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The complete characterization of selenium-enriched yeast in terms of selenium species has been the goal of extensive research for the last three decades. This contribution addresses the two outstanding questions: the mass balance of the identified and reported selenium species and the possible presence of inorganic selenium. For this purpose, four procedures have been designed combining, in diverse order, the principal steps of selenium speciation analysis in Se-rich yeast: extraction of the Se-metabolome, derivatization of cysteine and Se-cysteine (SeCys) residues, proteolysis, and definitive Se recovery using SDS extraction, followed by mineralization. The recovery of selenium in each step and its speciation were controlled by ICP MS and by reversed-phase HPLC-ICP MS, respectively. The study, carried out for the SELM-1 reference material, demonstrated the presence of about 10% of inorganic selenium and a serious risk of losses of SeCys during derivatization and proteolysis. As result of our work, we postulate the following values for SELM-1: Se-metabolome fraction (SeMF) 14.8 ± 0.7%; total selenomethionine (SeMet) 66.2 ± 2.7% (including ca. 1.5% SeMet present in the SeMF); total SeCys 12.5 ± 1.5% (including 2% of SeCys present in the Se-MF); total inorganic selenium 9.7 ± 1.7%, accounting for > 99.8% of the selenium. [ABSTRACT FROM AUTHOR]

Global warming has accelerated the iodine cycle in the Arctic Ocean, amplifying its significance in the global iodine cycle. However, some intricacies of the iodine cycle in the Arctic marine environment remain unclear. In this study, we present concentrations of stable- and radio-iodine (127I and 129I) in total iodine, iodide (I–), and iodate (IO 3 –) in seawater from the Beaufort, Chukchi, and Bering Seas. Results show a wide range of 129I/127I ratios of total iodine (3.2 × 10–12–9.3 × 10–9), indicating that the total 129I/127I ratio is a valuable fingerprint for identifying water masses and comprehending mixing processes. Iodine loss in surface seawater was quantitatively assessed using 129I, revealing that Arctic rivers substantially contribute to the emission of iodine into the atmosphere from the Arctic and subarctic seas. Our redox simulation in the Arctic intermediate layer shows the concentrations and 129I/127I ratios of I– and IO 3 – during its migration and provides the first evidence of an IO 3 – reduction process masked by the I– oxidation in the intermediate Arctic Ocean. Oxidation and reduction processes in the intermediate Arctic Ocean were characterized by extremely slow rates, at 0.95–2.41 and 0.26 ± 0.13 nM/year, respectively. Our findings demonstrate the effectiveness of anthropogenic 129I in tracking iodine cycling in the Arctic marine environment. [ABSTRACT FROM AUTHOR]

The release of nickel "Ni(II)" into aquatic environments is of great concern because of environmental and health issues. Metal-organic frameworks (MOFs) are one of the most promising technologies for removing heavy metals from water. In this work, an octahedral Co-based MOF (Co-MOF) was synthesized with a high Ni(II) removal capacity (qmax of 1534.09 ± 45.49 mg g−1) in aqueous media. For the first time, the effect of Co-MOF alone and in co-exposure with Ni(II) on nitrifying microbial consortium was assessed using dynamic microrespirometry. A single concentration of Co-MOF had no significant effects on nitrifying microbial consortium, while the concentration of Ni(II) exerted non-competitive inhibition on the nitrifying microbial consortium with an IC50 of 1.67 ± 0.03 mg L−1. In addition, the theoretical speciation analysis showed a decrease of 40% of IC50 when the free Ni(II) concentration was considered. Co-exposure of Co-MOF and Ni(II) during the nitrifying process allowed us to conclude that Co-MOF is an effective adsorbent for Ni(II) and can be used to mitigate the inhibitory effects of nickel on nitrifying microbial consortia, which is crucial for maintaining the good operation of wastewater treatment and balance of nitrogen cycle. [ABSTRACT FROM AUTHOR]

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The chloroplast (cp.) genome, also known as plastome, plays crucial roles in plant survival, adaptation, and evolution. The stable genetic structure of cp. genomes provides an ideal system for investigating species evolution. We sequenced three complete cp. genome sequences of Capsicum species and analyzed them using sequences of various Capsicum species retrieved from the NCBI database. The cp. genome of Capsicum species maintains a well-preserved quadripartite structure consisting of two inverted repeats (IRs) flanked by a large single copy (LSC) region and a small single copy (SSC) region. The sizes of cp. genome sequences ranged from 156,583 bp (C. lycianthoides) to 157,390 bp (C.pubescens). A total of 127–132 unique genes, including 83–87 protein-coding, 36–37 tRNA, and eight rRNA genes, were predicted. Comparison of cp. genomes of 10 Capsicum species revealed high sequence similarity in genome-wide organization and gene arrangements. Fragments of trnT-UGU/trnL-UAA, ccsA, ndhD, rps12, and ycf1 were identified as variable regions, and nucleotide variability of LSC and SSC was higher than that of IR. Phylogenetic speciation analysis showed that the major domesticated C. annuum species were the most extensively divergent species and closely related to C. tovarii and C. frutescens. Analysis of divergent times suggested that a substantial range of speciation events started occurring ~ 25.79 million years ago (Mya). Overall, comparative analysis of cp. genomes of Capsicum species not only offers new insights into their genetic variation and phylogenetic relationships, but also lays a foundation for evolutionary history, genetic diversity, conservation, and biological breeding of Capsicum species. [ABSTRACT FROM AUTHOR]

The hyphenation of HPLC with its high separation ability and ICP-MS with its excellent sensitivity, allows the analysis of Pt drugs in biological samples at the low nanomolar concentration levels. On the other hand, LC-MS provides molecular structural confirmation for each species. Using a combination of these methods, we have investigated the speciation of the photoactive anticancer complex diazido Pt(IV) complex trans, trans, trans-[Pt(N3)2(OH)2(py)2] (FM-190) in aqueous solution and biofluids at single-digit nanomolar concentrations before and after irradiation. FM-190 displays high stability in human blood plasma in the dark at 37 °C. Interestingly, the polyhydroxido species [{PtIV(py)2(OH)4} + Na]+ and [{PtIV(py)2(N3)(OH)3} + Na]+ resulting from the replacement of azido ligands, as determined by LC-MS, were the major products after photoirradiation of FM-190 with blue light (463 nm). This finding suggests that such photosubstituted Pt(IV) tri- and tetra-hydroxido species could play important roles in the biological activity of this anticancer complex. Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations show that these Pt(IV) species arising from FM-190 in aqueous media can be formed directly from a singlet excited state. The results highlight how speciation analysis (metallomics) can shed light on photoactivation pathways for FM-190 and formation of potential excited-state pharmacophores. The ability to detect and identify photoproducts at physiologically-relevant concentrations in cells and tissues will be important for preclinical development studies of this class of photoactivatable platinum drugs. [ABSTRACT FROM AUTHOR]

This study addresses the development and validation of an analytical method for speciation analysis of mercury (inorganic/Hg2+ and methylmercury/CH3Hg+) in fishery products. The Hg species are separated by reversed-phase (RP) high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The effective separation of Hg2+ and CH3Hg+ was achieved in <8 min using a peptide mapping RP column and a mobile phase containing 2-mercaptoethanol at 0.25% (v/v) and methanol at 1% (v/v). The optimization was carried out using an experimental design through response surface methodology (RSM) with central composite design (CCD), addressing both the HPLC separation and the sample extraction. The method validation was carried out based on the accuracy profile approach. For this purpose, six series of measurements were carried out in duplicate over a time span of 2 months. The limits of quantification (LOQ) were 2.5 µg/kg (wet weight, ww) for CH3Hg+ and 1.2 µg/kg (ww) for Hg2+. The intermediate reproducibility in terms of coefficient of variation (CVR) was <6%. The bias (%) obtained for the analysis of four certified reference materials (CRMs), namely TORT-3 (lobster hepatopancreas), SRM 1566-b (oyster tissue), SQID-1 (cuttlefish) and NMIJ CRM 7402-a (cod fish tissue) was <7%. This demonstrates the method robustness and suitability for routine speciation analysis of CH3Hg+ and Hg2+ in fishery products. The method is intended to be applied for the analysis of the panel of fishery products and fish-based foods in the framework of the (ongoing) third French Total Diet Study. [ABSTRACT FROM AUTHOR]

The issue of soil contamination by heavy metals is widely acknowledged. Some plants, including medicinal species like St. John's wort (Hypericum perforatum L.), exhibit accumulation traits, allowing them to accumulate elevated levels of metals, e.g., cadmium (Cd), within their cells. Selenium (Se) may increase the tolerance of plants to abiotic stress caused by the presence of heavy metal in the environment. Depending on its form (oxidation state, organic/inorganic), Se influences plant growth, secondary metabolite content, and biotic stress, as well as incorporates into shoots, providing economic and health benefits for consumers. So far, there are no data on the influence of organic Se(IV) on plants. Our study aimed to determine the effect of organic Se(IV) on the growth, active compound levels (anthranoids, polyphenols), and ultrastructure of St. John's wort without and under cadmium stress. The phytochemical analysis and microscopic examination was performed on shoots from different days of St. John's wort in vitro culture on a few variants of Murashige and Skoog medium with Cd (25 and 400 µM) and/or organic Se (IV). Exposure to Se(IV) did not affect hypericins but increased the polyphenol content in the shoots and the biomass. Se(IV) caused an increase in starch grain number in chloroplasts, whereas Cd exposure resulted in the degradation of the chloroplast structure, increased cell vacuolation, as well as swollen mitochondrial cristae. The addition of Se(IV) to these combinations reduced the degree of degradation and growth inhibition and a high content of Se(IV) in plants was observed. Se(IV) had no impact on Cd content at environmental Cd concentrations, but showed an effect at extremely high Cd concentrations. Thus, organic Se(IV) has a beneficial effect on St. John's wort growth, polyphenol content, and incorporation in shoots and prevents Cd toxicity. Media enriched with organic Se(IV) have both economic advantages and health benefits due to a higher plant growth rate and increased concentrations of polyphenols with strong antioxidant properties, relatively enriched with Se. However, organic Se(IV) should be used with caution in polluted areas. In perspective, speciation analysis and molecular study are crucial to understand the fate and effect of Se (IV) on plants. [ABSTRACT FROM AUTHOR]

Chromium occurs naturally in different oxidation states. Amongst them, hexavalent chromium is classified as both genotoxic and carcinogenic while trivalent chromium can be considered as an essential element. Therefore, speciation analysis is essential when conducting dietary exposure assessment. Several critical reviews have been published on chromium speciation analysis in foodstuffs in the last decade. However, a method that can account for species interconversion during the extraction procedure has not been reported in the reviews. In recent years, an online method using species-specific isotope dilution mass spectrometry has been developed for the simultaneous determination of trivalent and hexavalent chromium in foodstuffs. Apart from that, new methods based on offline analytical techniques, to analyse trivalent and hexavalent chromium separately, are still under development. Therefore, one of the objectives of this paper is to review these recently published analytical methods and assess whether they are fit for chromium speciation analysis in foodstuffs. Additionally, an objective is also to assess whether their limits of detection are sufficiently low for dietary exposure assessment with respect to the neoplastic effects of hexavalent chromium. Moreover, possible future research gaps are identified based on the current knowledge and existing literature. [ABSTRACT FROM AUTHOR]

This is the 16th Atomic Spectrometry Update (ASU) to focus on advances in elemental speciation and covers a period of approximately 12 months from January 2023. This ASU review deals with all aspects of the analytical atomic spectrometry speciation methods developed for: the determination of oxidation states; organometallic compounds; coordination compounds; metal and heteroatom-containing biomolecules, including metalloproteins, proteins, peptides and amino acids; and the use of metal-tagging to facilitate detection via atomic spectrometry. As with all ASU reviews the focus of the research reviewed includes those methods that incorporate atomic spectrometry as the measurement technique. However, because speciation analysis is inherently focused on the relationship between the metal(loid) atom and the organic moiety it is bound to, or incorporated within, atomic spectrometry alone cannot be the sole analytical approach of interest. For this reason, molecular detection techniques are also included where they have provided a complementary approach to speciation analysis. The number of publications covered this year has increased since last year but remains relatively low compared to many of the years that this ASU has been published for. However, there is a good breadth of elements covered, over 20 this year, with the most popular elements still being As, Hg and Se whilst Ge and Tc both make their first appearances this year. Another item to note is the decreasing quality of the abstract for many of the papers, with detail on the methodology, key results with data included, conclusions and implications thereof missing. This is likely to lead to fewer researchers reading the article. [ABSTRACT FROM AUTHOR]

One of the most important issues considered in ecotoxicology is the elevated accumulation of different elements in soil as a consequence of anthropogenic activities. In this paper, determination of nine elements in soil obtained from three different forest complexes (sycamore, beech, and spruce) in urbanized and non-urbanized regions of Tatra National Park is presented. Additionally, a comprehensive presentation of detailed results of correlation analyses between individual elements in accordance to each valley, as well as to selected species of trees, is shown. Speciation studies included chemical forms of the following elements: Fe, Mn, Zn, Cu, Pb, Cd, Ni, Cr, Co. Soil extracts were obtained in accordance with Rudd’s methodology and all species were determined using atomic absorption spectrophotometry (AAS). The study compares the content of selected chemical forms (exchangeable and adsorbed, organic solutions and carbonates) of chosen metals in soil of four valleys of Tatra National Park: Chochołowska, Strążyska, Mała Łąka, and Kościeliska. The first three (group A) are considered as non-urbanized areas, whereas the last four (group B), on the account of many home fireplaces located there, as urbanized areas. [ABSTRACT FROM AUTHOR]

The review reports on investigations and studies that have contributed in the last 20 years (2003–2023) to the clarification of the mechanisms governing the chemical vapor generation (CVG) of hydrides and other volatile metallic species using aqueous phase derivatization with tetrahydridoborate (1-)(THB) and amine boranes, which is widely used in determination and speciation analysis of trace elements by atomic optical and mass spectrometry. The discussion begins with the early investigations leading to definition of the mechanism of hydrolysis of aqueous THB and that of reaction conditions. The new knowledge represents important achievements for the clarification of controversial aspects that plagued CVG for more than 35 years and stimulated further studies which are discussed in detail. They concern with the mechanism of hydrolysis of amine boranes, the mechanism of interferences, the role played by chemical additives and the definition of more general reaction models for CVG, which are valid for both analytical and non-analytical reaction conditions. The latest developments and the analytical applications of the new knowledge to trace element analysis are discussed. [ABSTRACT FROM AUTHOR]

Introduction: Environmentally friendly and efficient biochar precursor materials and their modification methods are of great significance in solving the problem of soil cadmium pollution. Materials and methods: This study prepared apple pomace biochar (ABC) from discharged apple pomace by pyrolysis at 500 °C. ABC was modified by phosphoric acid impregnation (P-ABC), MnO2 loading (Mn-ABC), and MnO2 loading after phosphoric acid impregnation (Mn-P-ABC). The biochar and modified biochar were described by infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. The impacts of original and modified biochar on soil characteristics and the immobilization of original and modified biochar with different additions (4, 7, 10 and 13%) on Cd in contaminated soils were studied. Results and discussion: The outcomes show that ABC, P-ABC, Mn-ABC, and Mn-P-ABC are porous and amorphous materials rich in functional groups. All four types of biochar can enhance soil organic matter content, cation exchange capacity, and pH value, effectively improving soil properties. After application of biochar materials, the extractable Cd in soil was obviously reduced compared to the control, and 13% Mn-P-ABC reduced the extractable Cd in the soil by 43.84%. The results of Cd speciation analysis indicate that after the application of biochar materials, the acid soluble Cd in the soil reduced and the residual Cd increased. Conclusions: The treatment with 13% Mn-P-ABC resulted in a 35.57% decrease in acid soluble Cd in soil and a 30.18% increase in residual Cd, indicating the best immobilization effect on Cd. [ABSTRACT FROM AUTHOR]

Heavy metal pollution from compost is one of the most concerned environmental problems, which poses a threat to the ecosystem and human health. This study aims to reveal the heavy metal tolerance and detoxification mechanism mediated by heavy metal resistance genes (HMRGs) in compost habitat through metagenomics combined with chemical speciation analysis of heavy metals. The results showed that there were 37 HMRGs corresponding to 7 common heavy metal(loid)s in composting, and they had the ability to transform heavy metals into stable or low-toxic speciation by regulating enzyme transport, redox, methylation, etc. This study summarized the heavy metal metabolism pathway mediated by HMRGs, providing a new perspective for understanding the transformation of heavy metals in the composting process. [ABSTRACT FROM AUTHOR]

Antimony (Sb) contamination poses significant environmental and health concerns due to its toxic nature and widespread presence, largely from anthropogenic activities. This study addresses the urgent need for an accurate speciation analysis of Sb, particularly in water sources, emphasizing its migration from polyethylene terephthalate (PET) plastic materials. Current methodologies primarily focus on total Sb content, leaving a critical knowledge gap for its speciation. Here, we present a novel analytical approach utilizing frontal chromatography coupled with inductively coupled plasma mass spectrometry (FC-ICP-MS) for the rapid speciation analysis of Sb(III) and Sb(V) in water. Systematic optimization of the FC-ICP-MS method was achieved through multivariate data analysis, resulting in a remarkably short analysis time of 150 s with a limit of detection below 1 ng kg−1. The optimized method was then applied to characterize PET leaching, revealing a marked effect of the plastic aging and manufacturing process not only on the total amount of Sb released but also on the nature of leached Sb species. This evidence demonstrates the effectiveness of the FC-ICP-MS approach in addressing such an environmental concern, benchmarking a new standard for Sb speciation analysis in consideration of its simplicity, cost effectiveness, greenness, and broad applicability in environmental and health monitoring. [ABSTRACT FROM AUTHOR]

The aim of this work is to develop a simple, sensitive, and reliable colorimetric test method for the visual detection of Fe(II) and Fe(III) in water. The sample solution of Fe(III) was initially complexed with chromeazurol S (CAS) followed by ion-pair association with cetyltrimethylammonium bromide (CTAB) in the presence of perchlorate ions. This led to the formation of a bulky and insoluble fluffy precipitate involving the physical entrapment of the ternary complex of Fe-CAS-CTAB, which floats on the top of the solution. Depending on the concentration of Fe(III), this type of ternary complex produces an impressive color change from reddish magenta to purple and then to cyan-blue, easily detectable with the naked eye without the need for expensive instrumentation. The ternary-colored complex was formed instantly and remained stable for at least 8 h with constant absorbance. For the determination of total iron and Fe(II), complete oxidation of Fe(II) to Fe(III) was carried out using 100 μL of KMnO4 (0.005%). The minimal response with the test method was found to be about 5 ng/mL of Fe(III) in 2 min of the total sample testing procedure. However, Fe(III) could be quantified using a spectrophotometer after dissolving the fluffy precipitate in toluene solvent. The calibration graph was linear in the range of 5–30 ng/mL of Fe(III) with a correlation coefficient of 0.9931 and a limit of detection of 0.9 ng/mL. The relative standard deviation was found to be less than 6%. At the end of the study, the efficacy of the method was evaluated by its application to groundwater and thermal power plant coolant waters. [ABSTRACT FROM AUTHOR]

Selenium (Se) is an essential trace element for humans and animals, and an excess of or deficiency in Se is harmful to health. Research on the selenium enrichment zone began in the late 1970s in Shuang'an, Ziyang, southern Shaanxi Province. Naore village is only one selenosis area in Shuang'an, Ziyang, China. Different scholars have conducted systematic studies on the occurrence of selenium, its organic geochemistry and biomarkers, and its content and enrichment patterns in this area. This study applied the TIMA (TESCAN integrated mineral analyzer) for the first time to conduct detailed mineralogical work. The minerals included quartz, carbonate minerals (calcite and dolomite), feldspar (plagioclase, albite, and orthoclase), biotite and muscovite, clay minerals (chlorite and kaolinite), hematite, pyrite, and accessory minerals (almandine, olivine, zircon, and apatite) in Naore village, Ziyang, Shaanxi Province. The ATi index (100 × apatite/(apatite + tourmaline)) is used to determine the source of heavy minerals and the degree of heavy minerals' weathering. The content POS (100 × (pyroxene + olivine + spinel)/transparent heavy mineral) of olivine, pyroxene, and spinel in heavy minerals can reflect the contribution of basic and ultrabasic rocks in the source area. The ATi and POS indexes for the heavy minerals in the research area were 91.83~99.96 and 0.01~18.75, respectively, reflecting the abundance of volcanic rock material in their source. In addition, the migration, transformation, bioavailability, and toxicity of selenium in the environment are closely related to its species. The species of selenium in various selenium-rich areas (Naore, Wamiao, and Guanquan) mainly include unusable residues and organic forms, followed by humic-acid-bound selenium. The proportions of water-soluble, exchangeable, and carbonate-bound selenium are relatively small, and the proportion of Fe-Mn oxide-bound selenium is the lowest. [ABSTRACT FROM AUTHOR]

Analytical atomic spectrometry is a well-established and widely-used analytical technique for the sensitive detection of inorganic elements in diverse samples. Sample pretreatment methods are still a critical part of elemental analysis, which are usually used to remove interfering matrix components and preconcentrate the targets of interest before analysis. Significant advances in the development of sample separation and preconcentration techniques for elemental analysis have been made in recent years. This review focuses on the applications of sample separation and preconcentration techniques for analytical atomic spectrometry, including liquid phase (micro)extraction, cloud point extraction, solid phase (micro)extraction, microwave-assisted extraction, ultrasonic-assisted extraction, chemical vapor generation as well as hyphenated techniques. This review presents several applications of the above sample pretreatment methods in recent years, whose advantages and drawbacks were also discussed. [ABSTRACT FROM AUTHOR]

The mercury cell manufacturing process, which has been extensively used in chlor-alkali plants to produce chlorine and caustic soda by electrolysis, represents a major source of Hg environmental pollution. At Saline di Volterra (Tuscany, Italy), solution mining by pumping water into halite deposits was applied to produce brines for a mercury-cell chlor-alkali plant. The Hg-contaminated, exhausted brines were pumped back at depth into the rock salt field in order to renew the available resources. Activities ceased in 1994, following the leakage dispersion of highly contaminated Hg(0)-bearing brines into the environment. The mercury content in the soil, measured during a survey conducted in 2000, reached 334 mg/kg, highlighting diffuse contamination in the floodplain. By 2009, the Hg concentration had generally decreased and was mostly confined to the topsoil layer. In order to evaluate the present Hg soil pollution, a geochemical survey was carried out in 2023, almost thirty years after the contamination event. The obtained data indicated the occurrence of legacy Hg, which reached 25.5 mg/kg in some soil samples. Speciation analysis for the most contaminated soil revealed that Hg(0) represented about 17.3% of the total Hg and that water-soluble and organic Hg fractions were negligible. These results suggest that the originally released metallic mercury has volatilized and likely oxidized, becoming practically immobile in the soil. A risk assessment, performed by applying Hg speciation analysis, indicated that the mercury in the soil does not carry a risk of non-cancerous effects for different exposure routes in case of subsequent use of the site and that the formerly contaminated area can now be converted into a leisure area. [ABSTRACT FROM AUTHOR]

In the last decades, the determination of trace elements in biological materials has emerged as an important area of study because of its relevance to human health and the environment. Inductively coupled plasma mass spectrometry (ICP-MS) has proven to be a powerful tool for trace element analysis, owing to its high sensitivity and ability to determine several elements in a single measurement. However, given the complex nature of biological matrices and the presence of elements, most of them at ultratrace levels, it becomes crucial to complement ICP-MS with preconcentration techniques to increase the sensitivity and selectivity of analytical methods. This article presents an exhaustive overview of liquid- and solid-phase preconcentration techniques used in combination with ICP-MS for trace element determination in different biological samples from 2000 to the present. An in-depth discussion of the advances on the application of state-of-the-art solvents and materials in trace element extraction and preconcentration is presented. Special attention is given to different strategies for elemental speciation analysis, employing both chromatographic and non-chromatographic techniques. The role of automation in these methodologies is also described. Finally, future trends and challenges related to this topic are discussed. [ABSTRACT FROM AUTHOR]

Speciation analysis plays a key role in understanding the biological activity and toxicity of an element. So far, classical speciation analysis focused only on the dissolved fraction of an elemental species, whereas nanoparticle forms of analytes are being widely found in consumer and industrial products. A significant contributor to human exposure to nanoparticles is through food into which nanoparticles can be incorporated from endogenous sources or they may be formed naturally in the living organisms. Nanoparticles often undergo changes in the food matrices and upon consumption, in the gastrointestinal tract, which present a significant challenge to their characterisation. Therefore, a combination of both classical and nanoparticle speciation analytical techniques is needed for the characterisation of both dissolved and particulate forms of the chemical species. This article presents and discusses the current trends in analysis of nanoparticle behaviour in the gastrointestinal tract and formation and characterisation of biogenic nanoparticles. [ABSTRACT FROM AUTHOR]

Thallium (Tl) pollution have attracted widespread attention in recent years due to is its high toxicity as well as its increasing release into the environment by human activities. Furthermore, its bioaccumulation can lead to various diseases and even death. Hence, accurate determination of Tl in biological and environmental samples is of utmost importance. This review provides an overview of analytical methods for the determination of Tl, drawing from over 200 references published mainly between 2012 and 2022. The reported methods for Tl detection include atomic emission spectrometry, atomic absorption spectrometry, inductively coupled plasma mass spectrometry, and molecular spectroscopy. For detection of Tl in environmental and biological samples, the current trends of sample pretreatment techniques were summarized. Additionally, the speciation analysis of two wo Tl species (i.e., Tl+ and Tl3+) was also briefly discussed. [ABSTRACT FROM AUTHOR]

Hexavalent chromium (Cr(VI)) is known as the most hazardous species of chromium. Speciation analysis of Cr in foods is of a great significance for assessing its influences on human health. In this study, a fast HPLC-ICP-MS method for the determination of Cr(VI) was developed for determining the content of Cr(VI) and also investigating its transformation in foods. The developed method employs an alkali extraction and weak anion-exchange column separation for distinguishing the Cr species, facilitating accurate Cr(VI) quantification within 1.5 min. This technique was applied to determine the Cr(VI) levels in a range of food products, including yoghurt, milk powder, rice flour, orange juice, green tea, white vinegar, and whole wheat bread. The results showed that no Cr(VI) was detected in these food products. Spiking experiments revealed that the recovery rate of Cr(VI) decreased with the increase in its contact time with food products. A further exploration of Cr(VI) in various food components such as vitamin C, tea polyphenols, whey proteins, gelatin, fructose, and cellulose indicated the conversion of Cr(VI) to organic Cr(III) over a period from 20 min to 60 h. It was found that high temperatures and acidic conditions accelerated the rate of Cr(VI) conversion to organic Cr(III) in the six food components mentioned above. This evidence suggests that natural reducing substances in foods probably prevent the occurrence of Cr(VI). [ABSTRACT FROM AUTHOR]

The production of selenium-enriched fish can contribute to alleviating selenium deficiency in human diets. However, it is still unclear which selenium source, as an additive, can efficiently and cost-effectively produce high-quality selenium-enriched fish. This study evaluated the effects of selenium nanoparticles (SeNP), selenite, and selenomethionine (SeMet) on the growth, antioxidant capacity, selenium content, selenium speciation, and meat quality of grass carp. Ten diets were prepared, including a basal diet (BD) and three concentrations (0.1, 0.3, and 0.9 mg/kg) of SeNP, selenite, and SeMet. A total of 600 fish (250.79 ± 1.57 g) were randomly assigned to 30 tanks (3 tanks/group). Fish were fed the experimental diet three times daily for 60 d. In this study, SeNP most significantly promoted the growth and antioxidant capacity of grass carp, with 0.3 mg/kg SeNP identified as the optimal additive concentration. Additionally, SeNP demonstrated equally excellent bioavailability as SeMet and significantly increased the content of SeMet in grass carp (Ctenopharyngodon idella) muscle. Furthermore, compared to SeMet and selenite, dietary SeNP could more significantly enhance the content of selenocysteine (SeCys2) and methylselenocysteine (MeSeCys) in grass carp muscle tissue. In addition, we have demonstrated that SeCys2 and MeSeCys promote apoptosis of cancer cells (HeLa) through the mitochondrial apoptotic pathway (involving Bax and Bcl-2). Furthermore, as an additive, 0.3 mg/kg SeNP significantly improved the flesh quality of grass carp by reducing crude fat and heavy metal content, as well as increasing the levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) and the ratio of n-3/n-6 polyunsaturated fatty acid (PUFA). In summary, SeNP is the most suitable additive for producing selenium-enriched fish.

The passerine superfamily Certhioidea lacks a complete phylogeny despite decades of recognition as a clade and extensive systematic work within all its constituent families. Here, we inferred a near-complete species-level phylogeny of Certhioidea from a molecular supermatrix, including the first comprehensive sampling of the wrens (Troglodytidae), and used this phylogeny to infer its biogeographic and diversification histories. We also inferred an expanded phylogeny including nearly 100 putative phylospecies previously documented in the literature, and we found that including this diversity had notable impacts on the inferred evolutionary history of Certhioidea. This phylospecies-level tree documented a few instances of species paraphyly, some previously described in the literature and some novel. We found that Certhioidea originated largely in Eurasia and dispersed into North America five times in the last 20 million years, including at the origin of the "New World certhioids," wrens and gnatcatchers, a clade herein named Orthourae. After this initial dispersal event, both wrens and gnatcatchers diversified extensively across the hemisphere, with both lineages repeatedly crossing between continents. However, we detected no notable impact of the formation of the Isthmus of Panama on the frequency of dispersal events between North and South America. The inclusion of phylospecies altered this biogeographic inference in some portions of the tree but overall was largely consistent. With species-level sampling, we found that diversification rates within Certhioidea were largely constant through time with a detectable deceleration toward the present. By contrast, phylospecies-level sampling recovered a different diversification history with a significant rate increase at the crown node of Orthourae after dispersing into the Americas and increased speciation rates particularly within the genera Polioptila and Henicorhina. This largely resolved phylogeny for Certhioidea has yielded important insights into the evolutionary history of this group and provides a framework for future comparative work on this fascinating clade. [ABSTRACT FROM AUTHOR]

The treatment of laboratory waste containing arsenic compounds should be part of the chemical analysis protocol in educational and research institutions. An alternative procedure for the treatment of these residues is proposed for the development of a didactic analytical route in the detection of As3+, As5+, MMA (monomethylarsonic acid) and DMA (dimethylarsinic acid). The treatment is based on the coprecipitation of inorganic arsenic species with a quaternary ammonium salt (tetra-n-butylammonium perchlorate) in suspension. Detection occurred by controlling the hydride generation reactions and Atomic Absorption Spectrometry. The methylated species MMA and DMA remain in the supernatant and can be monitored by adjusting the pH, concentration of the borohydride reducer, and the use of auxiliary reducers (hydroxylamine hydrochloride and KI). Satisfactory selective detectability was obtained for each arsenic species present in the waste sample. This work contributes to the development of experiments to be implemented in Qualitative Analytical Chemistry and Instrumental Analysis classes. The results allow to approach the chemical vapor generation, which is generally not well explored in undergraduate classes. Discussion of this procedure is supported by a teaching proposal based on the theory of nascent hydrogen for inorganic arsenic species and the nucleophilic performance of the hydride ion for methylated species. This approach allows the student to contextualize important concepts such as Lewis structure, oxidation state and kinetics of arsenic hydride generation reactions. This interdisciplinary contextualization forms a common theoretical basis, preparing and enabling the student to research speciation analysis by hydride generation and to understand the most accepted theories. [ABSTRACT FROM AUTHOR]

This research evaluates the modification of the lithium carbonate (Li2CO3) production process and particularly the boron removal step, which currently employs a recirculated stream. This recirculated stream is a liquor with low boron content but rich in lithium, currently being wasted. In this process, the recirculating stream is substituted with a freshwater stream. Boron is re-extracted from the loaded organic stream to form an input stream for a boric acid process. Under certain operational conditions, the formation of emulsions was observed; due to this, the analysis of emulsion formation involved controlling the pH of each sample, which lead to the development of a procedure to prevent such formations. From this analysis, it was determined that emulsions form in water with pH values below 1.3 and above 6.9. In addition, a speciation analysis showed that the concentrations of the H2BO3− and H+ species influence the formation of emulsions. The mass balance of the process showed that by replacing the recirculated stream, boron recovery of 89% was achieved, without the need to add new stages or equipment. [ABSTRACT FROM AUTHOR]

Arsenic, which can be divided into inorganic and organic arsenic, is a toxic metalloid that has been identified as a human carcinogen. A common source of arsenic exposure in seafood is arsenolipid, which is a complex structure of lipid-soluble organic arsenic compounds. At present, the known arsenolipid species mainly include arsenic-containing fatty acids (AsFAs), arsenic-containing hydrocarbons (AsHCs), arsenic glycophospholipids (AsPLs), and cationic trimethyl fatty alcohols (TMAsFOHs). Furthermore, the toxicity between different species is unique. However, the mechanism underlying arsenolipid toxicity and anabolism remain unclear, as arsenolipids exhibit a complex structure, are present at low quantities, and are difficult to extract and detect. Therefore, the objective of this overview is to summarize the latest research progress on methods to evaluate the toxicity and analyze the main speciation of arsenolipids in seafood. In addition, novel insights are provided to further elucidate the speciation, toxicity, and anabolism of arsenolipids and assess the risks on human health. [ABSTRACT FROM AUTHOR]

The document is a contents list for the Journal of Analytical Atomic Spectrometry. It provides information about the articles included in the journal's latest issue, including the authors, page numbers, and images. The articles cover a range of topics related to analytical atomic spectrometry, such as fingerprint scanning, X-ray fluorescence spectrometers, and elemental analysis. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

The performance of a nitrogen (N2)-sustained Microwave Inductively Coupled Atmospheric-Pressure Plasma (MICAP) – Quadrupole Mass Spectrometer (QMS) was explored as an alternative to the traditional argon (Ar) equivalent for arsenic (As) analysis in rice. Conventional Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) can be limited by Ar-based spectral interferences depending on sample matrices. Specifically, for the analysis of As, argon chloride ions (40Ar35Cl+) can interfere with the detection of the monoisotopic 75As+, and this interference can lead to systematic errors in As quantification. With N2-sustained MICAP-QMS, major plasma background species are N2-based, which eliminates the spectral interference possibility at mass-to-charge (m/z) 75 from 40Ar35Cl+. In this work, we present the first combination of the N2-MICAP-MS with anion exchange chromatography for As speciation and quantification from several rice varieties. We used a slightly modified As-species extraction procedure per Food and Drug Administration (FDA) protocol EAM 4.11. In all rice samples, we quantified the As amount in the species arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and arsenate (As(V)), with detection limits of 0.26, 0.26, 0.13 and 0.22 μg kg−1, respectively. We validated our experimental method with Standard Reference Material (SRM) NIST 1568b rice flour and obtained 85–110% recoveries for quantification of As from species. Speciation results were comparable to total As concentration determined by MICAP-MS. The use of N2-MICAP-MS would allow for quantification of As in chloride containing matrices; here, we demonstrate strong matrix tolerance of the MICAP-MS for solutions with up to 1% (w/w) sodium chloride. These results suggest that the MICAP-MS is a promising approach for the analysis of As species in more complex matrices. [ABSTRACT FROM AUTHOR]

Graphite furnace atomic absorption spectrometry (GFAAS) (also called electrothermal atomization [ETAAS]) is commonly used for sensitive elemental analysis. Following a summary of its principles, recent fundamental developments, and applications are reviewed. Advances in atomization mechanisms and instrumentation are discussed, followed by applications of speciation. New developments in direct solid sampling (SS) are reviewed that provide convenient, rapid, and green methodology. Novel preconcentration approaches are considered that provide reduced detection limits and removal of the sample matrix. A number of direct analyses are reviewed for clinical/pharmaceutical, food, environmental, and industrial samples. The conclusion discusses future developments in GFAAS, including the continued development of green protocols and speciation analyses. [ABSTRACT FROM AUTHOR]

The data gap in food safety regulations have created misinformation leading to the rejection of commodities for trade. The evidence presented is the local regulation of arsenic in sea produce which is based on total arsenic, tAs, instead of toxic inorganic arsenic, iAs. Furthermore, tAs data in animal origin seafood has been widely proven to be dominated by the non-toxic Arsenobetaine, AsB. Therefore, if arsenic regulatory limit was set based only on tAs without reference to iAs data, seafood products might be wrongfully rejected for trade because of non-compliance to tAs limit. We provided analysis of tAs and iAs of 14 local prawn and shrimp commodities from three shrimp/prawn sector namely aquaculture (n = 3), capture (n = 5) and processed (n = 6) using effective extraction, as well as, a fit-for-purpose analytical method for iAs. A HVG-AAS method was developed and validated for iAs with LoQ of 1.6 ppb, analytical range of 0–6 ppb, repeatability RSDr of 0.5–3.1 %, coefficient of determination R2 of 0.9975, and percentage recovery of 90.9 %, while an existing method using ICP-MS was used to verify the tAs. Based on the AOAC Official Method 999.10 2005 with minor adjustments, seafood samples were digested with concentrated nitric acid and hydrogen peroxide under pressure in a closed vessel heated by a microwave digester. An additional step for iAs determination was necessary to ensure compatibility in HVG-AAS analysis. Further subdivision of the aquaculture and capture samples was done by dividing them into 3 fractions, namely head, flesh and peel. Comparison of tAs in all the three fractions indicated that for aquaculture sector, the highest tAs were found in the flesh (2nd highest in % weight) whereas for the capture sector, the highest amount of tAs correlated with the highest % weight of the fraction. On regulatory aspects, speciation analysis on the iAs indicated samples with quantifiable iAs value were in-compliance despite tAs were initially found to be higher than the national limits. Risk assessment of iAs indicated there were no risk for human daily intake based on the BDML0.5 value of 3.0 μg/kg b.w per day for an average 70 kg man. All findings concluded the need for doing arsenic speciation analysis of iAs along with tAs for routine monitoring of prawn/shrimp samples and to revise the local limits from tAs to iAs particularly for seafood commodities.

Numerous mechanisms can drive speciation, including isolation by adaptation, distance, and environment. These forces can promote genetic and phenotypic differentiation of local populations, the formation of phylogeographic lineages, and ultimately, completed speciation. However, conceptually similar mechanisms may also result in stabilizing rather than diversifying selection, leading to lineage integration and the long‐term persistence of population structure within genetically cohesive species. Processes that drive the formation and maintenance of geographic genetic diversity while facilitating high rates of migration and limiting phenotypic differentiation may thereby result in population genetic structure that is not accompanied by reproductive isolation. We suggest that this framework can be applied more broadly to address the classic dilemma of "structure" versus "species" when evaluating phylogeographic diversity, unifying population genetics, species delimitation, and the underlying study of speciation. We demonstrate one such instance in the Seepage Salamander (Desmognathus aeneus) from the southeastern United States. Recent studies estimated up to 6.3% mitochondrial divergence and four phylogenomic lineages with broad admixture across geographic hybrid zones, which could potentially represent distinct species supported by our species‐delimitation analyses. However, while limited dispersal promotes substantial isolation by distance, microhabitat specificity appears to yield stabilizing selection on a single, uniform, ecologically mediated phenotype. As a result, climatic cycles promote recurrent contact between lineages and repeated instances of high migration through time. Subsequent hybridization is apparently not counteracted by adaptive differentiation limiting introgression, leaving a single unified species with deeply divergent phylogeographic lineages that nonetheless do not appear to represent incipient species. [ABSTRACT FROM AUTHOR]

The removal of copper (Cu) in soils by green technology is less treated with urgency, as it is a plant micronutrient. We examined the efficiency of Cu shoot accumulation by herbaceous plants in Cu-contaminated and non-contaminated soils in Trhové Dusniky and Podles, respectively, in the Czech Republic. The total soil Cu content of 81 mg kg−1 in Trhové Dusniky indicated a slight contamination level compared to 50 mg kg−1, the permissible value by WHO, and < 35 in Podlesí, representing a clean environment. The Cu content was above the permissible value in plants (10 mg kg−1 by WHO) in herbaceous speciesat the control site without trees: Stachys palustris L. (10.8 mg kg−1), Cirsium arvense L. (11.3 mg kg−1), Achillea millefolium L. (12.1 mg kg−1), Anthemis arvense L. (13.2 mg kg−1), and Calamagrostis epigejos L. (13.7 mg kg−1). In addition, Hypericum maculatum Crantz (10.6 mg kg−1), Campanula patula L. (11.3 mg kg−1), C. arvense (15 mg kg−1), and the highest accumulation in shoot of Equisetum arvense L. (37.1 mg kg−1), all under the canopy of trees at the uncontaminated site, were above the WHO value. Leucanthemum Vulgare (Lam.) and Plantago lanceolata L. recorded 11.2 mg kg−1 and 11.5 mg kg−1, respectively, in the soil of the Cu-contaminated site. These herbaceous species can support the phyto-management of Cu-contaminated soils, especially E. arvense. Critical attention is well-required in the medicinal application of herbaceous plants in treating human ailments due to their Cu accumulation potentials above the threshold. Spontaneous surveys and analysis of Cu speciation in herbaceous species can reveal suitable plants to decontaminate soils and provide caution on consumable products, especially bioactive compounds. [ABSTRACT FROM AUTHOR]

Speciation analysis is a relevant topic since the (eco)toxicity, bioavailability, bio (geo)chemical cycles, and mobility of a given element depend on its chemical forms (oxidation state, organic ligands, etc.). The reliability of analytical results for chemical species of elements depends mostly on the maintaining of their stability during the sample pretreatment step and on the selectivity of further separation step. Solid-phase extraction (SPE) is a matter of choice as the most suitable and widely used procedure for both enrichment of chemical species of elements and their separation. The features of sorbent material are of great importance to ensure extraction efficiency from one side and selectivity from the other side of the SPE procedure. This review presents an update on the application of polymeric materials in solid-phase extraction used in nonchromatographic methods for speciation analysis. [ABSTRACT FROM AUTHOR]

Highlights in the field of air analysis included: a new focus on measuring tyre-wear particle emissions; an interest in using unmanned aerial vehicles for sampling purposes and an increased use of ICP-MS for measuring halogenated volatile organics, metals sampled directly from air and single particles. Workers have explored further the full capabilities of ICP-MS/MS, which continued to dominate water analysis, including the speciation analysis of non-metallic elements in environmental samples. By far the largest number of papers on water analysis involved preconcentration. The growing interest in reagents for green chemistry was evidenced by the publication of several reviews. Novelties included the direct introduction of magnetic nanoparticles into FAAS to boost sensitivity, and the simultaneous dual-drop preconcentration of oxidation state species that avoided the need for a sequence of elution steps by preconcentrating the analytes into specific reagents contained in the drops. Although the total reflection XRFS and LIBS techniques are close to achieving the detection limits needed to screen contaminated waters, users of these instruments often neglect to validate their methods adequately through the use of reference materials. In methods for the analysis of soils, plants and related materials, sustainable digestion, extraction and preconcentration methods featured strongly. The development of AAS, AES and AFS methods for the direct analysis of solid samples and for increasing sensitivity through analyte enrichment continued to be of considerable interest. The nitrogen-microwave inductively coupled atmospheric-pressure plasma showed promise for ICP-MS analyses. Applications of LIBS have increased dramatically in number with noteworthy developments including single-chamber laser-ablation LIBS and the analysis of plant leaves without the need for grinding and pelleting. However, many published studies lacked validation through e.g. analysis of CRMs or comparison with results obtained by other techniques. Efforts have continued on the characterisation of natural and synthetic materials that are sufficiently homogeneous to act as reference materials (RMs) in the analysis of geological materials. In particular, application of microanalytical techniques, such as LA-ICP-MS and SIMS, led to the availability of a variety of new RMs for in situ isotope ratio determinations. The application of portable LIBS instrumentation to mineral prospecting and ore processing has received much attention, with the development of new chemometric models to improve data quality. The enormous amount of analytical data produced by modern instrumentation prompted the development of software, most of which has been made freely available, for facilitating the processing and reduction of isotopic data. [ABSTRACT FROM AUTHOR]

Copyright of Chinese Journal of Inorganic Analytical Chemistry / Zhongguo Wuji Fenxi Huaxue is the property of Beijing Research Institute of Mining & Metallurgy Technology Group and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Levels of 14 trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Zn, As, Se, Cd, Sn, Hg, and Pb) and 5 arsenic species (arsenite/As(III), arsenate/As(V), monomethylarsonic acid/MA, dimethylarsinic acid/DMA, and arsenobetaine/AsB) were assessed in the gonads of sea urchin samples (Paracentrotus lividus) from North-West Mediterranean Sea (French coast). The samples were collected from 13 sites characterized by different types and levels of chemical contamination. Trace elements levels were measured by inductively coupled plasma-mass spectrometry (ICP-MS) following microwave (acid) digestion in a closed system, whereas As speciation analysis was carried out by ion-exchange liquid chromatography coupled with ICP-MS after microwave-assisted extraction. High levels of trace elements were found in sea urchins sampled from Corsica whereas the samples from Théoule were found to be the least contaminated. From all the analyzed urchin samples, none showed Cd, Hg, or Pb concentrations above the regulatory levels set by the European Community (EC) No. 1881/2006 for seafood or bivalve mollusks. Regarding arsenic speciation, AsB was confirmed to be the predominant species. Inorganic As (As(III) + As(V)) was mainly constituted by As(III), which was quantified in all samples. Methylated As forms (MA and DMA) represent 9 to 23% of the total As. [ABSTRACT FROM AUTHOR]

The electroplating process of copper pyrophosphate (Cu2P2O7) results in the production of a large volume of wastewater that contains a high concentration of copper (Cu). Currently, conventional lime precipitation creates a substantial amount of secondary pollution, which adds extra economic and environmental burdens. In this study, we suggest a straightforward method for on-site recovery of Cu from Cu2P2O7 electroplating wastewater. By optimizing various parameters, characterizing the resulting product, assessing its electroplating capabilities, and analyzing the speciation during the reaction, we comprehensively investigated the feasibility and mechanism of this technique. The results demonstrated that, under the optimal conditions (Cu/P molar ratio of 0.96, pH of 5.0, and a reaction time of 5.0 min), the concentration of residual Cu remained stable between 22.2 and 27.7 mg/L, even when the initial Cu concentrations varied. The addition of Cu triggered a series of hydrolysis and ionization reactions, primarily leading to the formation of Cu2P2O7·3H2O. The harvested Cu2P2O7·3H2O proved to be suitable for practical electroplating applications, exhibiting comparable performance to commercially available Cu2P2O7·3H2O. This demonstrates the feasibility of recovering high-purity Cu2P2O7·3H2O from copper electroplating wastewater, offering a promising approach for on-site copper reuse and concurrently reducing the demand for natural copper resources. Furthermore, this approach significantly reduces the generation of solid waste, aligning with the principles of sustainable development. [ABSTRACT FROM AUTHOR]

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15 min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45 mM HNO3, 0.015% 2-mercaptoethanol, and 1.5 mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3 weeks. The limits of quantification (LOQ) are in the range of 0.010–0.013 mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15 mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006 mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish. [ABSTRACT FROM AUTHOR]

Copyright of Chinese Journal of Inorganic Analytical Chemistry / Zhongguo Wuji Fenxi Huaxue is the property of Beijing Research Institute of Mining & Metallurgy Technology Group and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Introduction: Rice genomescontain endogenous viral elements homologous to rice tungro bacilliform virus (RTBV) from the pararetrovirus family Caulimoviridae. These viral elements, known as endogenous RTBV-like sequences (eRTBVLs), comprise five subfamilies, eRTBVL-A, -B, -C, -D, and -X. Four subfamilies (A, B, C, and X) are present to a limited degree in the genomes of the Asian cultivated rice Oryza sativa (spp. japonica and indica) and the closely related wild species Oryza rufipogon. Methods: The eRTBVL-D sequences are widely distributed within these and other Oryza AA-genome species. Fifteen eRTBVL-D segments identified in the japonica (Nipponbare) genome occur mostly at orthologous chromosomal positions in other AA-genome species. The eRTBVL-D sequences were inserted into the genomes just before speciation of the AA-genome species. Results and discussion: Ten eRTBVL-D segments are located at six loci,whichwere used for our evolutionary analyses during the speciation of the AA-genome species. The degree of genetic differentiation varied among the eRTBVL-D segments. Of the six loci, three showed phylogenetic trees consistent with the standard speciation pattern (SSP) of the AA-genome species (Type A), and the other three represented phylogenies different from the SSP (Type B). The atypical phylogenetic trees for the Type Bloci revealed chromosomeregion--specific evolution among the AA-genome species that is associated with phylogenetic incongruences: complex genome rearrangements between eRTBVL-D segments, an introgression between the distant species, and low genetic diversity of a shared eRTBVL-D segment. Using eRTBVL-Das an indicator, this study revealed the phylogenetic incongruence of local chromosomal regions with different topologies that developed during speciation. [ABSTRACT FROM AUTHOR]

Iron, a crucial element in our environment, plays a vital role in numerous natural processes. Understanding the presence and concentration of iron in the environment is very important as it impacts various aspects of our planet's health. The on-site detection and speciation of iron are significant for several reasons. In this context, the present work aims to evaluate the applicability of voltammetry for the on-site determination of iron and its possible speciation using a portable voltammetric analyzer. Voltammetry offers the advantage of convenience and cost-effectiveness. For iron (III) determination, the modification of a glassy carbon electrode (GCE) with an antimony-bismuth film (SbBiFE) using the acetate buffer (pH = 4) as a supporting electrolyte was used. The technique adopted was Square Wave Adsoptive Cathodic Stripping Voltammetry (SW-AdCSV), and we used 1-(2-piridylazo)-2-naphthol (PAN) as the iron (III) ligand. Linearity, repeatability, detection limit, and accuracy were determined using synthetic solutions; then, a Standard Reference Material (SRM) of 1643f Trace Elements in Water (iron content: 93.44 ± 0.78 µg L−1) was used for validation measurements in the real matrix. the accuracy of this technique was found to be excellent since we obtained a recovery of 103.16%. The procedure was finally applied to real samples (tap, lake, and seawater), and the results obtained were compared via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The amount of iron found was 207.8 ± 6.6 µg L−1 for tap water using voltammetry and 200.9 ± 1.5 µg L−1 with ICP-OES. For lake water, 171.7 ± 3.8 µg L−1, 169.8 ± 4.1 µg L−1, and 187.5 ± 5.7 µg L−1 were found using voltammetry in the lab both on-site and using ICP-OES, respectively. The results obtained demonstrate the excellent applicability of the proposed on-site voltammetric procedure for the determination of iron and its speciation in water. [ABSTRACT FROM AUTHOR]

The aim of this work was to study the distribution of relevant inorganic contaminants in environmental samples from Ciudad de la Costa, the second most populated city of Uruguay. For this task aluminum (Al), cadmium (Cd), chromium (Cr), nickel (Ni) and lead (Pb) levels were determined in sand, water, and plant material from six beaches that are located in the area. Analytical methods were successfully validated. Accuracy was ensured by using certified reference materials and spiking procedures. Average metal concentrations in sand and water samples were compared with the maximum limits established by international or national regulations (when available), being far below these limits in all cases. This may indicate that the inorganic contamination in the studied area is rather low, despite the rapid increase in anthropic activities in recent years. To give a deeper characterization of the ecosystem, metal accumulation and mobility within a common plant of the zone, Ammophila arenaria, were studied. Results showed that concentrations in roots were one order of magnitude higher in comparison to aerial parts. In addition, the bioaccumulation coefficient (BAC) showed that the plant accumulates Cd, Cr and Ni, while a low accumulation for Pb was observed. Finally, a Cr(VI) speciation analysis in Ammophila arenaria was performed, showing Cr(VI) percentages below 4.6%, which is relevant from the (eco)toxicological point of view due to the high environmental mobility and bioavailability of this valence state. This work constitutes the first environmental surveillance report of this kind, regarding this populated area of the country. [ABSTRACT FROM AUTHOR]

Bottom sediments were tested in order to determine the possibility of immobilization of heavy metals with the use of natural sorbents, chitosan and bentonite. The content of Cu, Zn, Cd and Pb was determined, and speciation analysis was performed using the sequential Tessier methodology. The use of sorbents clearly changes the speciation forms of all tested heavy metals by comparing the distribution of metals before and after the application of the sorbent for both chitosan and bentonite. The addition of natural sorbents affect the immobilization of metals deposited in bottom sediments of water reservoirs. However, the behavior of metals in the presence of sorbents results from their properties and the nature of the sorbent. The positive effect of sorbents on metal immobilization was not observed in every case. The addition of the tested sorbents in the case of cadmium caused an increase in the content of Cd in the mobile fractions, for Zn, Pb and Cu, stronger binding of metals was found in the stable fractions IV and V. Chitosan stabilized metals more strongly than bentonite, which moved Zn, Pb and Cu to the first mobile fraction. [ABSTRACT FROM AUTHOR]

Understanding the prevalent form of platinum (Pt) based antineoplastic agents, used in chemotherapy, is of importance to develop a remediation strategy that restricts aquatic exposure. The speciation of Pt-based compounds was measured in actual patients’ urine using hydrophobic interaction liquid chromatography (HILIC) equipped with an ICP-MS detector. Carboplatin showed poor metabolization and intact excretion 11 h after administration, whereas cisplatin underwent a rapid aquation in the first 7 h. To compare, the in vitro degradation rate of cisplatin, carboplatin and oxaliplatin was determined in synthetic human urine, mimicking true environmental conditions. The fraction of intact molecules was measured at regular intervals following incubation at 37 °C, resulting in degradation rate constants. The chemical stability was highest for carboplatin (k = 0.0143 ± 0.0012 min−1), versus faster degradation of oxaliplatin and cisplatin by exponential decay with k1 of 0.0026 ± 0.0001 min−1 and k2 = 5.59 ± 0.46 × 10−6 min−1, respectively. These kinetic parameters can serve as input to further expand modelling databases and improve the predictive power of speciation software to estimate eco-toxicity risks. Considering the strong residual cytotoxicity of the platinum antineoplastic molecules following renal clearance and human excretion, the contaminants are of high environmental concern and offer potential for metal recovery using advanced treatment steps. In such water treatment processes, especially carboplatin, above all cancerostatic platinum compounds, should be addressed since it is more persistent in the aquatic environment.

Application of tetramethylammonium hydroxide for the treatment of samples prior to elemental analysis over the last five years is approached in this review article. Characteristics and properties of this reagent are described for a better understanding of the treatment process. Its effect on analyte measurements performed by atomic spectrometry techniques (flame and graphite furnace atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma optical emission spectrometry and, inductively coupled plasma mass spectrometry) is discussed, mainly the possibilities of physical interferences. Ways of using the reagent in sample preparation, such as incubation at room temperature, use of ultrasound energy, microwave energy, among others, will be discussed, in addition to the use of the reagent in speciation and nanoparticles analyses. Tetramethylammonium hydroxide has proven to be a viable alternative in the treatment of samples that can improve the performance of methods based on atomic spectrometry in the determination of elements of great interest to society.

Objective: Four arsenic species of arsenic in aquatic products were analyzed using ultrasonic-assisted extraction combined with high performance liquid chromatography-atomic fluorescence spectrometry （HPLC-AFS）. Methods: Four arsenic compounds were extracted ultrasonically from the samples using 50%（v/v） methanol-aqueous solution as extraction solvent. The chromatographic separation was performed on Hamilton PRP-X100 anion exchange column using a mixture of 15 mmol/L ammonium dihydrogen phosphate solution with the pH adjust to 6.0 as the mobile phase. Results: Under the optimized conditions, there were good linear relationships in the range of 0~100 μg/L for four arsenic compounds, with correlation coefficients all above 0.998. The limit of detection （LODs） of four arsenic species MMA, DMA,As（Ⅲ）,As（Ⅴ）were 0.82, 0.94, 1.10, 0.78 μg/L respectively. The relative standard deviations were in the range of 0.8%~3.7%. The recoveries ranged from 86.0% to 110.0%. Conclusion: This method is simple, accurate, sensitive, and low reagent consumption costs, can be used for the determination of the arsenic species in aquatic products.

Selenium (Se) is an essential micronutrient that plays an important role in animal and human development and physiological homoeostasis. This review surveys the role of Se in the environment, plants and animal bodies, and discusses data on Se biofortification with different sources of supplementation, from inorganic to organic forms, with special focus on Se-enriched yeast (Se-yeast). Although Se-yeast remains one of the main sources of organic Se, other emerging and innovative sources are reviewed, such as Se-enriched insects and Se-nanoparticles and their potential use in animal nutrition. Se-enriched insects are discussed as an option for supplying Se in organic form to livestock diets. Se-nanoparticles are also discussed, as they represent a more biocompatible and less toxic source of inorganic Se for animal organisms, compared to selenite and selenate. We also provide up to date information on the legal framework in the EU, USA, and Canada of Se that is contained in feed additives. From the scientific evidence available in the literature, it can be concluded that among the inorganic forms, sodium selenite is still one of the main options, whereas Se-yeast remains the primary organic form. However, other potential sources such as Se-enriched insects and Se-nanoparticles are being investigated as they could potentially combine a high bioavailability and reduced Se emissions in the environment.

Antimony (Sb) contamination poses significant environmental and health concerns due to its toxic nature and widespread presence, largely from anthropogenic activities. This study addresses the urgent need for an accurate speciation analysis of Sb, particularly in water sources, emphasizing its migration from polyethylene terephthalate (PET) plastic materials. Current methodologies primarily focus on total Sb content, leaving a critical knowledge gap for its speciation. Here, we present a novel analytical approach utilizing frontal chromatography coupled with inductively coupled plasma mass spectrometry (FC-ICP-MS) for the rapid speciation analysis of Sb(III) and Sb(V) in water. Systematic optimization of the FC-ICP-MS method was achieved through multivariate data analysis, resulting in a remarkably short analysis time of 150 s with a limit of detection below 1 ng kg−1. The optimized method was then applied to characterize PET leaching, revealing a marked effect of the plastic aging and manufacturing process not only on the total amount of Sb released but also on the nature of leached Sb species. This evidence demonstrates the effectiveness of the FC-ICP-MS approach in addressing such an environmental concern, benchmarking a new standard for Sb speciation analysis in consideration of its simplicity, cost effectiveness, greenness, and broad applicability in environmental and health monitoring.