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The biological removal of a mixture of soil contaminants, namely, hydrocarbons, is not equally efficient for each compound. Some pollutants can be metabolized by the microbial consortium but also generated again as by-products from the removal of others. At the end of the runs, notwithstanding the high integral removal, single compounds can still be present with a relevant concentration. This paper presents the results achieved in a study of the aerobic degradation of diesel oil in three mesocosms carried out for several months with the same operative conditions. They differed in biological management: Natural Attenuation (NA), Biostimulated without inoculation (BS), and Biostimulated with Inoculation (BS + IN). At the end of the runs, the pollution removal was calculated by measuring the residual diesel oil, both as an average in the total amount of soil and only at the bottom of each column. The overall removal was around 2%, 66%, and 72% for NA, BS and BS + IN, reduced to 0%, 48%, and 47%, respectively, if measured only at the bottom. For the biostimulated mesocosms, the speciation of the hydrocarbons was carried out to assess their concentration. The findings evidence the need to delve deeper into this issue and assess the speciation of contaminants. [ABSTRACT FROM AUTHOR]

Cobalt (Co) is a hazardous element of significant environmental concern, primarily due to its potential leaching toxicity. However, the current assessments of leached Co residues have focused solely on the total cobalt concentration, often overlooking the distinct Co species that contribute to its hazardous nature. This study attempts to determine the impact of cobalt speciation on the toxicity of cobalt and the related hazardous characteristics. The objective of this study is to enhance the understanding of how different Co species influence the environmental toxicity of leached residues. Cobalt speciation is studied by a multivariate analysis including ignitability, reactivity, corrosiveness, acute toxicity, leaching toxicity, and toxic substance concentration. The tested concentrations are compared with the identification standards and technical specifications in China. Co species, particularly cobalt oxide, are identified as the main contributors to the toxicity of the leached Co residue. It is also noted that Co occurrence significantly affects the calculation results of cumulative toxicity, thus impacting the hazard characteristics of leached cobalt residue. The findings benefit risk evaluators and decision makers by offering a new approach for managing leached Co residues and providing a scientific foundation for the development of relevant laws and regulations in China. [ABSTRACT FROM AUTHOR]

Bixa orellana is a plant that has a variety of uses, such as applications in the food and cosmetic industries, as well as culinary uses, and body painting for Indigenous people. Despite its versatility, few studies have explored its inorganic composition, and its sulfur chemical speciation has only been assessed from the point of view of sulfurous amino acids. Here, we report on the inorganic composition of Bixa orellana fruits, pericarps, and seeds obtained using Wavelength Dispersive X-ray Fluorescence (WD-XRF) and sulfur chemical speciation using X-ray Absorption Near-Edge Structure (XANES). Our results show that the seed is a source of potassium, calcium, magnesium, and phosphorous. But also, the pericarp, which is considered waste, contains a high amount of nutrients. From the XANES measurements, the distribution of the oxidation state of the sulfur atom was obtained, and it was shown that although several oxidation states of sulfur are present, oxidized sulfur (sulfate) is the dominant form of sulfur in all samples. [ABSTRACT FROM AUTHOR]

Mercury (Hg) is a toxic element which impacts on biological systems and ecosystems. Because the toxicity of Hg species is highly dependent on their concentration levels and chemical forms, the sensitive identification of the chemical forms of Hg—i.e., Hg speciation—is of major significance in providing meaningful information about the sources of Hg exposure. In this study, a microfluidic-based device made of high-clarity poly(methyl methacrylate) (PMMA) was fabricated. Then, titanium dioxide nanoparticles (nano-TiO2s) were attached to the treated channel's interior with the aid of poly(diallyldimethylammonium chloride) (PDADMAC). After coupling the nano-TiO2-coated microfluidic-based photocatalyst-assisted reduction device (the nano-TiO2-coated microfluidic-based PCARD) with high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS), a selective and sensitive, hyphenated system for Hg speciation was established. Validation procedures demonstrated that the method could be satisfactorily applied to the determination of mercury ions (Hg2+) and methylmercury ions (CH3Hg+) in both human urine and water samples. Remarkably, the zeta potential measured clearly indicated that the PDADMAC-capped nano-TiO2s with a predominance of positive charges indeed provided a steady force for firm attachment to the negatively charged device channel. The cause of the durability of the nano-TiO2-coated microfluidic-based PCARD was clarified thus. [ABSTRACT FROM AUTHOR]

This study investigated the distribution of sedimentary phosphorus (P) species along an area of a rapid current at the southern coast of Zhoushan Island. The objective of this study was to improve the understanding of P cycling in a zone of rapid water cycling. Results showed that the average percentage of each P form to total P (TP) was in the following order: apatite P (Ca-P; 52%) was found in the most abundant, followed by organic P (OP; 16%), exchangeable-P (Ex-P; 14%), detrital P (De-P; 11%), and iron-bound P (Fe-P; 7%). Ca-P showed a trend of an increasing concentration from a location at the west (ZS1 has mean Ca-P = 45.6 mg kg−1) toward the east (ZS2 has mean Ca-P = 82.69 mg kg−1) and south-east (ZS3 has mean Ca-P = 82.17 mg kg−1); De-P also increased from 15.12 mg kg−1 at ZS1 to 22.53 mg kg−1 at ZS2 and 27.45 mg kg−1 at ZS3, but the three bioavailable P species, OP, Ex-P, and Fe-P, decreased from the west toward the east of the coastal area. Results along the cores showed the occurrences of sediment P adsorption and release throughout the time span from the 1930s to the present, with an overall trend of decreasing Ca-P and TP from the bottom to surface sediments. There was a tendency of Ca-P formation at the expense of Ex-P and OP release during transport and organic matter decomposition. The likely impact of climate change in the coastal zone would be an increased temperature resulting in elevated organic matter decomposition and P release. [ABSTRACT FROM AUTHOR]

A number of regolith-hosted REE occurrences have recently been discovered in the Esperance region in southern Western Australia. This paper summarizes major characteristics of REE mineralization and discusses contributing factors and potential controls. The main aim is to explain why there is a lack of highly sought-after ion-adsorption-clay-type REE deposits across the region despite the presence of the regolith-hosted REE mineralization on a regional scale. Local mineralization mostly occurs as continuous flat-lying enrichment "blankets" within the residual regolith developed over Archaean–Proterozoic granite gneisses and granitoids with elevated REE content. The enriched horizon is commonly located in the lower saprolite and saprock and is accompanied by an overlying REE-depleted zone. This distribution pattern, together with the data on HREE fractionation and the presence of the supergene REE minerals, indicates chemogenic type enrichment formed by supergene REE mobilization into groundwater, downward transport, and accumulation in the lower part of the weathering profile. Residual REE accumulation processes due to bulk rock volume and mass reduction during weathering also contribute to mineralization. It is proposed that climate and groundwater chemistry are the critical regional controls on the distribution of REEs in the weathering profile and on their speciation in the enrichment zone. Cenozoic aridification of climate in southwest Australia heavily overprinted pre-existing REE distributions in the weathering profile. Acidic (pH < 4), highly saline groundwaters intensely leached away any relatively weakly bound, adsorbed or colloidal REE forms, moving them downward. Dissolved REEs precipitated as secondary phosphates in neutral to alkaline environment at lower Eh near the base of the weathering profile forming the supergene enrichment zone. Low denudation rates, characteristic of areas of low relief under the arid climate, are favourable for the preservation of the existing weathering profiles with REE mineralization. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are attracting considerable attention as non-conventional media for electrodeposition processes. This opinion contribution discusses the debated nature and definition of these solvents as well as some practical considerations of relevance when performing electrodeposition studies in DESs. Using a few illustrative case studies, it is shown that speciation is a key factor determining the electrochemical behaviour of chemical elements in different DESs, and that accounting for the speciation strong similarities can often be found with more conventional or more documented solvents. The need for thermodynamic data is emphasised and it is suggested to expand the composition range of these solvents beyond fixed ratios between the components to exploit the full potentialities of DESs. [ABSTRACT FROM AUTHOR]

The current paper is devoted to the synthesis of ceria-supported nickel-based catalysts starting from different precursors of the nickel active phase. Thermal decomposition of metal-containing precursors, deposited onto stable supports by dry impregnation, belongs to the industrially preferred, simple ways of catalyst preparation. The synthesized series of NiOx/CeO2 catalysts have been tested in dry methane reforming (DMR), in which two greenhouse gases, i.e., CO2 and CH4, are simultaneously converted into syngas. Both reaction progress and stability of the catalyst strongly depend on nickel speciation, which in turn can be determined by the nature of the chosen precursor. Contrary to relatively many studies focused on the importance of synthetic methods and conditions on nickel speciation, the effect of precursor nature on structural, textural, and functional properties of catalytic systems has neither been discussed much nor fully understood. The main goal of this paper was to elucidate the effect of precursors on the properties of NiOx/CeO2. Consequences of the use of various nickel precursors (simple inorganic salts, organometallic complexes, and chelates) have been analyzed in detail from the viewpoint of their beneficial influence on the catalytic performance of NiOx/CeO2 system (containing 3 wt. % of Ni) tested in DMR. [ABSTRACT FROM AUTHOR]

Copper ores and concentrates thereof feature an increasingly notable content of impurities such as arsenic and other hazardous elements. As an alternative to the state-of-the-art partial roasting process, arsenic could be removed by the alkaline sulfide leaching of the copper concentrates. In order to optimize and understand the processes, knowledge of the speciation and oxidation states is essential. In addition to methods such as UV/Vis spectroscopy, chromatography and ICP/MS methods, 75As NMR spectroscopy may be useful for the differentiation and quantification of the various species. Although arsenate(V) has been characterized by 75As NMR some time ago, to our knowledge, there are no data on tetrathioarsenate(V) AsS43− and the mixed oxygen/sulfur substituted mono-, di- and trithioarsenates(V) AsOxS4−x3−, x = 3, 2, 1, respectively. Therefore, we investigated several model solutions and samples from Cu-As leaching with 75As NMR. The strongly alkaline conditions of the leaching solution proved to be very advantageous for that purpose. Both the tetrathioarsenate(V) and the mixed species AsOxS4−x3− (x = 1–3) could be characterized and provide valuable data for the quantification of the material flows in the leaching process. [ABSTRACT FROM AUTHOR]

Stabilizing materials were prepared by different ratios of attapulgite/humic acid composites, and the optimum proportion for the remediation of Cd-polluted soils was found. The results suggested that the bioavailability of Cd in soil was decreased by the application of material prepared with humic acid and attapulgite in a ratio of 1:5. CaCl2-Cd, diethylenetriaminepentaacetic acid (DTPA-Cd) and the toxicity characteristic leaching procedure (TCLP-Cd) were reduced by 34.03%, 26.62% and 43.66%, and the ecological risk was depressed accordingly. The addition of stabilizing materials could transform the acid-soluble and reducible speciation to residue speciation, with a ratio of 1:5, significantly increasing the residue proportion of Cd in soil. The content of the residue state was increased by 63.13%, and the content of the acid-soluble state was significantly decreased by 34.10% compared with the control. The bioavailability, acid-soluble and reducible speciation of Cd had a highly negative correlation with the growth of corn, and the accumulation of Cd in corn had a significantly negative correlation with the residue speciation. Attapulgite/humic acid composites can reduce the bioavailability and increase the ratio of residue Cd in soil effectively, and they have the potential to remediate the pollution of heavy metals in soil. [ABSTRACT FROM AUTHOR]

To assess the long-term stability of lead-contaminated loess treated with calcium-free Enzyme-Induced Carbonate Precipitation (EICP) technology while avoiding significant soil strength increases, various parameters such as the pH value, heavy metal ion leaching rate, and soil heavy metal speciation were evaluated. This study investigated the remediated soil's stability under complex environmental conditions, including dry–wet cycles and acid rain leaching. The intrinsic mechanisms were elucidated through the Zeta potential, scanning electron microscopy (SEM), and X-ray diffraction (XRD) analyses. The results showed that compared to the untreated lead-contaminated loess, the surface strength of the loess treated with EICP technology increased by 3.86 times, with a 1.47-fold increase observed with the calcium-free EICP treatment. Carbonate precipitation improved the erosion resistance by adsorbing or coating fine particles and forming bridging connections with coarse particles. As the number of dry–wet cycles increased, the soil pH gradually decreased but remained above 8.25. The heavy metal leaching rate increased with the leaching cycles until reaching a plateau. The acid rain influence showed a decrease in the Pb2+ content in the leachate as the acid rain solution pH increased, meeting hazardous waste disposal regulations. These findings offer new insights for improving heavy metal-contaminated loess site remediation and understanding the underlying geochemical mechanisms. [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]

Mercury is a naturally occurring metal found in various inorganic and organic forms within the environment. Due to its high toxicity, there is global concern regarding human exposure to this element. The combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS) is commonly used to analyze the different forms of mercury in a sample due to its high sensitivity and ability to selectively detect mercury. However, the traditional HPLC-ICP-MS methods are often criticized for their lengthy analysis times. In this study, we have refined the conventional approach by transitioning to ultra-high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (UHPLC-ICP-MS). This modification has resulted in significant reductions in runtime as well as reagent and argon usage, thereby offering a more rapid, environmentally friendly, and cost-effective method. We successfully adapted an HPLC-ICP-MS method to UHPLC-ICP-MS, achieving the analysis of Hg2+ and MeHg+ within 1 min with a mobile phase consumption of only 0.5 mL and a sample volume of 5.0 µL; this is a major advance compared to HPLC analysis with run times generally between 5 and 10 min. The method's performance was assessed by analyzing muscle and liver tissue samples (serving as reference material) from fish, demonstrating the versatility of the method in relation to different complex matrices. [ABSTRACT FROM AUTHOR]

The objective of this study is to develop a remediation technology for composited heavy metal-contaminated soil. Biochars (BC300, BC400, and BC500) derived from corn were combined with potassium dihydrogen phosphate (KH2PO4) to immobilize and remove heavy metal ions, including mercury (Hg2+), cadmium (Cd2+), and lead (Pb2+). The adsorption kinetics of metal ions in aqueous solutions with different concentrations was tested, and the fitting effects of the two models were compared. The findings demonstrate that the joint application of biochar and KH2PO4 could markedly enhance the immobilization efficacy of Pb2+, whereas the utilization of KH2PO4 on its own exhibited a more pronounced immobilization impact on Cd2+. Furthermore, the present study underscores the shortcomings of various remediation techniques that must be taken into account when addressing heavy metal-contaminated soils. It also emphasizes the value of comprehensive remediation techniques that integrate multiple remediation agents. This study offers a novel approach and methodology for addressing the intricate and evolving challenges posed by heavy metal contamination in soil. Its practical value and potential for application are significant. [ABSTRACT FROM AUTHOR]

The exploitation of iron ore could cause heavy metals pollution in the soils, which threatens the ecosystem and human health. In this study, soil, stream sediment, tailings, rock, and atmospheric deposition samples were collected from an iron mine in Baotou City. The concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb, Zn, Al2O3, CaO, K2O, MgO, Na2O, SiO2, and Fe2O3, as well as the mineral composition and heavy metal speciation of the samples, were analyzed for pollution assessment and source identification of heavy metals. The results reveal that the concentration of Cu in the soils was significantly higher than the background value, and an unpolluted to moderately polluted state was the main pollution level. By analyzing the relationship between Cu/Al2O3 and CaO in different samples, as well as the characteristics of the chemical index of alteration (CIA), mineral composition, and the chemical speciation of Cu in soils and profiles, the results suggest that tailings were the source of Cu pollution in soils. The distribution characteristics of Cu and CaO in stream sediments indicated that hydraulic transport may be one of the main migration pathways. In addition, wind transport may also be a pathway of migration. [ABSTRACT FROM AUTHOR]

To explore the contamination status and identify the source of the heavy metals in the sediments in the major inflow rivers of Dianchi Lake in China, sediment samples were collected and analyzed. Specifically, the distribution, source, water quality, and health risk assessment of the heavy metals were analyzed using correlation analysis (CA), principal component analysis (PCA), the heavy metal contamination factor (Cf), the pollution load index (PLI), and the potential ecological risk index (PERI). Additionally, the chemical fractions were analyzed for mobility characteristics. The results indicate that the average concentration of the heavy metals in the sediment ranked in the descending order of Zn > Cr > Cu > Pb > As > Ni > Cd > Hg, and most of the elements existed in less-mobile forms. The Cfwas in the order of Hg > Zn > Cd > As > Pb > Cr > Ni; the accumulation of Hg, Zn, Cd, and As was obvious. Although the spatial variability of the heavy metal contents was pronounced, the synthetical evaluation index of the PLI and PERI both reached a high pollution level. The PCA and CA results indicate that industrial, transportation, and agricultural emissions were the dominant factors causing heavy metal pollution. These results provide important data for improving water resource management efficiency and heavy metal pollution prevention in Dianchi Lake. [ABSTRACT FROM AUTHOR]

Artisanal small-scale gold mining (ASGM), an increasingly prevalent activity in South America, generates mercury-contaminated tailings that are often disposed of in the environment, leading to the introduction of mercury into ecosystems and the food web, where it bioaccumulates. Therefore, studying the geochemical processes involved in the desorption and dissolution of mercury in these tailings is essential for critical risk evaluations in the short and long term. For this purpose, sequential extraction procedures (SEPs) can be useful because they help to identify the phases to which Hg is associated, although they also have limitations such as a lack of selectivity and specificity. In this work, we propose a modified four-step SEP: exchangeable mercury (F1), oxidizable mercury (F2), mercury bound to Fe oxides (F3), and strongly bound mercury (F4). To test this adapted sequential extraction method, we evaluated the Hg contamination in mercury-contaminated tailings of the Amazon basin. The results revealed a total mercury concentration of 103 ± 16 mg·kg−1 in the tailings, with a significant portion in F1 (28% of the total), where Hg was bioavailable. The large Hg concentration in F3 (36%) suggested that Fe oxides likely contribute to mercury retention. Together, the SEP results emphasize the urgent need for improved surveillance of gold mining activities and responsible tailings management practices to mitigate environmental contamination and safeguard the health of the Amazon ecosystem. [ABSTRACT FROM AUTHOR]

This study focused on monitoring phosphorus (P) concentrations in the water of the Ramsar site, Lake Vembanad, with a special focus on the mouths of the river bodies draining into the lake, a known hotspot for eutrophication. Four phosphorus fractions—total reactive phosphorus (TRP), total acid hydrolysable phosphorus (TAHP), total organic phosphorus (TOP), and total phosphorus (TP)—were monitored during the pre-monsoon and post-monsoon seasons. The results revealed high levels of all monitored phosphorus fractions, with an average concentration exceeding 300 ppb P across both seasons, indicating a highly eutrophic state. Notably, TRP, TOP, and TP showed high concentrations in both the pre-monsoon and post-monsoon periods. These data suggest significant phosphorus input into the lake's surface water, potentially triggering excessive algal growth and threatening the biodiversity of this rich wetland ecosystem. [ABSTRACT FROM AUTHOR]

The treatment of large amounts of copper slag is an unavoidable issue resulting from the high demand for copper during the global transition to a sustainable development path. Metal-rich copper slag might serve as a potential source of metals through secondary recovery. In this study, two copper slags (CS1 and CS2) with different metallurgical properties were characterized, focusing on secondary metal recovery. The X-ray diffraction (XRD) results show that fayalite (Fe2SiO4) and magnetite (Fe3O4) were the main crystalline phases in both CS1 and CS2. In addition, CS2 exhibited a more stable amorphous silicate network than CS1, which was attributed to the differences in the content of Si-O-3NBO linkages. The sequential extraction of Zn, Cu, Fe, and Pb from the slags was also explored, with the Cu content in CS1 being substantially lower than that in CS2. All metals were distributed in the F5 residue fraction. Cu was the most mobile metal as a result of the large proportion of soluble fractions (F1–F3), followed by Zn and Fe. This study explored the chemical speciation of Zn, Cu, Fe, and Pb from copper slags, which has practical implications for secondary metal recovery from such materials. [ABSTRACT FROM AUTHOR]

The increasing presence of arsenic-containing impurities within Cu ores can adversely affect the smelting process and aggravate the environmental impact of slag tailing. This study investigates the geochemical, mineralogical, and chemical speciation characteristics to better understand the association and environmental stability of metal(loid)s in copper slag tailing. The results indicate that the predominant chemical compositions of the selected slag tailing are Fe2O3 (54.8%) and SiO2 (28.1%). These tailings exhibit potential for multi-elemental contamination due to elevated concentrations of environmentally sensitive elements. Mineral phases identified within the slag tailings include silicate (fayalite), oxides (magnetite and hematite), and sulfides (galena, sphalerite, arsenopyrite, and chalcopyrite). The consistent presence of silicate, iron, arsenic, and oxygen in the elemental distribution suggests the existence of arsenic within silicate minerals in the form of Si-Fe-As-O phases. Additionally, arsenic shows association with sulfide minerals and oxides. The percentages of arsenite (As(III)) and arsenate (As(V)) within the selected slag tailings are 59.4% and 40.6%, respectively. While the slag tailings are deemed non-hazardous due to the minimal amounts of toxic elements in leachates, proper disposal measures should be taken due to the elevated carbonate-bound levels of As and Cu present in these tailings. [ABSTRACT FROM AUTHOR]

About 2.5 billion people rely on groundwater as their main drinking water source, and arsenic pollution within the groundwater system can cause serious short- and long-term health issues. Within the natural environment, arsenic generally exists as oxyanions which have two oxidation states, As(III) and As(V). Under ambient pH conditions, As(V) is primarily present as an anion (i.e., H2AsO4−) while As(III) tends to be uncharged (i.e., H3AsO3), making it much more difficult to remove As(III) through existing treatment techniques such as adsorption and reverse osmosis (RO). In Eastern Wisconsin, the dolomite and dolomite/sandstone aquifers represent a major drinking water source and high arsenic concentrations have been observed. Previous studies showed that arsenic can be released into private drinking water wells due to the oxidation of sulfide-bearing minerals with arsenic impurities that are usually dispersed within the dolomite and sandstone bedrock. However, there is a lack of information on the concentrations of each arsenic species as well as arsenic dynamics during water pumping/usage. The primary goals of this research were (1) to quantify the baseline concentrations of each arsenic species within selected Eastern Wisconsin private drinking water wells, and (2) to determine how the arsenic concentrations and species could be affected by continuous water usage. Our results showed that As(III) was the dominant species of arsenic, and during continuous water usage, there could be an upward trend in arsenic concentration (there was minimal change in arsenic speciation). Upon the completion of water pumping, arsenic concentrations decreased over time and returned to pre-pumping levels. Our findings highlighted the importance of quantifying the speciation and dynamics of arsenic during water use to the assessment of public health risks and the design of appropriate water treatment techniques. [ABSTRACT FROM AUTHOR]

Iron (Fe) is one of the main nutrients present in dissolved, suspended, and colloidal states in river water. Predicting the composition and size of dissolved Fe compounds is crucial for assessing water quality. In this stud, we used a combination of physical methods (filtration), chemical techniques (ion exchange chromatography), and thermodynamic modeling (Visual MINTEQ) to characterize dissolved Fe speciation in boreal organic-rich rivers across a sizable south–north transect. We chose contrasting rivers with a predominance of either allochthonous or autochthonous organic compounds. We found that the dissolved organic matter (DOM) in the studied rivers varies in molecular weights and the degree of humification. Regardless of the climate parameters of the river watershed, the dominant status of dissolved Fe during the summer low-water period was essentially colloidal and dominated by anionic complexes of the type [MeL]n−. [ABSTRACT FROM AUTHOR]

Historical coal mining practices have caused various soil and water hazards, particularly through the dumping of mine waste. The primary environmental risk associated with this waste is the leaching of toxic metals from dumps of spoil or refuse into the subsurface soil or into nearby water resources. The extent of metal release is controlled via the oxidative dissolution of pyrite and potential re-sequestration through secondary Fe oxides. The characterization of the dominant Fe-bearing phase and the distribution of trace metals associated with these phases was determined via electron microscopy, synchrotron-based X-ray micro-fluorescence (μ-XRF) element and redox mapping from shallow mine soils from an impacted watershed in Appalachian Ohio. The dominant Fe-bearing phases were: (1) unweathered to partially weathered pyrite; (2) pseudomorphic replacement of pyrite with Fe(III) oxides; (3) fine-grained Fe oxide surface coatings; and (4) discrete Fe(III) oxide grains. Thicker secondary coatings and larger particles were sulfate rich, whereas smaller grains and thinner coatings were sulfate poor. The discrete Fe oxide grains exhibited the highest concentrations of Cr, Mn, Ni, and Cu, and sub-grain-scale concentration trends (Mn > Cr > Ni > Cu) were consistent with bulk soil properties. Predicting future metal transport requires an understanding of metal speciation and distribution from the sub-grain scale to the pedon scale. [ABSTRACT FROM AUTHOR]

Previous studies of cadmium and mercury immobilization in geopolymers have produced inconsistent results due to their different pozzolans, metal concentrations, and mixing procedures. Understanding the effects of these parameters on heavy metal immobilization is key to predicting their long-term stability. In this study, cadmium and mercury were incorporated into a metakaolin-based K-activated geopolymer by three mixing procedures and concentrations of 0.02–1.00 wt.%. The samples were then immersed in water for 90 d to determine their stability. The results show that mercury is readily leached from the geopolymer, but cadmium is retained. Adding the heavy metals in salt form converts the metals into cadmium hydroxide and mercury oxide that reside at the bottom of the geopolymer. Mixing the salts with water forms soluble heavy metals prior to geopolymerization. This procedure produces more-homogeneous geopolymers. Cadmium is associated with silicate and aluminate, giving a better stability, whereas mercury forms mercury oxide. Different cadmium and mercury concentrations do not change the metal speciation as mercury is affected by relativistic contribution. [ABSTRACT FROM AUTHOR]

Evidence of the precise biological pathway responsible for acute cardiovascular events triggered by particulate matter (PM) exposure from anthropogenic emissions is sparse. We investigated the associations of biomarkers relevant to the pathophysiology of atherothrombosis (ceramide metabolism, pro-inflammatory response, and blood coagulation) with primary and secondary components in particulate matter with aerodynamic diameters less than 2.5 μm (PM2.5). A total of 152 healthy participants were followed with four repeated clinical visits between September 2019 and January 2020 in Beijing. Exposure to ambient inorganic aerosols (sulfate, nitrate, ammonium, and chloride), as well as organic aerosols (OA) in PM2.5, was measured by a real-time aerosol chemical speciation monitor, and sources of OA were performed by positive matrix factorization. We found significant increases of 101.9–397.9% in ceramide indicators associated with interquartile-range increases in inorganic aerosols and OA prior to 72 h of exposure. Higher levels of organic and inorganic aerosols in PM2.5 were associated with increases of 3.1–6.0% in normal T cells regulated upon activation and expressed and secreted relevant to the pro-inflammatory response; increases of 276.9–541.5% were observed in D-dimers relevant to coagulation. Detrimental effects were further observed following OA exposure from fossil fuel combustion. Mediation analyses indicated that ceramide metabolism could mediate the associations of PM2.5 components with pro-inflammatory responses. Our findings expand upon the current understanding of potential pathophysiological pathways of cardiovascular events posed by ambient particulates and highlight the importance of reducing primary and secondary PM from anthropogenic combustions. [ABSTRACT FROM AUTHOR]

A new ionic liquid modified polymer gel containing methylimidazolium groups (poly(MIA)) is proposed as a sorbent for the separation and enrichment of trace inorganic and organic arsenic species in surface waters. The poly(MIA) was synthesized by chemical modification of polymeric precursor using post-polymerization modification of poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate). The composition, structure, morphology, and surface properties of the prepared particles were characterized using elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption–desorption measurements. Optimization experiments showed that at pH 8, monomethylarsonic acid (MMAs), dimethylarsinic acid (DMAs), and As(V) were completely retained on the poly(MIA), while the sorption of As(III) was insignificant. The desorption experiments revealed that due to the weaker binding of organic arsenic species, selective elution with 1 mol/L acetic acid for MMAs + DMAs, followed by elution with 2 mol/L hydrochloric acid for As(V), ensured their quantitative separation. The adsorption kinetic and mechanism were defined. The analytical procedure for As(III), As(V), MMAs, and DMAs determination in surface waters was developed and validated through the analysis of certified reference material. [ABSTRACT FROM AUTHOR]

Simple Summary: One of the most widespread bacteria associated with insects are those in the genus Wolbachia. These bacteria can cause a wide range of behavioral and physiological changes within their host species, but not all these interactions are well-documented. Specifically in ants, the diversity of Wolbachia has not been characterized fully leaving many open questions regarding its interactions with this globally distributed insect family. This study surveyed the genus Cephalotes for its Wolbachia diversity and aimed to characterize the singly infected samples found along with discovering any patterns in infections. Using multilocus sequence typing, novel genes and Wolbachia strains were discovered across the native distribution of Cephalotes. There were no clear patterns in infections nor any association with biogeographic distribution. Overall, the unique sequences should be investigated further but provide important information on the distribution and relationship between Cephalotes and Wolbachia at the genus level. This provides further information for future studies to continue investigating these unusual bacteria and their complex relationships with ant-hosts. Wolbachia is a widespread and well-known bacterium that can induce a wide range of changes within its host. Ants specifically harbor a great deal of Wolbachia diversity and are useful systems to study endosymbiosis. The turtle ants (Cephalotes) are a widespread group of tropical ants that rely on gut microbes to support their herbivorous diet for their survival, yet little is known of the extent of this diversity. Therefore, studying their endosymbionts and categorizing the diversity of bacteria within Cephalotes hosts could help to delimit species and identify new strains and can help lead to a further understanding of how the microbiome leads to survival and speciation in the wild. In our study, 116 individual samples were initially tested for positive infection with the wsp gene. Of the initial 116 samples, 9 samples were infected with only one strain of Wolbachia, and 7 were able to be used successfully for multilocus sequence typing (MLST). We used the new MLST data to infer a phylogeny with other Formicidae samples from the MLST online database to identify new Wolbachia strains and related genes, of which only one came back as an exact match. The 18 Wolbachia-positive samples ranged across 15 different species and 7 different countries, which we further test for species identity and geographic correlation. This study is the first comprehensive look into the diversity of Wolbachia in the turtle ants, providing insight into how endosymbionts are oriented in widespread species and providing a strong foundation for further research in host-microbe interactions. [ABSTRACT FROM AUTHOR]

Steroids are often considered valuable molecular tools for the development of anticancer agents with improved pharmacological properties. Conjugation of metal chelating moieties with a lipophilic sterane backbone is a viable option to obtain novel anticancer compounds. In this work, two estradiol-based hybrid molecules (PMA-E2 and DMA-E2) with an (N,N,O) binding motif and their Cu(II) complexes were developed. The lipophilicity, solubility, and acid-base properties of the novel ligands were determined by the combined use of UV-visible spectrophotometry, pH-potentiometry, and 1H NMR spectroscopy. The solution speciation and redox activity of the Cu(II) complexes were also investigated by means of UV-visible and electron paramagnetic resonance spectroscopy. Two structurally analogous ligands (PMAP and DMAP) were also included in the studies for better interpretation of the solution chemical data obtained. Three pKa values were determined for all ligands, revealing the order of the deprotonation steps: pyridinium-NH+ or NH(CH3)2+, secondary NH2+, and OH. The dimethylamine derivatives (DMA-E2, DMAP) are found in their H2L+ forms in solution at pH 7.4, whereas the fraction of the neutral HL species is significant (34–37%) in the case of the pyridine nitrogen-containing derivatives (PMA-E2, PMAP). Both estradiol derivatives were moderately cytotoxic in human breast (MCF-7) and colon adenocarcinoma (Colo-205) cells (IC50 = 30–63 μM). They form highly stable complexes with Cu(II) ions capable of oxidizing ascorbate and glutathione. These Cu(II) complexes are somewhat more cytotoxic (IC50 = 15–45 μM) than their corresponding ligands and show a better selectivity profile. [ABSTRACT FROM AUTHOR]

Selenium-enriched yeast possesses the unique ability of transforming chemical selenium, such as sodium selenite, into a biologically active form, which mitigates its toxic effects on the human body. The transformation product of this process, selenomethionine, can be safely and effectively absorbed and utilized by the human body; hence, it has been spiked into a selenium-enriched supplement. This study employs two distinct measurement strategies to determine the selenomethionine content in two candidate reference materials, a selenium-enriched yeast powder and supplement, using both organic and inorganic mass spectrometry. The concentrations of selenomethionine in the selenium-enriched yeast were determined using HPLC-ICP-MS and HPLC- ESI-MS/MS, with mass fractions measured at 718 mg SeMet kg−1 and 715 mg SeMet kg−1, respectively. Notably, both methods yielded consistent results for the selenium supplement, with a selenomethionine mass fraction of 59 mg SeMet kg−1. Ultimately, the certified values of these candidate reference materials were determined as 716 mg kg−1 and 59 mg SeMet kg−1 with expanded uncertainties of 36 mg SeMet kg−1 (k = 2) and 5 mg SeMet kg−1 (k = 2), respectively. The development of these candidate reference materials serves as a valuable reference for diverse methods aiming to determine the value of organic selenium speciation in complex food substrates. [ABSTRACT FROM AUTHOR]

A reliable, rapid, and low-cost procedure for determining very low concentrations of hexavalent chromium (Cr) in water is discussed. The procedure is based in the classical reaction of Cr6+ with diphenylcarbazide. Once this reaction has taken place, sodium dodecylsulfate is added to obtain an ion-pair, and Triton X-114 is incorporated. Next, the heating of the mixture allows two phases that can be separated by centrifugation to be obtained in a cloud point microextraction (CPE) process. The coacervate contains all the Cr6+ originally present in the water sample, so that the measurement by molecular absorption spectrophotometry allows the concentration of the metal to be calculated. No harmful organic solvents are required. The discrimination of hexavalent and trivalent forms is achieved by including an oxidation stage with Ce4+. To take full advantage of the pre-concentration effect inherent to the coacervation process, as well as to minimize reagent consumption and waste generation, a portable mini-spectrophotometer which is compatible with microvolumes of liquid samples is used. The preconcentration factor is 415 and a chromium concentration as low as 0.02 µg L−1 can be detected. The procedure shows a good reproducibility (relative standard deviation close to 3%). [ABSTRACT FROM AUTHOR]

Iron (Fe), the main component of non-exhaust particulates, is known to have variable health effects that depend on the chemical species of iron. This study characterized the possible contribution of iron oxides and hydroxides to airborne brake wear particles under realistic vehicle driving and braking conditions with different brake pad friction materials. We found significant differences in wear factors and PM10 and PM2.5 emissions between non-asbestos organic (NAO) and European performance (ECE) brake pads. Iron was the dominant contributor to PM10 and PM2.5 brake wear particles for both NAO and ECE. The iron concentration ratio in the particle mass (PM) was comparable to the disc-to-pads ratio measured by wear mass. The fact that magnetite, which is of interest with respect to health effects, was less abundant in NAO than in ECE suggested that tribo-oxidations occurred in NAO. Metallic iron is generated not only from abrasive wear but also from tribo-chemical reduction with magnetite as the starting material. We found that there were differences in PM emissions between brake friction materials, and that the phase transformations of iron differed between friction materials. These differences were apparent in the distribution of iron oxides and hydroxides. Heat, tribo-oxidation, and tribo-reduction are intricately involved in these reactions. [ABSTRACT FROM AUTHOR]

Copper (Cu) has been used to treat vines for a long time, which has led to its accumulation in vineyard soils. In the present work, the mobilization of copper from these soils and its transport, and diffusion outside the plots by drain water were investigated. For this, the distribution of copper between the dissolved and colloidal phases, and within the colloidal phase, of these waters was determined using an investigation strategy based on the coupling between a size separation technique, asymmetric flow field-flow fractionation, and several detectors. First, the total copper concentrations in water from different drains were monitored over a period of 2 years: Cu was mainly found in the fraction of < 450 nm. Then, the distribution of copper on the size continuum was more closely studied in water from one of the drains, sampled over a winter period. Between 45 and 75% of Cu was found in the 2–450 nm colloidal fraction. The <450 nm colloidal phase of the drain waters was found to be mainly composed of humic acids (~15 to 60 mg L−1) and clay-rich particles (~100 to 650 mg (Al) L−1). These particles also contained (hydr)oxides of iron and manganese. The concentrations of Fe and Mn were approximately 100 to 200 times lower than those of Al. The majority of humic acids had an apparent molar mass of ≤ 10 kDa. They were distributed along the size continuum: (i) in a population with an average size of ~20 nm, probably consisting of supramolecular entities, and (ii) associated with clay-rich particles with a size of ~120–200 nm. Copper was found to be complexed with humic acids and associated with clays via clay-humic complexes. Copper mobilization from the soil to the water and its transport to the drain water appeared governed by the soil humidity level and the rainfall. [ABSTRACT FROM AUTHOR]

In the present study we report the development of an advantageous optical sensor for the speciation of Fe(III)/Fe(II). The sensor is based on the selective reaction of Fe(III) with a Desferal (Deferoxamine) reagent at pH = 2, while both Fe(III) and Fe(II) react with the reagent at pH = 5 using an acetate/glycine buffer. In this way, frequently used extra oxidation (H2O2) or reduction (ascorbic acid or hydroxylamine) steps are avoided. Both species can be determined in the range of 25 to 150 μM using a 96-well plate platform and the instrument-free detection of the colored complex with an overhead book scanner. The LOD is 4 μM, and an additional advantage is that a single calibration curve can be utilized for quantitation. The applicability of the sensor was demonstrated by analyzing commercially available pharmaceutical formulations for quality control purposes. [ABSTRACT FROM AUTHOR]

Over the last four decades, vanadium compounds have been extensively studied as potential antidiabetic drugs. With the present review, we aim at presenting a general overview of the most promising compounds and the main results obtained with in vivo studies, reported from 1899–2023. The chemistry of vanadium is explored, discussing the importance of the structure and biochemistry of vanadate and the impact of its similarity with phosphate on the antidiabetic effect. The spectroscopic characterization of vanadium compounds is discussed, particularly magnetic resonance methodologies, emphasizing its relevance for understanding species activity, speciation, and interaction with biological membranes. Finally, the most relevant studies regarding the use of vanadium compounds to treat diabetes are summarized, considering both animal models and human clinical trials. An overview of the main hypotheses explaining the biological activity of these compounds is presented, particularly the most accepted pathway involving vanadium interaction with phosphatase and kinase enzymes involved in the insulin signaling cascade. From our point of view, the major discoveries regarding the pharmacological action of this family of compounds are not yet fully understood. Thus, we still believe that vanadium presents the potential to help in metabolic control and the clinical management of diabetes, either as an insulin-like drug or as an insulin adjuvant. We look forward to the next forty years of research in this field, aiming to discover a vanadium compound with the desired therapeutic properties. [ABSTRACT FROM AUTHOR]

The safe disposal and resource utilization of Fenton sludge (FS) are challenges due to the presence of heavy metals (HMs). Co-pyrolysis with biomass waste can effectively increase biochar quality and immobilize HMs, but research focusing on heavy metal stabilization from Fenton sludge using the co-pyrolysis approach is scattered. In this study, the co-pyrolysis of FS and pomelo peel (PP) was developed as a strategy to reduce the environmental risk of HMs. The results showed that co-pyrolysis greatly increased the pH and aromaticity of biochars, and the maximum specific surface area was 6.5 times higher than the corresponding FS-based biochar due to the sponge-like structure of PP, which was likely conducive to adsorbing HMs during pyrolysis. Meanwhile, the addition of PP promoted the enrichment of HMs in co-pyrolyzed biochars as well as induced the transformation of bio-available HM fractions to stable forms, especially at high temperatures. Finally, the presence of PP led to the decline in HM leachability in biochars; thus, the potential ecological risks of HMs decreased from considerable pollution levels to moderate and even clean levels. This study demonstrated that co-pyrolysis with PP is a promising approach to reduce the toxicity of HMs and improve the functionality of biochar for industrial sludge management. [ABSTRACT FROM AUTHOR]

The mobilization, speciation, and transformation of these pollutants in the soil and groundwater ecosystem vary greatly depending on the specific hydro-biogeochemical processes and environments. To effectively address soil pollution sources and manage the risks of groundwater pollution, it is essential to comprehend how complex geological and hydrogeological factors in soil-groundwater systems interplay with climate change and human activities. The common types of organic pollutants in soil and groundwater environments include polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), chlorinated solvents, polychlorinated biphenyls (PCBs), pesticides, and other emerging contaminants [[5], [7]]. The delicate balance of our ecosystems is under threat from the unrelenting release of contaminants into the environment. [Extracted from the article]

Land use has a greater impact on trace element (TE) concentration present in soils. In mountainous regions of the western Himalayas, some dominating geogenic and human-dependent anthropogenic factors are involved in the spatial distribution of TEs in various land uses. Soil samples were collected from permafrost, pasture, forest, and agricultural land-use systems of Babusar Valley and Fairy Meadows in Diamer districts and the Rama region in Astore Districts in replications for investigation of three TEs, i.e., copper (Cu), zinc (Zn), and nickel (Ni). These samples were analyzed for exchangeable, adsorbed, organically bound, carbonate precipitated, and residual forms. Significant differences among these TEs were observed. Differences in the levels of TEs within soil samples were observed to be influenced by land usage patterns. The physicochemical properties of soil samples were also investigated. Additionally, the total metals (Ni, Zn, Cu) were extracted and their concentrations were measured in all samples. The concentration of soil TEs was observed in the following order: adsorbed < organically bound < exchangeable < residual < carbonate precipitated form across all the land uses. The results indicate that the contents of TEs (Ni, Zn, Cu) in agricultural soils were greater than in the permafrost pasture and forest soil samples. The total TE concentration varied as Zn > Ni > Cu irrespective of the area and land uses. We believe this work will open avenues for researchers to explore TEs in various regions of the world. [ABSTRACT FROM AUTHOR]

In this study, determination of the inorganic and organic forms of tin in waters of different salinities is considered. The possibility of the separation of speciations of tin using liquid–liquid extraction (LLE); precipitation with fluorides, iodides, ammonia, and iron (III) chloride; and sorption of organotin compounds (OTCs) was studied. The LLE and analyte precipitation methods proved to be ineffective. Inorganic and organic forms of tin were separated by the sorption of OTCs using silica gel sorbent Diapak C18. Under optimized conditions, a technique for the separate determination of the forms of tin in natural waters was developed. The technique combines hydride generation and microwave mineralization of solutions followed by ICP spectrometry. The inorganic forms of tin were determined after their solid-phase separation from organotin compounds. The lower limits of analyte quantification were 0.03 μg/L (ICP-MS) and 0.05 μg/L (ICP-OES), which provide separate determinations of inorganic and organic forms of tin in waters with different salinities. The content of OTCs in water was determined by subtracting the inorganic concentration from the total concentration of tin. The technique will allow a comprehensive assessment of the toxicological impact of tin speciations on the aquatic ecosystem. [ABSTRACT FROM AUTHOR]

Arsenic (As)-contaminated gold mine waste is a global problem and poses a significant risk to the ecosystem and community (e.g., carcinogenic, toxicity). Arsenic concentrations of 77,000 mg/kg and 22,000 mg/kg in mine waste have been reported for Canada and Australia, respectively. Research is investigating environmentally sustainable techniques to remediate As-rich mine waste. Biological techniques involving plants (phytoremediation) and soil amendments have been studied to bioaccumulate As from soil (phytoextraction) or stabilise As in the rhizosphere (phytostabilisation). Identified plant species for phytoremediation are predominately fern species, which are problematic for arid to semi-arid climates, typical of gold mining areas. There is a need to identify native plant species that are compatible with arid to semi-arid climates. Arsenic is toxic to plants; therefore, it is vital to assess soil amendments and their ability to reduce toxicity, enhance plant growth, and improve soil conditions. The effectiveness of a soil-amending phytoremediation technique is dependent on soil properties, geochemical background, and As concentrations/speciation; hence, it is vital to use field soil. There is a lack of studies involving mine waste soil collected from the field. Future research is needed to design soil-amending phytoremediation techniques with site-specific mine waste soil and native plant species. [ABSTRACT FROM AUTHOR]

In the field of contaminated site remediation, risk analyses can be carried out by the use of appropriate mathematical models, based on simplified hypotheses of real sites. The possibility to have shared and accurate analytical methods is an important challenge for both routine laboratories and supervisory institutions. Although official methods (e.g., APH2009) are already available, they are lacking in some aspects, such as applicability to all the different sampling and analysis media and ease of use in routine analysis. Here, we report our recent advances in the implementation of an empirical method for hydrocarbon speciation in an air matrix, previously developed by the authors and published in 2015. The validation results led to a coefficient of variation (CV%) between 10–15% for the hydrocarbon fractions investigated (C5-C8 aliphatic, C9-C12 aliphatic, C9-C10 aromatic and C11-C12 aromatic) and recovery of ≤20%, in agreement with the required characteristics for the analytical methods. Several real samples were analyzed by the proposed method and the results were compared to those obtained by the official approach. The comparison led to an average bias (that is, the difference between the results from the developed method and those from the conventional one) of about 10%, confirming that the innovative approach is robust, accurate and can be applied to all the analytical media used for air sampling, such as soil gas. [ABSTRACT FROM AUTHOR]

Phosphorus (P) is one of the main limiting nutrients in subtropical forest soils. Both soil type and aggregate structure affect the P sorption capacity of soil; thus, determining soil P supply and leaching characteristics. However, the mechanism of their interactions on soil P sorption and leaching at an aggregate level remains unclear. We classified soil aggregates from red soils and limestone soils in a subtropical forest via wet-sieving and carried out P isothermal sorption experiments. The P sorption maximum (Qm), P sorption strength (KL, KF), P sorption index (PSI) and maximum buffer capacity (MBC) were obtained by fitting to Langmuir and Freundlich isotherm equations. Moreover, different P fractions were determined to estimate the degree of P sorption saturation (DPS) of aggregates. The results showed that the Qm of the two soils were similar, but the sorption strength (KL, KF) and MBC of the limestone soil were higher than those of the red soil. Higher contents of free iron (Fe) oxide and amorphous aluminum (Al) oxide in the limestone soil may enhance the P sorption capacity and, thus, reduce P availability, resulting in a higher total P retention capacity than in the red soil. A higher content of complex Fe in red soil may reduce P sorption and, therefore, play a role in maintaining the supply capacity of soil-available P. The 0.25–0.5 mm aggregates of the two soils had the largest MBC among all aggregate sizes, and their P sorption and buffering capacity were stronger than other aggregates. The DPS of different aggregate sizes were all low, indicating that the soils of subtropical forests were in a state of P deficiency; thus, the risk of P leaching was low. The <0.1 mm aggregate in red soil had relatively high DPS and significantly lower PSI than the other aggregate sizes, indicating that it was more prone to P leaching. The results provide further insight into forest management to improve P availability and reduce P leaching in subtropical forest soils. [ABSTRACT FROM AUTHOR]

Cu-containing hierarchical SAPO-34 catalysts were synthesized by the bottom-up method using different mesoporogen templates: CTAB encapsulated within ordered mesoporous silica nanoparticles (MSNs) and sucrose. A high fraction of the Cu centers exchanged in the hierarchical SAPO-34 architecture with high mesopore surface area and volume was achieved when CTAB was embedded within ordered mesoporous silica nanoparticles. Physicochemical characterization was performed by using structural and spectroscopic techniques to elucidate the properties of hierarchical SAPO-34 before and after Cu introduction. The speciation of the Cu sites, investigated by DR UV-Vis, and the results of the catalytic tests indicated that the synergy between the textural properties of the hierarchical SAPO-34 framework, the high Cu loading, and the coordination and localization of the Cu sites in the hierarchical architecture is the key point to obtaining good preliminary results in the NO selective catalytic reduction with hydrocarbons (HC-SCR). [ABSTRACT FROM AUTHOR]

This paper considers the features of determining the total tin content in waters with different salinity. Direct ICP-spectrometric analysis of sea waters with a salinity of more than 6‰ significantly reduced the analytical signal of tin by 70% (ICP-MS) and 30% (ICP-OES). The matrix effect of macrocomponents was eliminated by generating hydrides using 0.50 M sodium borohydride and 0.10 M hydrochloric acid. The effect of transition metals on the formation of tin hydrides was eliminated by applying L-cysteine at a concentration of 0.75 g/L. The total analyte concentrations, considering the content of organotin compounds, were determined after microwave digestion of sample with oxidizing mixtures based on nitric acid. The generation of hydrides with the ICP-spectrometric determination of tin leveled the influence of the sea water matrix and reduced its detection limit from 0.50 up to 0.05 µg/L for all digestion schemes. The developed analysis scheme made it possible to determine the total content of inorganic and organic forms of tin in sea waters. The total content of tin was determined in the waters of the Azov and Black seas at the levels of 0.17 and 0.24 µg/L, respectively. [ABSTRACT FROM AUTHOR]

The U.S. Department of Energy's Co-Optima initiative simultaneous focused on diversifying fuel sources, improving efficiency, and reducing emissions through using novel combustion strategies and sustainable fuel blends. For medium-duty/heavy-duty diesel engines, research in this area has led to the development of a multimode strategy that uses premixed charge compression ignition (PCCI) at low loads and conventional diesel combustion (CDC) at mid–high loads. The aim of this study was to understand how emissions were impacted when using PCCI instead of CDC at low loads and switching to an oxygenated biofuel blend. It provides a detailed speciation of the hydrocarbon (HC) and particulate matter (PM) emissions from a multimode medium-duty engine operating at low loads in PCCI and CDC modes and high loads in CDC. The effect of the oxygenated biofuel blend on emissions was studied at all three mode–load conditions using #2 ULSD and a bio-derived fuel (25% hexyl hexanoate (HHN)) blended in #2 ULSD. The PCCI mode effectively decreased NOx, total HC, and PM/PN emissions, with a substantial decrease in larger particles (≥50 nm). A PM/PN reduction was observed at high loads with the 25% HHN fuel. While the total HC emissions were not impacted by fuel type, the detailed HC analysis exposed changes in the HC's composition. [ABSTRACT FROM AUTHOR]

Selenium can either be essential or toxic depending on the concentration and oxidation state. In this study, the concentrations of inorganic selenium [Se(IV)] in water samples were determined in the presence of hexavalent selenium [Se(VI)} in water. Water samples were collected from ten different sampling sites in Blood and Mokolo Rivers in Limpopo Province, South Africa. A solid phase extraction (SPE) method with Dowex 1 × 2 resin (chloride form) as an adsorbent material was used to preconcentrate and separate Se(IV) selectively in the presence of Se(VI) in water samples. Concentrations of Se(IV) were quantified by inductively coupled plasma-mass spectrometry (ICP-MS) and ranged from 0.0411 to 0.820 µg/L and 0.135 to 2.79 µg/L in Blood and Mokolo Rivers, respectively. The presence of Se(IV) in water samples collected from Blood and Mokolo Rivers suggests that industrial and agricultural activities around these rivers have an impact on water quality. [ABSTRACT FROM AUTHOR]

Several methods have been used to assess heavy metal contamination in sediments. However, an assessment that considers both composite heavy metal speciation and concentration is necessary to accurately study ecological risks. This study improved the potential ecological risk index method and calculated the toxicity coefficients of seven heavy metals: Arsenic (As), Cadmium (Cd), Chromium (Cr), Copper (Cu), Nickel (Ni), Lead (Pb), and Zinc (Zn). The newly calculated toxicity coefficients were validated by using previously published heavy metal distribution data of the Henan section of the Yellow River. The calculation procedure is based on the principle that the abundance of heavy metals in the environment and their bioavailable forms affect the toxicity of heavy metals. The toxicity coefficients for the seven heavy metals were calculated as follows: As = 10, Cd = 20, Cr = 5, Cu = 2, Ni = 5, Pb = 5, Zn = 1. Ecological risk assessment of the Henan section of the Yellow River using the improved toxicity coefficients revealed that the ecological risk of Cd and total heavy metals is higher than previous calculations, reaching the strength and moderate risk levels, respectively. The improved potential ecological risk index method is more sensitive to heavy metal pollution and thus provides a better indication of ecological risk. This is a necessary improvement to provide more accurate pollution assessments. [ABSTRACT FROM AUTHOR]

Rice can accumulate more organic and inorganic arsenic (iAs) than other crop plants. In this study, the localization of As in rice grains was investigated using High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) based on 26 rice varieties collected from two provinces. In all the samples, the total As contents in polished rice were 0.03–0.37 mg/kg, with average values of 0.28 and 0.21 mg/kg for two sample sets. The results of the determination of arsenic speciation in different components of rice grain showed that in the polished and brown rice the mean value of arsenite (As(III)) was nearly twice than that of arsenate (As(V)). The regional difference was observed in both total As contents and As speciation. The reason may be that As(III) is more mobile than As(V) in a dissociated form and because of soil properties, rice varieties, and the growing environment. The proportion of iAs and the total As in rice bran was higher than that in polished rice, and this is because As tends accumulate between the husk and the endosperm. In our study, selenium could alleviate the risk of arsenic toxicity at the primary stage of rice growth. Co-exposure to As and Se in germinated rice indicated that the reduction in As accumulation in polished rice reached 73.8%, 76.8%, and 78.3% for total As, As(III), and As(V) when compared with rice treated with As alone. The addition of Se (0.3 mg/kg) along with As significantly reduced the As amount in different parts of germinated rice. Our results indicated that Se biofortification could alleviate the As accumulation and toxicity in rice crops. [ABSTRACT FROM AUTHOR]

Studying and understanding the complexity and interactions of different factors influencing stream sediment quality is necessary for the development of successful water quality management strategies. This study aims to evaluate the level of contamination by potentially toxic elements (PTEs) (As, Co, Cr, Cu, Mn, Ni, Pb, V, Zn) of the stream sediments of the Nile River. During the spring of 2019, river sediments were sampled at 23 sites along the Nile River. For each sample, one aliquot was digested in aqua regia and analyzed by ICP-MS for pseudo-total concentration, while for another aliquot, sequential extraction procedures were applied to determine chemical speciation. Compositional data analysis (CoDa) and k-means were applied to recognize the contribution of natural and anthropogenic sources, while pollution indices (EF, RAC) and sediment quality guidelines (SQGs) were applied to assess the ecological risk to biotic species. The results reveal that elements such as Cr, Mn, V and Fe, found in high concentrations in almost all samples (Cr up to 739 mg/kg, Mn up to 1942 mg/kg, V up to 507 mg/kg, Fe up to 98,519 mg/kg), have a natural origin, while the concentrations of Cu (up to 69 mg/kg), Ni (up to 88 mg/kg), Co (up to 42 mg/kg) and As (up to 9.8 mg/kg) are linked to both natural and anthropogenic processes. Sequential extraction shows that Mn, Co, Ni and, in some sites, Cu and Zn, are the most bioavailable elements. These elements present a high risk of toxicity, while the remaining elements imply a low-to-moderate risk. [ABSTRACT FROM AUTHOR]

The development of new tools for assessing the health of cultured shellfish larvae is crucial for aquaculture industries to develop and refine hatchery methodologies. We established a large-volume ecotoxicology/health stressor trial, exposing mussel (Perna canaliculus) embryos to copper in the presence of ethylenediaminetetraacetic acid (EDTA). GC/MS-based metabolomics was applied to identify potential biomarkers for monitoring embryonic/larval health and to characterise mechanisms of metal toxicity. Cellular viability, developmental abnormalities, larval behaviour, mortality, and a targeted analysis of proteins involved in the regulation of reactive oxygen species were simultaneously evaluated to provide a complementary framework for interpretative purposes and authenticate the metabolomics data. Trace metal analysis and speciation modelling verified EDTA as an effective copper chelator. Toxicity thresholds for P. canaliculus were low, with 10% developmental abnormalities in D-stage larvae being recorded upon exposure to 1.10 μg·L−1 bioavailable copper for 66 h. Sublethal levels of bioavailable copper (0.04 and 1.10 μg·L−1) caused coordinated fluctuations in metabolite profiles, which were dependent on development stage, treatment level, and exposure duration. Larvae appeared to successfully employ various mechanisms involving the biosynthesis of antioxidants and a restructuring of energy-related metabolism to alleviate the toxic effects of copper on cells and developing tissues. These results suggest that regulation of trace metal-induced toxicity is tightly linked with metabolism during the early ontogenic development of marine mussels. Lethal-level bioavailable copper (50.3 μg·L−1) caused severe metabolic dysregulation after 3 h of exposure, which worsened with time, substantially delayed embryonic development, induced critical oxidative damage, initiated the apoptotic pathway, and resulted in cell/organism death shortly after 18 h of exposure. Metabolite profiling is a useful approach to (1) assess the health status of marine invertebrate embryos and larvae, (2) detect early warning biomarkers for trace metal contamination, and (3) identify novel regulatory mechanisms of copper-induced toxicity. [ABSTRACT FROM AUTHOR]

The optimization and application of a new hyphenated procedure for iron ionic speciation, i.e., high performance liquid chromatography (HPLC) with short cation–exchange column (50 mm × 4 mm) coupled to high resolution inductively coupled plasma optical emission spectrometry (ICP hrOES), is presented in this paper. Fe(III) and Fe(II) species were separated on the column with the mobile phase containing pyridine–2,6–dicarboxylic acid (PDCA). The total time of the analysis was approx. 5 min, with a significantly low eluent flow rate (0.5 mL min−1) compared to the literature. Additionally, a long cation-exchange column (250 mm × 4.0 mm) was used as reference. Depending on the total iron content in the sample, two plasma views were chosen, e.g., an attenuated axial (<2 g kg−1) and an attenuated radial. The standard addition method was performed for the method's accuracy studies, and the applicability was presented on three types of samples: sediments, soils, and archaeological pottery. This study introduces a fast, efficient, and green method for leachable iron speciation in both geological and pottery samples. [ABSTRACT FROM AUTHOR]