive motility and total motility using a logistic regression model (P < 0.05). Additionally, our results also revealed a significant inverse relationship between aluminum (Al) and both sperm concentration and count, while cobalt (Co) demonstrated a positive association with sperm concentration (P < 0.05). Notably, the WQS model indicated a significant positive association between exposure to metal/metalloid mixtures and the risk of abnormal progressive motility (OR: 1.57; 95%CI: 1.10, 2.24) and abnormal total motility (OR: 1.53; 95%CI: 1.06, 2.19), with this association primarily driven by Li, Mg, and Zn. In summary, our findings indicate that exposure to metal/metalloid mixtures might have an adverse effect on semen quality.

In vitro chronic phytotoxicity of heavy metals and metalloids to Lepidium sativum (garden cress).

The paper presents the results of studies on the influence of selected concentrations (10-100 mg L-1) of heavy metals (Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Zn) and metalloids (As, Sb, Se) on the germination and root elongation of garden cress (Lepidium sativum L). There are not many studies on phytotoxicity of heavy metals and metalloids with the complex use of single plant species so far. On the basis of the germination index (GI) and inhibition concentration IC50, the following order of phytotoxicity of the tested elements was determined: Se> As> Hg> Sb > Mo > Cd> Co > Zn > Ni. The other metals showed no phytotoxicity or even stimulating effect. In our study the stimulating effect of the majority of Pb concentrations and the lowest concentrations of Cd and Hg has been revealed. These metals do not play any role in living organisms, however some authors confirm their stimulating effect on plants at low concentrations. Toxic concentration of metals and metalloids calculated as IC50 are lower than the concentration calculated as GI (not phytotoxic). It is well known that seeds are more independent and tolerant to toxicants when they contain reserve substances which are used during the germination period. On the basis of conducted research, high tolerance of L. sativum to heavy metals and metalloids was found, which may indicate its usefulness for phytotoxicity assessment of leachate from contaminated soil or waste (e.g. foundry waste) and its application for bioremediation to manage heavy metal pollution of soils or foundry wastes containing heavy metals and metalloids. The understanding of heavy metal and metalloids toxicity will facilitate bioremediation.

Snow Contamination by Metals and Metalloids in a Polar Town: A Case Study of Nadym, Russia.

Snow composition depends on the long-range transport of pollutants. This article examines aspects of snow composition in the town of Nadym in Western Siberia. During fieldwork conducted in 2021 and 2022, we determined dust load, concentrations and ratio of dissolved and suspended forms of metals and metalloids (MMs). Moreover, we analyzed air mass trajectories using the HYSPLIT model, and the results showed that industrial regions of the southern Urals, southeastern Siberia, and Kazakhstan were the sources of MMs. Content of the insoluble fraction was increased by 23-fold in Nadym. The dust load in Nadym was higher than that in urban communities situated in the temperate zone, even though this town is relatively small in population and has little industrial infrastructure. This significant increase in dust load led to a ten- to 100-fold increase in the content MMs. Local soils (Fe, Al), vehicles (W), building dust (Mg, Ca), and anti-icing agents (Na) were found to be the sources of pollution. We found that the high dust load is caused by meteorological factors, such as temperature inversion and a large number of calm days, which reduce the dispersion of pollution. This case study demonstrates that winter air quality in polar settlements can be worse than that in urban areas in the temperate zone, even with few local sources of pollution. Furthermore, the trend toward an increase in the number of windless days, such as observed in Siberia as a result of global climate change, increases the risk of anthropogenic pollution of the atmosphere of polar cities.

Multilevel Regulation of Membrane Proteins in Response to Metal and Metalloid Stress: A Lesson from Yeast.

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.

Fast and efficient As(III) removal from water by bifunctional nZVI@NBC.

As a notable toxic substance, metalloid arsenic (As) widely exists in water body and drinking As-contaminated water for an extended period of time can result in serious health concerns. Here, the performance of nanoscale zero-valent iron (nZVI) modified N-doped biochar (NBC) composites (nZVI@NBC) activated peroxydisulfate (PDS) for As(III) removal was investigated. The removal efficiencies of As(III) with initial concentration ranging from 50 to 1000 µg/L were above 99% (the residual total arsenic below 10 µg/L, satisfying the contaminant limit for arsenic in drinking water) within 10 min by nZVI@NBC (0.2 g/L)/PDS (100 µM). As(III) removal efficiency influenced by reaction time, PDS dosage, initial concentration, pH, co-existing ions, and natural organic matter in nZVI@NBC/PDS system were investigated. The nZVI@NBC composite is magnetic and could be conveniently collected from aqueous solutions. In practical applications, nZVI@NBC/PDS has more than 99% As(III) removal efficiency in various water bodies (such as deionized water, piped water, river water, and lake water) under optimized operation parameters. Radical quenching and EPR analysis revealed that SO4·- and ·OH play important roles in nZVI@NBC/PDS system, and the possible reaction mechanism was further proposed. These results suggest that nZVI@NBC activated peroxydisulfate may be an efficient and fast approach for the removal of water contaminated with As(III).

Heavy metal and metalloid concentrations in red deer (Cervus elaphus) and their human health implications from One Health perspective.

The red deer is an ungulate and large game species. The contamination of the ecosystems by metal(loid)s may lead to the exposure of animals (as well as humans) through water and food resources. The direct contact of hunters and wild animal meat consumers with deer carcasses may be a potential contaminant source. This study aimed to determine the metal(loid)s' concentrations in the liver and kidney of red deer from two regions of Portugal (Idanha-a-Nova and Lousã), and to relate these with histopathologic lesions. Thirteen young male deer were submitted to metal(loid) determination (As, Cd, Co, Cr, Cu, Pb, and Zn) by inductively coupled plasma mass spectrophotometry (ICP-MS) and histopathology examination. Renal Cd (8.072 ± 5.766 mg/kg dw) and hepatic Pb (3.824 ± 6.098 mg/kg dw) mean values were high, considering the maximum values for consumption established by the European Commission. The hepatic mean value of Cu was significantly higher in Idanha-a-Nova (150.059 ± 33.321 mg/kg dw), and it is at the Cu toxicity limit considered for ruminants (150 mg/kg). The pollution induced by Panasqueira mines (Castelo Branco) may be a possible explanation for some of the findings, especially the higher values of hepatic Cu and Pb found in Idanha-a-Nova deer. These results have high importance under a One Health perspective, since they have implications in public health, and pose at risk the imbalance of animal populations and ecosystems.

Historical co-enrichment, source attribution, and risk assessment of critical nutrients and heavy metal/metalloids in lake sediments: insights from Chaohu Lake, China.

In Chinese freshwater lakes, eutrophication often coincides with heavy metal/metalloids (HM/Ms) pollution, yet the coevolution of critical nutrients (P, S, Se) and HM/Ms (Cd, Hg, etc.) remains understudied. To address this gap, we conducted a sedimentary chemistry analysis on a 30 cm-deep core, dating back approximately 200 years, retrieved from Chaohu Lake, China. The age-depth model revealed a gradual increase in deposition rates over time. Notably, the concentrations and enrichment factors (EFs) of most target elements surged in the uppermost ~ 15 cm layer, covering the period from 1953 to 2013, while both the concentrations and EFs in deeper layers remained relatively stable, except for Hg. This trend indicates a significant co-enrichment and near-synchronous increase in the levels and EFs of both nutrients and HM/Ms in the upper sediment layers since the mid-twentieth century. Anthropogenic factors were identified as the primary drivers of the enrichment of P, Se, Cd, Hg, Zn, and Te in the upper core, with their contributions also showing a coupled evolutionary trend over time. Conversely, geological activities governed the enrichment of elements in the lower half of the core. The gradual accumulation of anthropogenic Hg between the - 30 to - 15 cm layers might be attributed to global Hg deposition resulting from the industrial revolution. The ecological risk index (RI) associated with HM/Ms loading has escalated rapidly over the past 50 years, with Cd and Hg posing the greatest threats. Furthermore, the PMF model was applied to specifically quantify source contributions of these elements in the core, with anthropogenic and geogenic factors accounting for ~ 60 and ~ 40%, respectively. A good correlation (r2 = 0.87, p < 0.01) between the PMF and Ti-normalized method was observed, indicating their feasibility and cross-validation in source apportionment. Finally, we highlighted environment impact and health implications of the co-enrichment of nutrients and HM/Ms. This knowledge is crucial for developing strategies to protect freshwater ecosystems from the combined impacts of eutrophication and HM/Ms pollution, thereby promoting water environment and human health.