As an essential micronutrient for animals with a narrow range between essentiality and toxicity, selenium (Se) usually coexists with chromium (Cr) in contaminated aquatic environments. This study investigated effects of three diets (Microcystis aeruginosa, Chlorella vulgaris and biofilms) exposed to Se or/and Cr on Aedes albopictus as a vector for the aquatic-terrestrial transfer of Se and Cr. Se(IV)-exposed mosquitoes concentrated Se up to 66-fold faster than Se(VI)-exposed ones, corresponding to the greater Se enrichment in Se(IV)-treated diets. Analysis using synchrotron-based X-ray absorption spectroscopy (XAS) showed that Se(0) (61.9–74.6%) dominated Se(VI)-exposed mosquitoes except for the C. vulgaris-fed larvae (organo-Se, 94.0%), while organo-Se accounted for 93.3–100.0% in Se(IV)-exposed mosquitoes. Cr accumulation in larvae (56.40–87.24 μg Cr/g DW) or adults (19.41–50.77 μg Cr/g DW) was not significantly different among all Cr(VI) treatments, despite varying diet Cr levels. With Cr(0) being dominant (57.7–94.0%), Cr(VI)-exposed mosquitoes posed little threat to predators. Although mosquitoes exposed to Se or Cr had shorter wings, adults supplied with C. vulgaris or biofilms co-exposed to Se(VI) and Cr(VI) had wings significantly (1.1–1.2 fold) longer than Se(VI) only exposed ones. Overall, our study reveals the role of Ae. albopictus in transferring waterborne Se and Cr from the contaminated aquatic ecosystem to the terrestrial ecosystem with the resulting eco-risks to wildlife in both ecosystems.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

Chromium (Cr) is a toxic element among which hexavalent chromium [Cr(VI)] is more toxic than trivalent chromium [Cr(III)]. Chromium can be reduced or oxidized in soil because soil is a complex medium and various soil components affect redox reaction of Cr in soil. Therefore, Cr speciation in hydroponics and soil was compared and Cr uptake and speciation by lettuce grown in the media were evaluated. Higher phytotoxicity was found in Cr(III) spiked soil than in Cr(VI) spiked soil, while Cr toxicity was higher in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Chromium was mainly accumulated in lettuce roots as Cr(III), and more Cr was translocated from roots to shoots grown in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Accumulation of Cr in roots grown in Cr(III) treated nutrient solution reduced Fe, K, Ca, Mg, and P uptake in lettuce. Chromium valence state was Cr(III) in lettuce leaves and roots grown in both Cr(III) and Cr(VI) treated hydroponics and soil. Chromium speciation in hydroponically grown lettuce roots was Cr(III) coordinated with 6 oxygens in the first shell and 2 or 4 carbons in the second shell as analyzed by X-ray absorption spectroscopy (XAS), which was similar to chromium acetate. The valence state of Cr in Cr(III) and Cr(VI) treated nutrient solution was not changed, while Cr(VI) was reduced to Cr(III) in Cr(VI) spiked soil by soil organic matter. Spiking of Cr(III) induced reduction of Mn in soil, which resulted in an increase of bioavailable Mn concentration in the Cr(III) spiked soil. Therefore, the increased phytotoxic effect for lettuce in Cr(III) spiked soil can be attributed to the reduction of Mn and subsequent release of Mn(II). For Cr(III) contaminated soil, Mn speciation should be considered, and bioavailable Mn concentration should be monitored although Cr existed as Cr(III) in soil.

Present study reports the laboratory and field scale application of different organic and inorganic amendments to immobilize cadmium (Cd) and lead (Pb) in a co-contaminated alluvial paddy soil. For that purpose, lime, biochar, Fe-biochar and two composite amendments (CA) composed of biochar, lime, sepiolite and zeolite (CA1: composite amendment 1) and manure, lime and sepiolite (CA2: composite amendment 2) were firstly tested in an incubation experiment to ameliorate Cd and Pb co-contaminated alluvial soil. It was observed that liming and CA2 elevated the soil pH and reduced DTPA extractable Cd and Pb in the incubated soil leading to higher metal immobilization. Therefore, efficiency of lime and CA2 was further investigated in field conditions with mid rice as the test crop to evaluate field scale immobilization and precise application rate for the tested soil type. DTPA and CaCl₂ extractable Cd (46 and 51%) and Pb (68 and 70%) in field soil were decreased with applied treatments. Speciation of Cd and Pb also promoted conversion of metal exchangeable contents to less-available forms. Activated functional groups on amendments’ surface (_OH bonding, C_O and CO, -O-H, Si–O–Si, carboxylic and ester groups) sequestered metals by precipitation, adsorption, ion exchange or electro static attributes. Application of lime at 2400 kg/acre (T4) and CA2 at 1200 kg/acre was more effective in reducing rice shoot and grains metal contents. Moreover, obtained results in terms of pH, extractable content, speciation and yield, and microanalysis of amendments highlights the remarkable efficiency of lime and composite amendment to sorb Cd and Pb providing the key evidence of these amendments for metals immobilization and environmental remediation. Considering these results, lime and CA2 are potential amendments for co-contaminated rice field especially in context of alluvial soil.

As a well-known toxic element, antimony occurred in a wide range of concentrations in the geothermal waters discharging from Rehai and Daggyai, two representative hydrothermal areas in the Yunnan-Sichuan-Tibet Geothermal Province of China. Antimony speciation in different types of the hot springs in Rehai and Daggyai varied greatly as well, and tri- and tetrathioantimonate were detected in most neutral to alkaline Rehai hot springs. Neutral to alkaline pH, high sulfide concentrations, and high sulfide to antimony ratios were the critical factors promoting the formation of thioantimonates. The fact that no thioantimonates were detected in neutral to alkaline Daggyai hot springs is attributed to high concentrations of coexistent arsenic capable of inhibiting the thiolation of oxyantimony anions, because thioantimonates are kinetically more labile than thioarsenates. Upon discharge of the hot springs, both total aqueous antimony and arsenic decreased rapidly and substantially via immobilization to the sediments in the spring vents and their outflow channels. Some of the common iron-bearing minerals in the spring sediments, like pyrite and goethite, are known sinks for antimony and arsenic. Yet, an interesting difference was observed with antimony and iron contents in the sediment samples showing a significant correlation that was lacking for arsenic and iron contents. The explanation might be that for arsenic, sorption affinities are known to vary significantly with aqueous arsenic speciation and mineral phases. Typically, thiolation increases, and oxidation decreases arsenic mobility. Sorption experiments for antimony conducted in the present study, in contrast, showed that different antimony species were comparably sorbed to pyrite over a wide range of initial antimony concentrations and to goethite at relatively low initial antimony concentrations (but still covering the concentration range of antimony in common natural waters), so neither thiolation nor oxidation contributed significantly to the mobility of antimony in the hot springs investigated in this study.

The present study proposes a maize sprouts hydroponic growth model to evaluate the As, Cd, Cr and Pb translocation from multinutrient fertilizer and to do speciation of As and Cr in this fertilizer and As in parts of plant in order to predict their phytoavailability. X-ray absorption near edge structure (XANES) was employed to speciate As and Cr directly on fertilizer solid sample. Arsenate (Asⱽ) and a solid solution of FeCrO₃ were the major species identified in the samples. The sprouts were hydroponically cultivated in water, fertilizer slurry and fertilizer extract media. Concentrations of As, Cd and Pb measured on leaves of maize sprouts ranged from 0.061 to 0.31 mg kg⁻¹, whereas Cr was not translocated to the aerial parts of sprouts. High performance liquid chromatographic with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) analysis was used to determine As speciation in maize sprouts, as well as in the fertilizer extracts and slurries. Arsenate was the only species identified in the initial fertilizer extract and this information is in agreement with the XANES results. However, the reduction of arsenate to arsenite was observed in extracts and slurries collected after sprout growth, probably due to the action of exudates secreted by plant roots. Arsenite was the predominant species identified in sprouts, the high phosphate concentration in the medium may have contributed to reduce arsenate phytoavailability.

Arsenic (As) contamination of water poses severe threats to human health and thus requires effective remediation methods. In this study, Synechocystis PCC6803, a model cyanobacterium common in aquatic environments, was used to investigate the role of extracellular polymeric substances (EPS) in As toxicity, accumulation, and transformation processes. We monitored the growth of Synechocystis with As exposure, measured the zeta potential and binding sites on the cell surface, and analysed As accumulation and speciation in Synechocystis cells with and without EPS. After EPS removal, the binding sites and zeta potential of the cell surface decreased by 44.43% and 31.9%, respectively. The growth of Synechocystis decreased 49.4% and 43.7% with As⁽ᴵᴵᴵ⁾ and As⁽ⱽ⁾ exposure, and As accumulation in the cells decreased by 12.8–44.5% and 14–42.7%, respectively. As absorption was enhanced in cells with EPS removed. The oxidation of As⁽ᴵᴵᴵ⁾ and reduction of As⁽ⱽ⁾ were significantly greater in cells with intact EPS compared to those with EPS removed. Fourier transform infrared spectroscopy (FTIR) showed that functional groups of EPS and Synechocystis cells, including –NH, –OH, CO, and CC, interacted with As species. Together the results of this work demonstrate that EPS have significant impacts on cell surface properties, thereby affecting As accumulation and transformation in Synechocystis PCC6803. This work provides a basis for using EPS to remedy As pollution in aquatic environments.

The microbe-driven iron cycle plays an important role in speciation transformation and migration of arsenic (As) in soil-rice systems. In this study, pot experiments were used to investigate the effect of bacterial iron (Fe) reduction processes in soils on As speciation and migration, as well as on As uptake in soil-rice system. During the rice growth period, pH and electrical conductivity (EC) in soil solutions initially increased and then decreased, with the ranges of 7.4–8.8 and 116.3–820 mS cm⁻¹, respectively. The concentrations of Fe, total As and As(III) showed an increasing trend in the rhizosphere and non-rhizosphere soil solutions with the increasing time. Fe concentrations were significantly positively correlated with total As and As(III) concentrations (***p < 0.001) in the soil solutions. The abundances of the arsenate reductase gene (arsC) and the As(III) S-adenosylmethionine methyltransferase gene (arsM) in rhizosphere soils were higher than those in non-rhizosphere soils, while the abundance of the Fe-reducing bacteria (Geo) showed an opposite trend. Moreover, it showed that the Geo abundance was significantly positively correlated with that of the arsC (***p < 0.001) and arsM (**p < 0.01) genes, respectively. The abundances of Geo, arsC and arsM genes were significantly positively correlated with the concentrations of Fe, total As and As(III) in the soil solutions (*p < 0.05). Moreover, the abundances of arsC and arsM genes were significantly negatively correlated with total As and As(III) in rice grains (*P < 0.05). These results showed that the interaction of bacterial Fe reduction process and radial oxygen loss from roots promoted the reduction and methylation of As, and then decreased As uptake by rice, which provided a theoretical basis for alleviating As pollution in paddy soils.

The synergistic cooperation of microbial cells and their extracellular polymeric substances (EPS) in biofilms is critical for the biofilm’s resistance to heavy metals and the migration and transformation of heavy metals. However, the effects of different components of biofilms have not been fully understood. In this study, the spatial distribution and speciation of copper in the colloidal EPS, capsular EPS, cell walls and membranes, and intracellular fraction of unsaturated Pseudomonas putida (P. putida) CZ1 biofilms were fully determined at the subcellular level. It was found that 60–67% of copper was located in the extracellular fraction of biofilms, with 44.7–42.3% in the capsular EPS. In addition, there was 15.5–20.1% and 17.2–21.2% of copper found in the cell walls and membranes or the intracellular fraction, respectively. Moreover, an X-ray absorption fine structure spectra analysis revealed that copper was primarily bound by carboxyl-, phosphate-, and hydrosulfide-like ligands within the extracellular polymeric matrix, cell walls and membranes, and intracellular fraction, respectively. In addition, macromolecule quantification, fourier-transform infrared spectroscopy spectra and sulfur K-edge x-ray absorption near edge structure analysis further showed the carboxyl-rich acidic polysaccharides in EPS, phospholipids in cell walls and cell membranes, and thiol-rich intracellular proteins were involved in binding of copper in the different components of biofilm. The full understanding of the distribution and chemical species of heavy metals in biofilms not only promotes a deep understanding of the interaction mechanisms between biofilms and heavy metals, but also contributes to the development of effective biofilm-based heavy metal pollution remediation technologies.

Potentially toxic elements (PTEs) are of major concern due to their high persistence and toxicity. Recently, rare earth elements (REEs) concentration in aquatic ecosystems has been increasing due to their application in modern technologies. Thus, this work aimed to study, for the first time, the influence of REEs (lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium and yttrium) and of salinity (10 and 30) on the removal of PTEs (Cd, Cr, Cu, Hg, Ni and Pb) from contaminated waters by living macroalgae (Fucus spiralis, Fucus vesiculosus, Gracilaria sp., Osmundea pinnatifida, Ulva intestinalis and Ulva lactuca). Experiments ran for 168 h, with each macroalga exposed to saline water spiked with the six PTEs and with the six PTEs plus nine REEs (all at 1 μmol L⁻¹) at both salinities. Results showed that all species have high affinity with Hg (90–99% of removal), not being affected neither by salinity changes nor by the presence of other PTEs or REEs. Cd showed the lowest affinity to most macroalgae, with residual concentrations in water varying between 50 and 108 μg L⁻¹, while Pb removal always increased with salinity decline (up to 80% at salinity 10). REEs influence was clearer at salinity 30, and mainly for Pb. No substantial changes were observed in Ni and Hg sorption. For the remaining elements, the effect of REEs varied among algae species. Overall, the results highlight the role of marine macroalgae as living biofilters (particularly U. lactuca), capable of lowering the levels of top priority hazardous substances (particularly Hg) and other PTEs in water, even in the presence of the new emerging contaminants - REEs. Differences in removal efficiency between elements and macroalgae are explained by the contaminant chemistry in water and by macroalgae characteristics.