A review on the removal of heavy metals and metalloids by constructed wetlands: bibliometric, removal pathways, and key factors.

Heavy metals and metalloids (HMMs) pose a serious threat to both environmental and human health. The unique characteristics and environmental toxicity of HMMs make their removal from the environment a major challenge. Constructed wetlands (CWs) are increasingly being used as an eco-friendly system for the removal of HMMs from aqueous environments. In this review, bibliometric analysis was performed using the Scopus database using VOSviewer software to assess the developing use of CWs in recent years. Heavy metal and metalloid (HMM) removal pathways were reviewed (such as precipitation, co-precipitation, adsorption and ion exchange, plant action and microbial action) along with the impact of key factors (pH, chemical oxygen demand, dissolved oxygen, HMM concentration, and temperature). This review aimed to establish the connections between published results, to help effectively optimize the use of CWs for the removal of HMMs and identify the most critical factors for their effective removal. Important aspects that require further research include assessing the synergistic toxicity between different pollutants and combining the use of CWs with other technologies to optimize pollutant remediation efficiency.

Parallel and comparative non-targeted metabolomic speciation analysis of metalloids and their non-metal analogues by HPLC-ICPMS/MS in mushrooms.

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.

First Characterization of the Formation of Anthocyanin-Ge and Anthocyanin-B Complexes through UV-Vis Spectroscopy and Density Functional Theory Quantum Chemical Calculations.

The occurrence of anthocyanin (ACN) and metal (Me) complexes has been widely supported by many research works while the possibility that ACNs bind to metalloids (Mds) is yet to be proven. Here, metalloids (H3BO3 for B; GeO2 for Ge) were added to cyanidin-based solutions at pH 5, 6, and 7 and ACN-Md stoichiometric ratios of 1:1, 1:10, 1:100, and 1:500, and UV-vis transmittance spectroscopy as well as density functional theory (DFT) calculations were performed to test this hypothesis. Ge and B addition caused bathochromic and hyperchromic shifts on ACN UV-vis spectra, particularly pronounced at pH 5 and a 1:500 (ACN:Md) ratio. ACN-Me complexation reactions have been evaluated where Ge showed a higher capability to bind to ACNs than B. Among the complexes envisioned, those labeled as b1, b2, and b3 feature UV-vis spectra compatible with experiments. The combination of experimental and computational data offers for the first time evidence of the formation of ACN-Md complexes.

Effects of aging and weathering on immobilization of trace metals/metalloids in soils amended with biochar.

Biochar is an effective amendment for trace metal/metalloid (TMs) immobilization in soils. The capacity of biochar to immobilize TMs in soil can be positively or negatively altered due to the changes in the surface and structural chemistry of biochar after soil application. Biochar surfaces are oxidized in soils and induce structural changes through physical and biochemical weathering processes. These changes in the biochar surface and structural chemistry generally increase its ability to immobilize TMs, although the generation of dissolved black carbon during weathering may increase TM mobility. Moreover, biochar modification can improve its capacity to immobilize TMs in soils. Over the short-term, engineered/modified biochar exhibited increased TM immobilization capacity compared with unmodified biochar. In the long-term, no large distinctions in such capacities were seen between modified and unmodified biochars due to weathering. In addition, artificial weathering at laboratories also revealed increased TM immobilization in soils. Continued collection of mechanistic evidence will help evaluate the effect of natural and artificial weathering, and biochar modification on the long-term TM immobilization capacity of biochar with respect to feedstock and synthesis conditions in contaminated soils.

Molecular and Functional Characterization of Grapevine NIPs through Heterologous Expression in aqy-Null Saccharomyces cerevisiae.

Plant Nodulin 26-like Intrinsic Proteins (NIPs) are multifunctional membrane channels of the Major Intrinsic Protein (MIP) family. Unlike other homologs, they have low intrinsic water permeability. NIPs possess diverse substrate selectivity, ranging from water to glycerol and to other small solutes, depending on the group-specific amino acid composition at aromatic/Arg (ar/R) constriction. We cloned three NIPs (NIP1;1, NIP5;1, and NIP6;1) from grapevine (cv. Touriga Nacional). Their expression in the membrane of aqy-null Saccharomyces cerevisiae enabled their functional characterization for water and glycerol transport through stopped-flow spectroscopy. VvTnNIP1;1 demonstrated high water as well as glycerol permeability, whereas VvTnNIP6;1 was impermeable to water but presented high glycerol permeability. Their transport activities were declined by cytosolic acidification, implying that internal-pH can regulate NIPs gating. Furthermore, an extension of C-terminal in VvTnNIP6;1M homolog, led to improved channel activity, suggesting that NIPs gating is putatively regulated by C-terminal. Yeast growth assays in the presence of diverse substrates suggest that the transmembrane flux of metalloids (As, B, and Se) and the heavy metal (Cd) are facilitated through grapevine NIPs. This is the first molecular and functional characterization of grapevine NIPs, providing crucial insights into understanding their role for uptake and translocation of small solutes, and extrusion of toxic compounds in grapevine.

Quantifying the Coupled Kinetic Reactions of Metals/Metalloids on Iron and Manganese Oxides.

Quantifying the coupled kinetic reactions of metals/metalloids on iron and manganese oxides is essential for predicting the fate of contaminants in the environment. In this perspective, a few key issues related to developing the quantitative models for the coupled kinetic reactions of metal and metalloids are discussed, including adsorption/desorption processes, redox reactions, and mineral dissolution/transformation. Future research areas are also briefly discussed.

Prevention of sulfide oxidation in waste rock by the addition of lime kiln dust.

During the operation of a mine, waste rock is often deposited in heaps and usually left under ambient conditions allowing sulfides to oxidize. To focus on waste rock management for preventing acid rock drainage (ARD) formation rather than ARD treatment could avoid its generation and reduce lime consumption, costs, and sludge treatment. Leachates from 10 L laboratory test cells containing sulfide-rich (> 60% pyrite) waste rock with and without the addition of lime kiln dust (LKD) (5 wt.%) were compared to each other to evaluate the LKD's ability to maintain near neutral pH and reduce the sulfide oxidation. Leaching of solely waste rock generated an acidic leachate (pH < 1.3) with high concentrations of As (21 mg/L), Cu (20 mg/L), Fe (18 g/L), Mn (45 mg/L), Pb (856 µg/L), Sb (967 µg/L), S (17 g/L), and Zn (23 mg/L). Conversely, the addition of 5 wt.% LKD generated and maintained a near neutral pH along with decreasing of metal and metalloid concentrations by more than 99.9%. Decreased concentrations were most pronounced for As, Cu, Pb, and Zn while S was relatively high (100 mg/L) but decreasing throughout the time of leaching. The results from sequential extraction combined with element release, geochemical calculations, and Raman analysis suggest that S concentrations decreased due to decreasing sulfide oxidation rate, which led to gypsum dissolution. The result from this study shows that a limited amount of LKD, corresponding to 4% of the net neutralizing potential of the waste rock, can prevent the acceleration of sulfide oxidation and subsequent release of sulfate, metals, and metalloids but the quantity and long-term stability of secondary minerals formed needs to be evaluated and understood before this method can be applied at a larger scale.

Metal(loid) oxide (Al2O3, Mn3O4, SiO2 and SnO2) nanoparticles cause cytotoxicity in yeast via intracellular generation of reactive oxygen species.

In this work, the physicochemical characterization of five (Al2O3, In2O3, Mn3O4, SiO2 and SnO2) nanoparticles (NPs) was carried out. In addition, the evaluation of the possible toxic impacts of these NPs and the respective modes of action were performed using the yeast Saccharomyces cerevisiae. In general, in aqueous suspension, metal(loid) oxide (MOx) NPs displayed an overall negative charge and agglomerated; these NPs were practically insoluble (dissolution < 8%) and did not generate detectable amounts of reactive oxygen species (ROS) under abiotic conditions. Except In2O3 NPs, which did not induce an obvious toxic effect on yeast cells (up to 100 mg/L), the other NPs induced a loss of cell viability in a dose-dependent manner. The comparative analysis of the loss of cell viability induced by the NPs with the ions released by NPs (NPs supernatant) suggested that SiO2 toxicity was mainly caused by the NPs themselves, Al2O3 and SnO2 toxic effects could be attributed to both the NPs and the respective released ions and Mn3O4 harmfulness could be mainly due to the released ions. Al2O3, Mn3O4, SiO2 and SnO2 NPs induced the loss of metabolic activity and the generation of intracellular ROS without permeabilization of plasma membrane. The co-incubation of yeast cells with MOx NPs and a free radical scavenger (ascorbic acid) quenched intracellular ROS and significantly restored cell viability and metabolic activity. These results evidenced that the intracellular generation of ROS constituted the main cause of the cytotoxicity exhibited by yeasts treated with the MOx NPs. This study highlights the importance of a ROS-mediated mechanism in the toxicity induced by MOx NPs.

Hydrothermal carbonisation of peat-based spent sorbents loaded with metal(loid)s.

Hydrothermal carbonisation (HTC) is a wet and relatively low-temperature process where, under autogenous pressures, biomass undergoes a chain of reactions leading to the defragmentation of organic matter. As well as its other uses (e.g. for producing low-cost carbon-based nano-compounds), HTC is utilised for the treatment of wet wastes, such as manure and biosludge. This study aimed to determine if hydrothermal carbonisation is a feasible treatment method for spent sorbents that are highly enriched with arsenic, chromium, copper, and zinc. The chemical properties of hydrochar and process liquid were evaluated after HTC treatment, where peat-based spent sorbents were carbonised at 230 °C for 3 h. Analysis of Fourier transform-infrared spectra revealed that during HTC, the oxygenated bonds of ethers, esters, and carboxylic groups were cleaved, and low-molecular-weight organic fragments were dissolved in the process liquid. A large fraction of arsenic (up to 62%), copper (up to 25%), and zinc (up to 36%) were transferred from the solids into the process water. Leaching of these elements from the hydrochars increased significantly in comparison with the spent sorbents.

Impact of declining oxygen conditions on metal(loid) release from partially oxidized waste rock.

The best available technology for preventing the formation of acid drainage water from the sulfidic waste rock at mine closure aims to limit the oxygen access to the waste. There is, however, a concern that contaminants associated with secondary minerals become remobilized due to changing environmental conditions. Metal(loid) mobility from partially oxidized sulfidic waste rock under declining and limited oxygen conditions was studied in unsaturated column experiments. The concentrations of sulfate and metal(loid)s peaked coincidently with declining oxygen conditions from 100 to < 5 sat-% and to a lesser extent following a further decrease in the oxygen level during the experiment. However, the peak concentrations only lasted for a short time and were lower or in the similar concentration range as in the leachate from a reference column leached under atmospheric conditions. Despite the acid pH (~ 3), the overall quality of the leachate formed under limited oxygen conditions clearly improved compared with atmospheric conditions. In particular, the release of As was two orders of magnitude lower, while cationic metals such as Fe, Cu, Mn, and Zn also decreased, although to a lesser extent. Decreased sulfide oxidation is considered the primary reason for the improved water quality under limited oxygen conditions. Another reason may be the immobility of Fe with the incorporation of metal(loid)s in Fe(III) minerals, in contrast to the expected mobilization of Fe. The peaking metal(loid) concentrations are probably due to remobilization from solid Fe(III)-sulfate phases, while the relatively high concentrations of Al, Mn, and Zn under limited oxygen conditions were due to release from the adsorbed/exchangeable fraction. Despite the peaking metal(loid) concentrations during declining oxygen conditions, it is clear that the primary remediation goal is to prevent further sulfide oxidation.

Metals and metalloids in traditional medicines (Ayurvedic medicines, nutraceuticals and traditional Chinese medicines).

Traditional medicine (TM) including Ayurvedic medicines, traditional Chinese medicines and nutraceuticals are popular across the globe as dietary supplements and traditional and alternative medicines. Health risks from these remedies continue to present serious concerns, with occurrences of poisoning by metals and metalloids present at concentrations above acceptable regulatory standards. This review overviews the prevalence of TM use, cases of metal and metalloid poisoning following TM consumption, and forms of TM contamination and adulteration. The review summarises regulations by the World Health Organization (WHO) and other relevant bodies. Finally, the review recommends how to protect consumers.

Characterization and screening of metals, metalloids and biomarkers in crude oil by ICP-MS/OES, and GC-MS techniques after digestion by microwave-induced combustion.

A method for digestion of light and medium Iraqi crude oils (Basrah and Khanaken oils) using microwave-induced combustion (MIC) in closed vessels is described for the determination of Hg, Au, Cu, Al, Ca, Co, K, Mg, Si and Sr by inductively coupled plasma optical emission spectrometry (ICP-OES) and Mo, Ti, Mn, Li, Se-1 , Rb, Ag, Ba, Pb, As, Cd, Cr, Fe, Ni, V and Zn by inductively coupled plasma mass spectrometry (ICP-MS). Upon using MIC it was possible to obtain lower limits of detection by ICP-MS and also by ICP-OES compared with those obtained by microwave-assisted digestion. The MIC was the best choice with regard to the possibility of using dilute nitric acid as an absorbing solution, which is important to minimize the interference encountered by ICP-MS and ICP-OES.The physicochemical parameters and some contaminants of crude oil samples were analyzed to classify and assess the quality of the crude oils. This study determines the viability of the use of Fourier transform infrared spectroscopy as an alternativee to traditional petroleum geochemical methods for crude oil characterization. The infrared fingerprints agree with the results obtained from GC-MS analysis.

Removal of Heavy Metals and Metalloids by Amino-Modified Biochar Supporting Nanoscale Zero-Valent Iron.

Nanoscale zero-valent iron (nZVI), an environmentally benign material, has been used to remove heavy metals and metalloids from the aqueous phase because of its high reactivity and abundant reactive sites. To improve the stability of nZVI, nanoscale zero-valent iron supported by amino-modified biochar (ZVIA-BC) was prepared and characterized. Its ability to remove heavy metals and metalloid was investigated. Fourier transform infrared spectroscopy analyses showed that the amino group was chemically bound to the functional groups of biochar. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction revealed that zero-valent iron was loaded on the biochar surface. High-resolution transmission electron microscope images showed that the particle size of iron was ∼50 nm and the particles consisted of roughly spherical cores covered with a shell that was uniformly 2- to 3-nm thick. Furthermore, measuring the zeta potentials at various pH values indicated that the iso-electric points occurred within the pH range of 7.50 to 7.56. Additionally, heavy metals and metalloids, including Cd(II), Ni(II), Cu(II), Cr(VI) and As(V) adsorption isotherms, on ZVIA-BC were significantly nonlinear, and ZVIA-BC exhibited a superior ability to remove these heavy metals and metalloids, especially for Cr(VI) and As(V). Characterization with high-resolution XPS revealed that reduction of heavy metals and metalloids occurred on the surface of ZVIA-BC. The main mechanisms for removal were reduction, complexation, co-precipitation, and electrostatic interaction.

Typical Gaseous Semi-Volatile Metals Adsorption by Meta-Kaolinite: A DFT Study.

Kaolinite can be used as in-furnace adsorbent to capture gaseous semi-volatile metals during combustion, incineration, or gasification processes for the purposes of toxic metals emission control, ash deposition/slagging/corrosion inhibition, ultrafine particulate matter emission control, and so on. In this work, the adsorptions of typical heavy metals (Pb and Cd) and typical alkali metals (Na and K) by meta-kaolinite were investigated by the DFT calculation. The adsorption energies followed the sequence of NaOH-Si surface > KOH-Si surface > PbO-Al surface ≈ CdO-Al surface ≈ NaOH-Al surface > KOH-Al surface > NaCl-Al surface ≈ Na-Si surface > Na-Al surface > KCl-Al surface > Pb-Al surface > PbCl2-Al surface > CdCl2-Al surface ≈ K-Si surface ≈ PbCl-Al surface > K-Al surface > CdCl-Al surface > NaCl-Si surface > KCl-Si surface > Cd-Al surface. Si surface was found available to the adsorptions of Na, K, and their compounds, although it was invalid to the adsorptions of Pb, Cd, and their compounds. The interactions between adsorbates and surfaces were revealed. Furthermore, the discussion of combining with the experimental data was applied to the subject validity of calculation results and the effect of chlorine on adsorption and the effect of reducing atmosphere on adsorption.

Exploring the potential of electroless and electroplated noble metal-semiconductor hybrids within bio- and environmental sensing.

Over the last two decades, the rapid development and widespread application of nanomaterials has significantly influenced research in various fields, including analytical chemistry and biosensing technologies. In particular, the simple functionalization and tuning of noble metal nanoparticle (NP) surface chemistry resulted in the development of a series of novel biosensing platforms with quick read-out and enhanced capabilities towards specific analyte detection. Moreover, noble metal NPs possess a number of unique properties, viz. high surface-to-volume ratio and excellent spectral, optical, thermal, electrical and catalytic characteristics. This manuscript provides an elaborate review on galvanic noble metal NPs deposited onto semiconductor surfaces, from the preparation stage towards their application in biosensors and gas sensing. Two types of deposition approaches, viz. galvanic displacement/electroless and conventional electroplating, are introduced and compared. Furthermore, the analytical merit of hybrid nanomaterials towards the improvement of sensing abilities is highlighted. Finally, some limitations and challenges related to progress in the development and application of analytical devices based on electroless and electroplated noble metal NPs-semiconductor hybrids (NMNPsHs) in biochemical and environmental sensing are discussed.

Distribution of metals and metalloids in dried seaweeds and health risk to population in southeastern China.

Concern about metals and metalloids, especially heavy metals in seaweeds has risen due to potential health risk. This study investigated the distribution of 10 metals and metalloids in 295 dried seaweeds (brown and red) and estimated the possible health risk via hazard index (HI). Elements in seaweeds can be sequenced in descending order by mean values: Al > Mn > As > Cu > Cr > Ni > Cd > Se > Pb > Hg. The levels of Cd, Cu, Mn and Ni in red seaweeds were significantly higher than those in brown seaweeds (P < 0.01). Correlation analysis showed contents of Ni-Cr (r = 0.59, P < 0.01) in seaweeds had moderate positive correlations. Seaweeds from different geographical origins had diverse element distribution. Risk assessment showed that HI at mean level was less than the threshold of 1. It indicates that for the general people there is low health risk to these elements by the intake of seaweeds. Furthermore, in terms of the confirmative toxicity of some metals, such as Cd, Pb and Hg, surveillance of metals in seaweeds should be performed continuously.

Reaction of 11 C-benzoyl chlorides with metalloid reagents: 11 C-labeling of benzyl alcohols, benzaldehydes, and phenyl ketones from [11 C]CO.

In this article, we describe the carbon-11 (11 C, t1/2  = 20.4 minutes) labeling of benzyl alcohols, benzaldehydes, and ketones using an efficient 2-step synthesis in which 11 C-carbon monoxide is used in an initial palladium-mediated reaction to produce 11 C-benzoyl chloride as a key intermediate. In the second step, the obtained 11 C-benzoyl chloride is further treated with a metalloid reagent to furnish the final 11 C-labeled product. Benzyl alcohols were obtained in moderated to high non-isolated radiochemical yields (RCY, 35%-90%) with lithium aluminum hydride or lithium aluminum deuteride as metalloid reagent. Changing the metalloid reagent to either tributyltin hydride or sodium borohydride, allowed for the reliable syntheses of 11 C-benzaldehydes in RCYs ranging from 58% to 95%. Finally, sodium tetraphenylborate were utilized to obtain 11 C-phenyl ketones in high RCYs (77%-95%). The developed method provides a new and efficient route to 3 different classes of compounds starting from aryl iodides or aryl bromides.

Effect doses for protection of human health predicted from physicochemical properties of metals/metalloids.

Effect doses (EDs) of metals/metalloids, usually obtained from toxicological experiments are required for developing environmental quality criteria/standards for use in assessment of hazard or risks. However, because in vivo tests are time-consuming, costly and sometimes impossible to conduct, among more than 60 metals/metalloids, there are sufficient data for development of EDs for only approximately 25 metals/metalloids. Hence, it was deemed a challenge to derive EDs for additional metals by use of alternative methods. This study found significant relationships between EDs and physicochemical parameters for twenty-five metals/metalloids. Elements were divided into three classes and then three individual empirical models were developed based on the most relevant parameters for each class. These parameters included log-ßn, ΔE0 and Xm2r, respectively (R2 = 0.988, 0.839, 0.871, P < 0.01). Those models can satisfactorily predict EDs for another 25 metals/metalloids. Here, these alternative models for deriving thresholds of toxicity that could be used to perform preliminarily, screen-level health assessments for metals are presented.

Comparison of sample preparation procedures on metal(loid) fractionation patterns in lichens.

The effects of different sample preparation strategies and storage on metal(loid) fractionation trends in plant material is largely underresearched. In this study, a bulk sample of lichen Parmotrema austrosinense (Zahlbr.) Hale was analysed for its total extractable metal(loid) content by ICP-MS, and was determined to be adequately homogenous (<5% RSD) for most elements. Several subsets of this sample were prepared utilising a range of sample preservation techniques and subjected to a modified sequential extraction procedure or to total metal extraction. Both experiments were repeated after 1-month storage at 4 °C. Cryogenic freezing gave the best reproducibility for total extractable elemental concentrations between months, indicating this to be the most suitable method of sample preparation in such studies. The combined extraction efficiencies were >82% for As, Cu, Mn, Pb, Sr and Zn but poor for other elements, where sample preparation strategies 'no sample preparation' and 'dried in a desiccator' had the best extraction recoveries. Cryogenic freezing procedures had a significantly (p < 0.05) negative effect on metal extractability, and is therefore inappropriate for sequential extraction procedures in lichens. Biotransformation over a period of a month is suspected for most elements, with the exception of Sr and Zn, where changes in the fractionation patterns were statistically significant (p < 0.05), indicating the need for minimal delay in sample cleaning and preservation when species fractionation patterns are of interest. This study also shows that the assumption that species stability can be ensured through cryopreservation and freeze drying techniques needs to be revisited.