Cadmium transport by mammalian ATP-binding cassette transporters.

Cellular responses to toxic metals depend on metal accessibility to intracellular targets, reaching interaction sites, and the intracellular metal concentration, which is mainly determined by uptake pathways, binding/sequestration and efflux pathways. ATP-binding cassette (ABC) transporters are ubiquitous in the human body-usually in epithelia-and are responsible for the transfer of indispensable physiological substrates (e.g. lipids and heme), protection against potentially toxic substances, maintenance of fluid composition, and excretion of metabolic waste products. Derailed regulation and gene variants of ABC transporters culminate in a wide array of pathophysiological disease states, such as oncogenic multidrug resistance or cystic fibrosis. Cadmium (Cd) has no known physiological role in mammalians and poses a health risk due to its release into the environment as a result of industrial activities, and eventually passes into the food chain. Epithelial cells, especially within the liver, lungs, gastrointestinal tract and kidneys, are particularly susceptible to the multifaceted effects of Cd because of the plethora of uptake pathways available. Pertinent to their broad substrate spectra, ABC transporters represent a major cellular efflux pathway for Cd and Cd complexes. In this review, we summarize current knowledge concerning transport of Cd and its complexes (mainly Cd bound to glutathione) by the ABC transporters ABCB1 (P-glycoprotein, MDR1), ABCB6, ABCC1 (multidrug resistance related protein 1, MRP1), ABCC7 (cystic fibrosis transmembrane regulator, CFTR), and ABCG2 (breast cancer related protein, BCRP). Potential detoxification strategies underlying ABC transporter-mediated efflux of Cd and Cd complexes are discussed.

Chemical fractionation and mobility of Cd, Mn, Ni, and Pb in farmland soils near a ceramics company.

Soil contamination due to industrial activity in ceramics production is of concern because of the risk of heavy metal pollution. Successive extraction was used to measure and identify the concentrations of Cd, Mn, Ni, and Pb in farming soils near a ceramics company in Nigeria. Furthermore, soil pH and particle size analyses were determined. The concentration of Pb was the highest, followed by that of Ni, Mn, and Cd (lowest), and the mean level of Cd exceeded the regulatory allowed limit of 1.4 mg kg-1. The order of the metals' mobility factors was as follows: Cd > Mn > Ni, Pb. While the Fe-Mn oxide phase had 37% (Mn) and 20 to 83% (Ni), the residual fraction had approximately 30% (Cd) and 19 to 50% (Pb). Soil pollution evaluation was performed using enrichment factor (EF), contamination factor (CF), pollution load index (PLI), and geoaccumulation index (Igeo). Values of EF indicated significant enrichment for all metals, as the EF mean values for Cd, Ni, and Pb in soil were > 1.5. Total EF is of the order Cd > Pb > Ni > Mn. CF results revealed moderate to very high contamination (CF < 1: 3 ≤ CF ≥ 6). Similarly, the PLI indicated moderately to severely polluted soil. The order is 100 m > 200 m > 300 m > 400 m. The Igeo ranged from 1.46 to 2.76 (Cd), 0.07 to 1.62 (Ni), and 0.05 to 2.81 (Pb). The PCA, CA, and EF analyses suggest that the metals are a consequence of anthropogenic activities.

Trace metal speciation trends in Mazowe dam, Zimbabwe, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture.

The present study aimed to assess trace metal speciation trends in the water and sediments of Mazowe Dam, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture in Zimbabwe. The elements studied include Al, As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, and Zn. Elemental speciation in the water column was determined using Visual MINTEQ version 3.1 geochemical computer modelling, while speciation in the sediment phase was determined using sequential extraction techniques. For each element, the data obtained were subjected to extensive correlation analysis to identify intra- and inter-metal species interactions in the water column and the sediment phase, as well as across the water-sediment interface. Possible mechanisms to account for the observed species interactions are proposed. In the water column, Co was predicted to have the highest number of chemical species (9), Cd and Zn (8), Mn and Fe (7), Ni (6), Pb (5), Al and Cu (3), Cr, Hg, and As have the least (2). In the sediment, Al, As, Co, Cr, Cu, Fe, Ni and Fe mainly exist in the residual fraction, while Zn and Mn concentrations in fractions vary per sampling site, with no fraction that is dominant across the sampling sites. Equilibrium exchange reactions across the water-sediment interface were observed e.g., for Cd species /FA2Cd (aq) and Co species /FACo+2G (aq), and /FA2Co (aq). This study is valuable in highlighting trace metal speciation in a tropical dam ecosystem in Africa and adds to the growing knowledge about the behaviour of trace metals in aquatic ecosystems in the region and globally.

Dynamic modelling the effects of ionic strength and ion complexation on trace metal speciation during anaerobic digestion.

Dosing trace metals into anaerobic digestors is proven to improve biogas production rate and yield by stimulating microorganisms involved in the metabolic pathways. Trace metal effects are governed by metal speciation and bioavailability. Though chemical equilibrium speciation models are well-established and widely used to understand metal speciation, the development of kinetic models considering biological and physicochemical processes has recently gained attention. This work proposes a dynamic model for metal speciation during anaerobic digestion which is based on a system of ordinary differential equations aimed to describe the kinetics of biological, precipitation/dissolution, gas transfer processes and, a system of algebraic equations to define fast ion complexation processes. The model also considers ion activity corrections to define effects of ionic strength. Results from this study shows the inaccuracy in predicting trace metal effects on anaerobic digestion by typical metal speciation models and the significance of considering non-ideal aqueous phase chemistry (ionic strength and ion pairing/complexation) to define speciation and metal labile fractions. Model results show a decrease in metal precipitation and increase in metal dissolved fraction and methane production yield with increase in ionic strength. Capability of the model to dynamically predict trace metal effects on anaerobic digestion under different conditions, like changing dosing conditions and initial iron to sulphide ratio, was also tested and verified. Dosing iron increases methane production and decreases hydrogen sulphide production. However, when iron to sulphide ratio is greater than 1, methane production decreases due to increase in dissolved iron which reaches inhibitory concentration levels.

Enhanced lead phytoextraction and soil health restoration through exogenous supply of organic ligands: Geochemical modeling".

Phytoremediation of lead (Pb) contaminated soil is a green technology to reduce Pb exposure and root exudates-derived organic acids play a vital role in this treatment process. In this study, Pb hyperaccumulator Pelargonium hortorum was chosen to investigate root-induced organic acid secretions and their subsequent role in Pb phytoextraction. In the first step, root exudation of P. hortorum was investigated in hydroponic experiments (0.2X Hoagland solution) under control and Pb stress conditions. Possible chemical interactions between Pb and the observed root exudates were then analyzed using Visual MINTEQ modeling. In the next step, the effects of the exogenous application of organic acids on Pb phytoextraction and soil enzymatic activities were studied in a pot experimental setup. Results indicated significant exudation of malic acid > citric acid > oxalic acid > tartaric acid in root exudates of P. hortorum under 50 mg L-1 Pb. Visual MINTEQ modeling results revealed that organic acids directly affect Pb dissolution in the nutrient solution by modulation of solution pH. Experimental results revealed that malic acid and citric acid significantly increased available Pb contents (7.2- and 6.7-folds) in the soil with 1500 mg kg-1 Pb contamination. Whereas, in shoot and root, the highest increase in Pb concentration was observed with citric acid (2.01-fold) and malic (3.75-fold) supplements, respectively. Overall, Pb uptake was notably higher when malic acid was applied (2.8-fold) compared to other organic acids, followed by citric acid (2.7-fold). In the case of soil enzymatic activities, oxalic acid significantly improved dehydrogenase, alkaline phosphatase, and microbial biomass by 1.6-, 1.4- and 1.3-folds, respectively. The organic acids were successful in reviving enzyme activity in Pb-contaminated soil, and might thus be used for long-term soil regeneration.

Responses of rhizosphere microbial community structure and metabolic function to heavy metal coinhibition.

Metal mineral mining results in releases of large amounts of heavy metals into the environment, and it is necessary to better understand the response of rhizosphere microbial communities to simultaneous stress from multiple heavy metals (HMs), which directly impacts plant growth and human health. In this study, by adding different concentrations of cadmium (Cd) to a soil with high background concentrations of vanadium (V) and chromium (Cr), the growth of maize during the jointing stage was explored under limiting conditions. High-throughput sequencing was used to explore the response and survival strategies of rhizosphere soil microbial communities to complex HM stress. The results showed that complex HMs inhibited the growth of maize at the jointing stage, and the diversity and abundance of maize rhizosphere soil microorganisms were significantly different at different metal enrichment levels. In addition, according to the different stress levels, the maize rhizosphere attracted many tolerant colonizing bacteria, and cooccurrence network analysis showed that these bacteria interacted very closely. The effects of residual heavy metals on beneficial microorganisms (such as Xanthomonas, Sphingomonas, and lysozyme) were significantly stronger than those of bioavailable metals and soil physical and chemical properties. PICRUSt analysis revealed that the different forms of V and Cd had significantly greater effects on microbial metabolic pathways than all forms of Cr. Cr mainly affected the two major metabolic pathways: microbial cell growth and division and environmental information transmission. In addition, significant differences in rhizosphere microbial metabolism under different concentrations were found, and this can serve as a reference for subsequent metagenomic analysis. This study is helpful for exploring the threshold for the growth of crops in toxic HM soils in mining areas and achieving further biological remediation.

Elucidation of Metal Local Environments in Single-Atom Catalysts Based on Carbon Nitrides.

The ability to tailor the properties of metal centers in single-atom heterogeneous catalysts depends on the availability of advanced approaches for characterization of their structure. Except for specific host materials with well-defined metal adsorption sites, determining the local atomic environment remains a crucial challenge, often relying heavily on simulations. This article reports an advanced analysis of platinum atoms stabilized on poly(triazine imide), a nanocrystalline form of carbon nitride. The approach discriminates the distribution of surface coordination sites in the host, the evolution of metal coordination at different stages during the synthesis of the material, and the potential locations of metal atoms within the lattice. Consistent with density functional theory predictions, simultaneous high-resolution imaging in high-angle annular dark field and bright field modes experimentally confirms the preferred localization of platinum in-plane in the corners of the triangular cavities. X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and dynamic nuclear polarization enhanced 15 N nuclear magnetic resonance (DNP-NMR) spectroscopies coupled with density functional theory (DFT) simulations reveal that the predominant metal species comprise Pt(II) bound to three nitrogen atoms and one chlorine atom inside the coordination sites. The findings, which narrow the gap between experimental and theoretical elucidation, contribute to the improved structural understanding and provide a benchmark for exploring the speciation of single-atom catalysts based on carbon nitrides.

Effect of chloride concentration on the cytotoxicity, bioavailability, and bioreactivity of copper and silver in the rainbow trout gut cell line, RTgutGC.

Chloride (Cl-) influences the bioavailability and toxicity of metals in fish, but the mechanisms by which it influences these processes is poorly understood. Here, we investigated the effect of chloride on the cytotoxicity, bioavailability (i.e., accumulation) and bioreactivity (i.e., induction of mRNA levels of metal responsive genes) of copper (Cu) and silver (Ag) in the rainbow trout gut cell line (RTgutGC). Cells were exposed to metals in media with varying Cl- concentrations (0, 1, 5 and 146 mM). Metal speciation in exposure medium was analyzed using Visual MINTEQ software. Cytotoxicity of AgNO3 and CuSO4 was measured based on two endpoints: metabolic activity and membrane integrity. Cells were exposed to 500 nM of AgNO3 and CuSO4 for 24 h in respective media to determine metal bioavailability and bioreactivity. Ag speciation changes from free ionic (Ag+) to neutral (AgCl), to negatively charged chloride complexes (AgCl2-, AgCl3-) with increasing Cl- concentration in exposure media whereas Cu speciation remains in two forms (Cu2+ and CuHPO4) across all media. Chloride does not affect Ag bioavailability but decreases metal toxicity and bioreactivity. Cells exposed to Ag expressed significantly higher metallothionein mRNA levels in low Cl- media (0, 1, and 5 mM) than in high Cl- medium (146 mM). This suggests that chloride complexation reduces silver bioreactivity and toxicity. Conversely, Cu bioavailability and toxicity were higher in the high chloride medium (146 mM) than in the low Cl- (0, 1, and 5 mM) media, supporting the hypothesis that Cu uptake may occur via a chloride dependent mechanism. CLINICAL TRIALS REGISTRATION: This study did not require clinical trial registration.

Zinc transport and partitioning of a mine-impacted watershed: An evaluation of water and sediment quality.

Watershed systems influenced by mining waste products can persist for many years after operations are ceased, leading to negative impacts on the health of the surrounding environment. While geochemical behaviors of these trace metals have been studied extensively at the benchtop-scale, much fewer studies have looked at controls on their distributions at the watershed-level. In this study, trace metals (As, Cd, Cr, Cu, Ni, and Zn) were reported from water and stream bed sediments at eight sites between the years 2014-2018 along a watershed undergoing active remediation efforts. Zn was determined to be the only trace metal analyzed with concentrations above EPA and Kansas Department of Health guidelines for both water and sediment in the watershed, and thus was the primary focus for determining the health of the watershed system. Controls on trace metal pollution distribution over the watershed were investigated to determine where remediation efforts should be focused. Surface cover seemed to have the highest effectivity with pasture lands having a strong positive correlation to Zn concentrations. Initial remediation efforts were assessed by calculating the geoaccumulation index (Igeo) and the contamination factor (Cf-sediment) from sediments and contamination factor from water (Cf-water) after decades of chat pile removal efforts. Most of the sites showed significant reduction in metal concentration values compared to previous studies in the watershed for water and sediment, with four sites still reporting concentrations that reveal potential health risks. Results from this study will inform management and policy makers for areas to focus their remediation efforts on the Spring River Watershed as well as providing a framework for assessing pollution at a watershed scale.

Speciation of Cu, Cd, Pb and Zn in a contaminated harbor and comparison to environmental quality standards.

The water column of harbors contains significant amounts of (priority) hazardous trace metals that may be released into coastal areas of high societal and economic interests where they may disturb their fragile equilibria. To deepen our understanding of the processes that influence the transport of the various metal fractions and allow for a more rigorous environmental risk assessment, it is important to spatially monitor the relevant chemical speciation of these metals. It is of particular interest to assess their so-called dynamic fraction, which comprises the dissolved chemical forms that are potentially bioavailable to living organisms. In this study this was achieved in the Genoa Harbor (NW Italy) for copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) by applying a multi-method approach. For the first time in this system the dynamic fractions of the target metals (CuDyn, CdDyn, PbDyn, ZnDyn) were observed in real-time on-board by voltammetry using innovative electrochemical sensing devices. Trace metals in the operationally defined dissolved <0.2 µm and <0.02 µm fractions were equally quantified through sampling/laboratory-based techniques. The obtained results showed a clear spatial trend for all studied metals from the enclosed contaminated part of the harbor towards the open part. The highest CuDyn and CdDyn fractions were found in the inner part of the harbor while the highest PbDyn fraction was found in the open part. The proportion of ZnDyn was negligible in the sampled area. Small and coarse colloids were involved in Cu, Cd and Zn partitioning while only coarse colloids played an important role in Pb partitioning. The determined concentrations were compared to the Environmental Quality Standards (EQS) established by the EU and those determined by the Australia and New Zealand to trigger for 99 and 95% species protection values. The results of this work allow us to highlight gaps in the EQS for which metal concentration thresholds are excessively high or non-existent and should urgently be revised. They also reflect the need to quantify the potentially bioavailable fraction of hazardous trace metals instead of just their total dissolved concentrations. The data support the establishment of environmental quality standards and guidelines based on realistic risk assessment to protect aquatic life and resources and ultimately human health.

Metal Removal by a Free Surface Constructed Wetland and Prediction of Metal Bioavailability and Toxicity with Diffusive Gradients in Thin Films (DGT) and Biotic Ligand Model (BLM).

The H-02 constructed wetland is a free water surface wetland to remove copper (Cu) and zinc (Zn) from the industrial wastewater. In this study, we evaluated the performance of the wetland from 2018 to 2019 and coupled the diffusive gradients in thin films (DGTs) and biotic ligand model (BLM) to explore metal speciation and bioavailability in wetland waters. Surface water samples were collected and piston DGTs were deployed in different sites of the wetland. The H-02 wetland functioned well during the sampling period with high removal efficiencies (Cu: 73.8 ± 1.2% and Zn: 75.2 ± 16.0%). In our study, with the assumption that the combination of BLM predicted inorganic metals species, BLM Cu(II) and BLM Zn(II), were the bioavailable and toxic species, DGT-Cu did not correlate to BLM Cu(II) (P = 0.47), but DGT-Zn positively correlated to BLM Zn(II) (R2 = 0.35, P < 0.001). Compared to the modeling results of BLM, DGT-indicated labile and/or bioavailable Cu included not only free Cu ions and inorganic Cu complexes but also a high percentage of Cu-labile organic matter complexes. DGT-indicated Zn included free Zn ion, inorganic Zn, and only a low percentage of Zn-labile organic matter complexes. Our findings illustrated the appropriate use of passive sampling techniques and geological modeling when biomonitoring could be substituted. The close monitoring of metal concentrations, speciation, and bioavailability helps us understand metal biogeochemistry and metal removal processes and ensure the long-term sustainability of the constructed wetland.

Ecotoxicology of Heavy Metal(loid)-Enriched Particulate Matter: Foliar Accumulation by Plants and Health Impacts.

Atmospheric contamination by heavy metal-enriched particulate matter (metal-PM) is highly topical nowadays because of its high persistence and toxic nature. Metal-PMs are emitted to the atmosphere by various natural and anthropogenic activities, the latter being the major source. After being released into the atmosphere, metal-PM can travel over a long distance and can deposit on the buildings, water, soil, and plant canopy. In this way, these metal-PMs can contaminate different parts of the ecosystem. In addition, metal-PMs can be directly inhaled by humans and induce several health effects. Therefore, it is of great importance to understand the fate and behavior of these metal-PMs in the environment. In this review, we highlighted the atmospheric contamination by metal-PMs, possible sources, speciation, transport over a long distance, and deposition on soil, plants, and buildings. This review also describes the foliar deposition and uptake of metal-PMs by plants. Moreover, the inhalation of these metal-PMs by humans and the associated health risks have been critically discussed. Finally, the article proposed some key management strategies and future perspectives along with the summary of the entire review. The abovementioned facts about the biogeochemical behavior of metal-PMs in the ecosystem have been supported with well-summarized tables (total 14) and figures (4), which make this review article highly informative and useful for researchers, scientists, students, policymakers, and the organizations involved in development and management. It is proposed that management strategies should be developed and adapted to cope with atmospheric release and contamination of metal-PM.

Chemical speciation of selected toxic metals and multivariate statistical techniques used to assess water quality of tropical Mexican Lake Chapala.

Mexican Lake Chapala is used as water supply for human consumption. Consequently, water quality of this lake is of paramount importance for the lake's wellbeing. The contribution presented in this paper investigates monitoring and assessment of lake water quality using water quality index (WQI), metal chemical speciation, and multivariate statistical techniques. Descriptive statistics shows total metal concentrations undetected conferring the lake a healthy status. Dissolved Cd and Pb exceed criterion continuous concentration limit, whereas Zn is below this limit indicating that water quality is satisfactory for aquatic life. However, WQI indicates poor water quality attributed to failure of conductivity, total solids, nitrogen, and phosphates, due to industrial and agro-industrial effluents. Metal speciations indicate that the presence of low concentrations of dissolved metals reflect interactions with gills of fish through metal-biotic ligand complexes affecting water quality. Positive correlations are obtained between conductivity and nitrates, indicating that agricultural activities and fertilizer runoffs increase the conductivity and that the environmental state of lake is being altered by human activities. Factors F1 (31%), F2 (19%), and F3 (11%) represent 61% of variability; F1 and F2 corroborate the pressure exerted by pollutants related with fertilizers and agrochemicals; F3 contains Zn and Pb with positive loads attributed to influx of tourist visitors. Sites S4, S5, S6, and S9 are identified as the most environmentally affected by COD, Alk*, pH, Cl-, nitrites, phosphates, and TS. Multivariate techniques permit to conclude that environmental stress of Lake Chapala is caused by variables pertaining to agrochemical, fertilizers and municipal wastes.

Arabidopsis halleri shows hyperbioindicator behaviour for Pb and leaf Pb accumulation spatially separated from Zn.

Lead (Pb) ranks among the most problematic environmental pollutants. Background contamination of soils is nearly ubiquitous, yet plant Pb accumulation is barely understood. In a survey covering 165 European populations of the metallophyte Arabidopsis halleri, several field samples had indicated Pb hyperaccumulation, offering a chance to dissect plant Pb accumulation. Accumulation of Pb was analysed in A. halleri individuals from contrasting habitats under controlled conditions to rule out aerial deposition as a source of apparent Pb accumulation. Several elemental imaging techniques were employed to study the spatial distribution and ligand environment of Pb. Regardless of genetic background, A. halleri individuals showed higher shoot Pb accumulation than A. thaliana. However, dose-response curves revealed indicator rather than hyperaccumulator behaviour. Xylem sap data and elemental imaging unequivocally demonstrated the in planta mobility of Pb. Highest Pb concentrations were found in epidermal and vascular tissues. Distribution of Pb was distinct from that of the hyperaccumulated metal zinc. Most Pb was bound by oxygen ligands in bidentate coordination. A. halleri accumulates Pb whenever soil conditions render Pb phytoavailable. Considerable Pb accumulation under such circumstances, even in leaves of A. thaliana, strongly suggests that Pb can enter food webs and may pose a food safety risk.

The influence of humic and fulvic acids on Cd bioavailability to wheat cultivars grown on sewage irrigated Cd-contaminated soils.

The soil cadmium (Cd) contamination is a ubiquitous environmental problem that has resulted from intense irrigation with wastewater. This pot trial was conducted with aim to produce safe food with Cd tolerant wheat cultivar in wastewater irrigated soils. For this purpose, two wheat cultivars NARC-2011 (Cd tolerant) and Shafaq-2006 (Cd sensitive) were screened out and selected, after conducting a pilot trial of twelve local wheat cultivars against Cd stress. Both cultivars were grown in naturally contaminated soils with Cd concentrations (4.18, 3.23, 2.29 and 1.25 mg kg-1). After harvesting, NARC-2011 showed significant photosynthetic attributes, grain biochemical parameters and yield. Additionally, Cd concentrations in edible grains of NARC-2011 cultivars were found within standard limits (200 mg kg-1), in all contaminated soils. Furthermore, a marked decrease in Cd bioavailability was noted with cultivar NARC-2011, where contribution of mobile Cd fractions (exchangeable and reducible) percentage was decreased, while immobile Cd fractions percentage increased (oxidizable and residual). Fourier transform infrared (FTIR) spectroscopy reflects the maturity and stability of humic and fulvic like acid fractions and revealed that humification of these compounds after prolonged sludge enriched wastewater irrigation lowered the Cd availability. The wheat cultivar NARC-2011 (Cd tolerant) could be opted to grow on soils irrigated with wastewater for a long time, as Cd bioavailability decreased with ageing due to stabilized humic substances and varietal tolerance.

Effects of chemical interaction of nutrients and EDTA on metals toxicity to Pseudokirckneriella subcapitata.

We studied the effect of the chemical interaction of nutrients and the ethylenediamine tetraacetic acid (EDTA) on metals toxicity. Growth inhibition tests of Pseudokirchneriella subcapitata by nutrient metals copper (Cu) and zinc (Zn), and the non-nutrient metal lead (Pb), were performed. The high-enriched Bold's Basal medium (BBm) and two low-enriched standard media, recommended by the Organization for Economic Cooperation and Development (OECDm) and Environmental Protection Agency-algal assay procedure medium (AAPm), were used in this study. The metals toxicity was affected by the interaction of nutrients and EDTA. Cu+2 was more toxic in the OECDm (EC50 20.3 µg/L), while Pb+2 (EC50 23.1 µg/L) and Zn+2 (EC50 99.4 µg/L) in the AAPm. Non-toxic effect of these metals was observed in BBm, but the exclusion of EDTA shifted it into a toxic medium. Finally, we found that the toxicity of the studied nutrient metals is mainly influenced by EDTA, which reduced the concentration of ionized metals, while the toxicity of the non-nutrient metal is affected by EDTA and phosphates.

Effect of soil washing on heavy metal removal and soil quality: A two-sided coin.

Heavy metal contamination in soil due to human activities is a global environmental problem. To find a washing solution that can significantly decontaminate heavy metals and minimize damage to soil quality, six washing solutions (H3PO4, K2CO3, CH3COOK, KH2PO4, HNO3 and KNO3) were used at different concentrations to treat contaminated soil collected from the field. Furthermore, changes in soil physicochemical properties and heavy metal speciation among prewashed, postwashed and neutralized samples were tested. Additionally, soil enzyme activities and soil microbial diversities in contaminated soil among the prewashed, postwashed and neutralized samples were also measured. Finally, a pot experiment was conducted with Mentha haplocalyx to test the efficiency of soil washing. The results revealed that the optimum washing solution was 1% HNO3 and that the removal rates of Cd and Pb were 75.7% and 60.6%, respectively, under treatment conditions of 35 °C, 90 min and a solid-liquid ratio of 1:10. The pH, total phosphorous, available potassium, soil enzyme activities and soil microbial diversity decreased significantly after washing. However, after the neutralization of washed soil with Ca(OH)2, the available phosphorous, total nitrogen and some microorganisms increased significantly compared with those of the soil before washing. After treatment with 1% HNO3, the chemical forms of Cd and Pb in soil mainly existed as F1 (exchangeable) fractions, but the main forms of the two metals changed to F5 (residual) and F3 (bound to Fe-Mn oxides) fractions after neutralization with Ca(OH)2. In addition, the plant height, root length, and fresh and dry weight of M. haplocalyx were not significantly affected by soil neutralization, while the Pb, Cu and As concentrations in the aboveground parts significantly decreased. Therefore, although soil washing could effectively remove Pb and Cd in soil, it also resulted in a significant decline in soil quality, but soil neutralization could effectively alleviate the negative effects during soil washing.

Snapshots of Iron Speciation: Tracking the Fate of Iron Nanoparticle Drugs via a Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Approach.

Nanomedicines are nanoparticle-based therapeutic or diagnostic agents designed for targeted delivery or enhanced stability. Nanotechnology has been successfully employed to develop various drug formulations with improved pharmacokinetic characteristics, and current research efforts are focused on the development of new innovator and generic nanomedicines. Nanomedicines, which are often denoted as complex or nonbiological complex drugs, have inherently different physicochemical and pharmacokinetic properties than conventional small molecule drugs. The tools necessary to fully evaluate nanomedicines in clinical settings are limited, which can hamper their development. One of the most successful families of nanomedicines are iron-carbohydrate nanoparticles, which are administered intravenously (IV) to treat iron-deficiency anemia. In the U.S., the FDA has approved six distinct iron-carbohydrate nanoparticles but only one generic version (sodium ferric gluconate for Ferrlecit). There is significant interest in approving additional generic iron-carbohydrate drugs; however, the lack of a direct method to monitor the fate of the iron nanoparticles in clinical samples has impeded this approval. Herein we report a novel liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS) method that allows for the direct quantification of the iron-carbohydrate drugs in clinical samples, while simultaneously measuring the speciation of the iron released from the nanoparticles in biological samples. To our knowledge, this is the first time that iron nanoparticles have been observed in clinical samples, opening the door for direct pharmacokinetic studies of this family of drugs. This method has potential applications not only for iron-nanoparticle drugs but also for any nanomedicine with an inorganic component.

The interplay between chemical speciation and physiology determines the bioaccumulation and toxicity of Cu(II) and Cd(II) to Caenorhabditis elegans.

Using the well-documented model organism Caenorhabditis elegans, a combined analysis of metal speciation in the exposure medium and body burdens of metals (Zn, Cu and Cd) was performed, and factors that are predictive of toxicological endpoints in single metal and mixed metal exposures were identified. Cu, and to a lesser extent Cd, is found to associate with Escherichia coli in the exposure medium (the food source for C. elegans) as evidenced by the observed decrease in both their dissolved and free metal ion concentrations. Together with a critical analysis of literature data, our results suggest that free metal ion concentrations and thus aqueous uptake routes are the best predictor of internal concentrations under all conditions considered, and of metal toxicity in single metal exposures. Additional factors are involved in determining the toxicity of metal mixtures. In general, the eventual adverse effects of metals on biota are expected to be a consequence of the interplay between chemical speciation in the exposure medium, timescale of exposure, exposure route as well as the nature and timescale of the biotic handling pathways.

Establishing a health risk assessment for metal speciation in soil-A case study in an industrial area in China.

An improved method was proposed which integrates the distribution of metal speciation simulated by chemical equilibrium model, different exposure models and average daily intake dose modified by analytic hierarchy process for human health risk assessment of metal species (MS). With the rapid development of economic and urbanization, the metals pollution had become more serious in industrial areas. Adverse effects of soil contaminants on human health in typical industrial area should be assessed to evaluate the risks of soils in these areas. The method was applied to study nickel (Ni) species health risks in soil of industrial areas. The pH possessed significant impact to determine distribution/existence and solubility of Ni species, followed by DOC. The non-carcinogenic risk (HQ) of Ni species were less than 1 in each sampling points, except Ni2+. In addition, the carcinogenic risk (CR) of different Ni species were less than 10-6, except for FANi and Ni2+.