Sources Of Metals Research Articles

Novel Nonsymmetrically benzimidazolium salts and their silver(I)-N-heterocyclic carbene complexes: Synthesis, crystal structure, DFTstudies and anticancer activities

Due to the success of Ag-NHCs in biological applications, interest in the synthesis and applications of such compounds is increasing rapidly. Therefore, in this study, preparation and structural definition of silver(I)–NHC complexes were accomplished. These complexes were synthesized by combining a metal source, Ag2O, with imidazolium salts in dichloromethane. A comprehensive characterization process was carried out for both the ligands and their resulting complexes. This involved utilizing various analytical techniques, such as elemental analysis, LC-MS, FTIR and NMR spectroscopy. Further, structure of the 3 h complex was determined by X-ray crystallography. A single-crystal of 3 h shows that coordination geometry is a slightly distorted linear coordination geometry around the silver(I) center. Furthermore, our combined experimental and theoretical approach provided insights into the crystal structure, coordination geometry, and intermolecular interactions stabilizing the complex’s lattice. Density functional theory (DFT) optimization revealed its geometry, while time-dependent DFT (TD-DFT) calculations shed light on its optical properties. Furthemore the newly synthesized ligands and silver(I) complexes were evaluated for their in vitro anticancer activity against three human cancer cell lines including hepatocellular carcinoma (HePG2), lung adenocarcinoma (A549) and breast adenocarcinoma (MCF7). Most of the newly synthesized silver(I) complexes exhibited better activity than the ligands, and the results have been compared with Cisplatin as a reference drug.

Sulfide trace element enrichments in the metamorphic basement-hosted Xinhua Pb-Zn-Cu vein-type deposit, eastern Guizhou province (SW China)

Cambrian carbonate formations are widespread in the western Hunan-eastern Guizhou (WHEG) region (southwestern China), which hosts many Mississippi Valley-Type (MVT) lead–zinc (Pb-Zn) deposits. Regional Pb-Zn mineralization is well developed in the low-grade metamorphic rocks of the basal Proterozoic Banxi Group. The mineralization is associated with quartz veins and generally distributed along NE-trending fault zones. Moreover, these deposits have an extensive distribution and high grade, and are associated with Cu-Ag endowment. However, geological and geochemical research on these Pb-Zn vein-type deposits is relatively limited, and their relationship with the regional MVT mineralization remains unclear. The representative Xinhua deposit in Danzhai district is selected as the study subject. We conducted in situ trace element analyses on the sphalerite and chalcopyrite from the various metallogenic stages, and compared them with published sphalerite trace element data from the MVT Pb-Zn deposits in the western Hunan-eastern Guizhou metallogenic belt. Seven orebodies in Xinhua Pb-Zn deposit have been discovered so far, with a metal resource of over 120,000 metric tonnes of Zn + Pb. Field geology and microscopic petrography have revealed two mineralization stages: An early-stage black sphalerite (Sp-I) followed by reddish-brown sphalerite (Sp-II) mineralization, which corresponds to the main chalcopyrite mineralization stage, and a later-stage light-yellow sphalerite (Sp-III), Cu ore-barren mineralization.LA-ICPMS data indicate that the sphalerite from Xinhua has similar trace element compositions to those from the MVT Pb-Zn deposits in the region. They are relatively enriched in Ga, Cd, and Ge, while depleted in Fe, Co, and Mn. Critical metal Ge and Ga are particularly enriched in sphalerite, especially in Sp-I (Ge max 937 ppm, Ga max 824 ppm). The substitution mechanism of Ge and Ga in sphalerite are likely 2Cu+ + Ge4+ ↔ 3Zn2+ and Cu+ + Ga3+ ↔ 2Zn2+. Indium and Sn are mainly present in Sp-I and Sp-III. Chalcopyrite contains Zn and Sn both exceeding 100 ppm. Contents of Se, Ag, In, and Sn in chalcopyrite are significantly higher than those in sphalerite. Calculation of the sphalerite trace element geothermometer (GGIMFis) suggests that the average sphalerite ore-forming temperatures are 164 °C (Sp-I), 156 °C (Sp-II), and 205 °C (Sp-III), implying medium- to low-temperature mineralization. This indicates a possible influx of high-temperature, in-bearing fluid during the late-stage mineralization.In summary, the faults-controlled vein-type Pb-Zn deposits (e.g., Xinhua) may have been products of the same Kwangsian orogeny as other strata bound MVT deposits, and the Xinhua deposit features two mineralization stages with multiple ore metal sources. During the ore-forming fluid ascent, some ore-forming materials may have precipitated in the fluid conduits. And exposed after the erosion of the shallower stratiform orebodies and strata. Consequently, the Xinhua Pb-Zn deposit represents the preserved ore-fluid conduit phase (in the basement strata) of the MVT mineralization.

Enhancing photocatalytic performance of rose-shaped Co/Ni bimetallic organic framework for reducing CO2 to CO under visible light

Co-MOF-74, composed of Co salt as the metal source and 2,5-dihydroxyterephthalic acid as the organic ligand, is widely used as a catalyst for the photocatalytic reduction of CO2 due to its open metal sites, high porosity, large specific surface area, and high CO2 adsorption capacity. However, its effectiveness in CO2 conversion is limited by weak electron transfer capabilities and a high rate of electron/hole pair recombination. To address these limitations, a bimetallic strategy was employed to significantly improve the catalytic performance of Co-MOF-74 for photocatalytic CO2 reduction. Stable bimetallic Co/Ni-MOF-74-x (x = 1, 2, 3) with controllable morphology and metal ratios were synthesized by adjusting the molar ratios of Co2+ and Ni2+ and combining them with 2,5-dihydroxyterephthalic acid. The introduction of Ni2+ led to a significant increase in the specific surface area, from 204.999 m2/g (Co/Ni-MOF-74) to 790.873 m2/g (Co/Ni-MOF-74-1). In addition, the band gap of bimetallic Co/Ni-MOF-74-1 was narrowed to 1.4 eV, which enhanced charge transfer. As a result, photocatalytic experiments demonstrated that the CO2 conversion efficiency of bimetallic Co/Ni-MOF-74-1 was significantly improved, reaching 4.539 mmol/g/h, compared to that of the monometallic Co-MOF-74. Finally, a synergistic photocatalytic mechanism involving ligand activation was proposed to explain the reaction process of the bimetallic Co/Ni-MOF-74 catalyst. Meanwhile, this study highlights that the bimetallic strategy is an effective approach to optimizing the performance of MOF catalysts for the photocatalytic reduction of CO2.

Quantification of heavy metal contamination and source in urban water sediments using a statistically determined geochemical baseline

Geochemical baselines (GBs) play a crucial role in discerning natural variability from anthropogenic impacts on elemental composition within the environment. However, their applicability in quantifying the contribution of pollution sources to heavy metal contamination in sediments remains understudied. This research aimed to assess the degree of contamination and local pollution source attribution by leveraging geochemical baselines derived from statistical techniques, specifically the relative cumulative frequency (RCF) and 2σ-iterative (2σ-I) methods. In the urban water systems of Ma’anshan City, the major iron ore centre in eastern China, we observed concentration ranges of Cr, Cu, Ni, Pb and Zn in 36 sediment samples ranging from 66.89 to 352.08 mg/kg, 22.01 to 133.37 mg/kg, 22.66 to 50.80 mg/kg, 14.66to 264.37 mg/kg and 73.30 to 2707.46 mg/kg, respectively. RCF and 2σ-I techniques yielded similar GBs with no significant differences (p > 0.05). The geo-accumulation index and contamination factor analysis showed a sediment heavy metal accumulation rank of Zn > Pb > Cr > Cu > Ni. The contribution percentage of pollution sources varied with land functional type of watershed. For industry-influenced sediments, the contribution of local sources to Cr, Cu, Pb and Zn was significant, with shares of 43%–88%. Overall, this study highlights the valuable insights provided by GBs for effective management of urban aquatic environments.

Iron capture mechanism for harmless recovering platinum group metals from spent automobile catalyst

ABSTRACT Automotive catalysts are the largest consumption source of platinum group metals (PGMs). When it exceeds its useful life, spent automotive catalysts (SACs) are the most important secondary PGMs resource and are classified as hazardous solid waste. Recycling SAC is a promising solution to alleviate the shortage of PGMs resources for projects and reduce environmental pollution. The technology for recovering PGMs by iron-melting collection can obtain Fe-PGMs alloy and harmless glass slag. In this paper, the spontaneous aggregation and growth behaviour of Fe and PGMs in slag at melting temperature were studied, and the settling velocity of Fe-PGMs particles in the slag was calculated to be 6.68 × 10−3 m/s. The effects of melting time, melting temperature and Fe dosage on PGMs recovery were determined, and the optimal conditions were 10 wt% Fe, 1500°C and 40 min. The toxicity test verifies that the slag obtained is a clean slag harmless to the environment. This work explains the mechanism of Fe collection of PGMs and provides a pathway for efficient and harmless recovery of PGMs from SAC.

Three-dimensional MOFs confined Anderson-type POMs clusters—Templated fabrication of porous Co-NiMo/Cr2O3 catalyst with superior NH3-SCR catalytic activity

Fabricating ecofriendly and high-performance NOx reduction catalysts is significant but challenging. This study introduces an innovative approach for creating homogeneous and porous Co-NiMo/Cr2O3 composites by employing a POMs@MOFs (POMs = polyoxometalates, MOFs = metal organic frameworks) core − shell template as a precursor and subsequent high-temperature treatment, in which the Anderson-type POMs are confined within the MIL-101 MOFs as secondary building units. The well-organized architecture of NiMo6@MIL-101 made it possible to provide a widely dispersed metal source and later transform into defect-rich catalyst. This confinement strategy allows the prepared Co-NiMo/Cr2O3 catalysts to be uniformly dispersed without aggregation and exposes abundant active sites. It also triggers more electron transfer, producing a strong synergistic effect that results in an increase in specific surface area, Olatt/Otol ratio and the number of acidic sites. Boosted by synergistically multidoping effect, the as-prepared Co-NiMo/Cr2O3 catalyst exhibits superior activity in NOx reduction (95 %, 150 °C), which is 3 times that of Cr2O3 derived from pure MOFs under the same condition. This work may shed the light on the design and fabrication of multifunctional nanoporous metal oxide composites materials and inspire the application of polyoxometalates in NOx removal processes.

Assessment of soil environmental capacity for heavy metals in Shantou City, Guangdong Province, China: source analysis and enrichment evaluation.

Most studies assessing soil environmental capacity (EC) often overlook the impact of heavy metal sources. Analyzing the sources of heavy metals (HMs) provides a better understanding of regional environmental capacity characteristics and their dynamic changes. The current study focuses on the surface soil of Shantou, using 511 soil samples to assess the soil environmental capacity. Results indicate that the contents of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn in Shantou's surface soil are notable, with lead moderately enriched and other metals lightly enriched. The principal component analysis (PCA) identifies five primary sources of heavy metals: mixed natural and agricultural sources, mixed agricultural and industrial sources, industrial sources, mining sources, and quarrying sources. The primary source contributing significantly to soil HM concentrations in Shantou City is a complex interplay between natural geological processes and extensive agricultural practices. In terms of static environmental capacity, Zn, Cr, Ni, Pb, Cu, As, Hg, and Cd are ranked in descending order. The overall environmental capacity for heavy metals in the soil is at a medium level, influenced by geological backgrounds. However, regions such as Yanhong Town, Guiyu Town, and Chendian Town face lower environmental capacities due to comprehensive human activities, posing certain risks. This study provides a scientific reference for forecasting, controlling soil heavy metal pollution, and improving soil quality and environmental capacity in Shantou City.

Incorporating source apportionment and health risk assessment of heavy metals from indoor dust of an industrial area in Dhaka, Bangladesh

A total of 45 deposited dust samples were collected from the preselected 15 households near an industrial area at Savar, Bangladesh. The concentrations of metals were measured by EDXRF spectroscopy and was found at the following trend: Ca > Fe > K > Ti > Mn > Zr > Sr > Rb > Zn > Cu > Pb > Co. The average concentrations of Cu, Zn, Zr, and Pb were found to be higher than that of the soil background values set by Chinese Environmental Protection Administration (CEPA) and the upper continental crust (UCC), while the average concentrations of K, Ti, Fe, and Rb were found to be higher than that of the background values and lower than that of UCC. Alternately, %RSD for some toxic metals (i.e., Fe, Co, Zn and Pb) in the dust samples were ranged broadly (%RSD: 33.54–86.88 %), which indicates that these trace metals might be present in indoor dust samples due to anthropogenic sources, which is consistent with the ANOVA test. In this study, the contamination levels of metals were assessed based on the enrichment factor (EF), pollution load index (PLI), and geo-accumulation index (Igeo). The two ways ANOVA (Fcal = 3.86 >Fcritic = 1.78, df = 14) for EF data had revealed the heterogeneity of metal enrichment in the study area, whereas PLI values were close to 1.0 or > 1, which indicated that the indoor dust samples in the study area might be deteriorated of site quality by the studied metals. The analysis of Igeo also revealed that these dust samples are slightly to extremely polluted. Conversely Pearson correlation analysis, principal component analysis, and cluster analysis were employed to identify the possible sources of such heavy metals, which suggested that the anthropogenic sources are the main sources of the examined heavy elements. Subsequently, the human health risk assessment strategies were applied to identify the routes of exposures based on the US EPA health risk models. For non-cancer effect, ingestion of dust particles is the main exposure route to both the children and adults. The total hazard index (HI) values indicate that both children and adults are vulnerable to non-carcinogenic effect, but children are more vulnerable than adults (tstat = 1.97 >tcritic = 2.039, p = 0.029) at a 95 % confidence level. Nevertheless, no significant carcinogenic health risk due to the presence of Co was found for both children and adults in the study area. According to sensitivity analysis, the ingestion rate (IR) and the concentration of Co posed the most significant impact (> 79.9 %) on cancer risk estimation.

Assessment of health risks based on different populations and sources of heavy metals on agricultural lane in Tengzhou City by APCS-MLR models.

To identify the sources of heavy metals in local soils and their risks to human health. This study quantified the concentrations of eight heavy metals in 504 soil samples collected in Tengzhou, China. The ecological risks of a single heavy metal (EI), a comprehensive ecological risk index (RI), and a health risk assessment model were used to evaluate the level of contamination in the city. The results of the research study indicate that there are different levels of heavy metal pollution in rural and urban agricultural areas in Tengzhou. Moreover, the spatial variability of mercury (Hg) is considerable, reaching 0.96, indicating a significant impact of anthropogenic activities. For the ecological risk, the heavy metal element with the highest EI value was mercury with a mean value of 67.22 and a peak value of 776.00. The heavy metal with the lowest mean EI value was Zn with only 1.03. Meanwhile, the average RI is only 128.59, but some areas have an RI as high as 842.2. The sources of heavy metals were identified using principal component analysis, correlation analysis, and an absolute principal component score multiple linear regression model (APCS-MLR). The non-carcinogenic risk for children, the carcinogenic risk for children, and the carcinogenic risk for adults were 1.23, 2.42×10-4 and 1.00×10-4, respectively, and these values exceeded their respective recommended values, and As and Cr had some carcinogenic hazards. Heavy metals in the soil come from natural, industrial, traffic and agricultural sources and represent 39.59%, 29.48%, 25.17% and 5.77%, respectively. The main source of heavy metals in local agricultural soils is the geological background, and the government needs to strengthen the monitoring of As and Cr in drinking water resources, as well as reduce traffic pollution and factory waste emissions to reduce Hg in soils.

Correction: Alkaline igneous rocks, a potential source of rare metals and radioactive minerals: Case study at Amreit area, south Eastern Desert, Egypt

Correction: Alkaline igneous rocks, a potential source of rare metals and radioactive minerals: Case study at Amreit area, south Eastern Desert, Egypt

Cobalt/nitrogen co-doped carbon nanosheets from coal-based graphene quantum dots boosted oxygen reduction

We report on cobalt/nitrogen co-doped carbon nanosheets (Co/NCNs) as a highly efficient electrocatalyst for the oxygen reduction reaction (ORR). The Co/NCNs were synthesized through pyrolysis at 900 °C using coal-based graphene quantum dots that contain nitrogen as a source of both carbon and nitrogen, NaCl as a template, and trace amounts of cobalt salt as a metal source. The Co/NCNs-0.1 exhibited ORR activity that was equivalent to that of Pt/C, with a half-wave potential of 0.85 V and a limiting current density of 4.9 mA cm−2. Furthermore, the zinc-air battery incorporating Co/NCNs-0.1 demonstrated an open circuit voltage of 1.423 V, a maximum power density of 149 mW cm−2, and a specific capacity of 806.5 mAh g−1 at a current density of 20 mA cm−2. The results of density functional theory calculations indicate that metal Co, when protected by graphitic-N-doped carbon, holds a greater negative charge and exhibits a lower energy barrier compared to other types of nitrogen species. This property contributes to the catalytic activity of the ORR.

Analysis of Electrochemical Deposition of Polyaniline and Polyaniline Composites in Sodium Tungstate and Sodium Molybdate Solutions

Although polyaniline has a high electroactivity in environments below pH 5, it loses its electroactivity in neutral and basic environments. In addition, polyaniline film does not give physically stable film when it becomes thick. For these reasons, polyaniline has been synthesized in the presence of other monomers or inorganic/organic species, leading to the obtaining of composite polymers with some new electrochemical and physical properties. In this study, novel composite polymer films of polyaniline were synthesized electrochemically in the presence of different concentrations of Na2MoO4.2H2O and Na2WO4.2H2O, and these composite polymer films were examined in monomer-free solutions for electrochemical investigation. As a result, the cathodic charge of polyaniline increased from 0.25 mC to 1.50 mC in the presence of 0.05 M Na2MoO4.2H2O. Also, the polyaniline/WO3 composite achieved a charge transfer of 0.42 mC in the presence of 0.25 M NiSO4.2H2O, 0.05 M NiCl2.6H2O, Na2WO4, Na2MoO4.2H2O, 0.4 M Na3C6H5O7.2H2O and 0.05 Na2WO4.2H2O as a metal source. These prove the better charge transfer during the redox reaction of the polyaniline composite film.

Source and health risks of trace metals in Clarias batrachus and Chrysichthys nigrodigitatus from surface waters in Bayelsa State, Nigeria: a probabilistic model

IntroductionHuman activities have inadvertently led to the release of harmful substances, including trace metals, into aquatic environments, with consequential impacts on aquatic organisms and potential health risks for consumers. This research assessed the presence, origins, and health implications of trace elements within the muscles of Clarias batrachus and Chrysichthys nigrodigitatus from the Bomadi and Gbotebo rivers and their surroundings in Bayelsa State, Nigeria.MethodsThirty samples from each fish species were collected and analyzed to conduct the study. Through the use of an atomic absorption spectrophotometer, the researchers determined the concentrations of trace metals, including iron, copper, zinc, lead, nickel, cadmium, and cobalt, in the fish tissues.Results and discussionThe concentrations of the metals within the two fish species varied, with notable differences in zinc and cadmium levels. Utilizing statistical analyses like Pearson correlation, principal component analysis (PCA), and hierarchical cluster analysis (CA), it was established that the trace metals originated from diverse sources. The study then evaluated health risks associated with these trace elements, considering both non-carcinogenic and carcinogenic hazards for different age groups. The results indicated that children’s total target hazard quotient fell below 1 for both fish species, implying a limited tendency toward non-carcinogenic risks through lifelong fish consumption. However, in some adult fish samples, the quotient exceeded 1, indicating a higher potential for non-carcinogenic risks. Regarding carcinogenic hazards, the mean risks were generally lower than the accepted threshold, except for lead in both fish species among adults and children. Stricter values highlighted that only lead concentrations in fish from both categories were deemed acceptable. Consequently, this study highlights the importance of raising awareness among consumers who buy fish from the studied region. Moreover, consistent monitoring of potentially harmful trace elements in water, sediments, and fish is recommended to safeguard consumer health and well-being.

Assessing Trace Metal Contamination and Associated Risks in the Kossan River Ecosystem, Southern Côte d'Ivoire

Trace metals accumulate in aquatic systems and can pose a threat to human health and wildlife. In recent decades, human activity has become the main source of metals in the environment. In order to gain a better understanding of metal contamination in Ivorian rivers impacted by human activity, and to help set up a database, we studied the distribution of arsenics (As), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) in the Kossan River. A total of 21 surface water and sediment samples were taken at 7 stations along the River Kossan between March 2019 and July 2020. Total concentrations of the metals were analyzed by atomic absorption spectroscopy (AAS). Carcinogenic and non-carcinogenic risks were assessed in surface water. Contamination indices such as EF, CF; Igeo and PLI were calculated to determine the level of sediment contamination. Ecological risk indices Er and RI were used to assess the potential risks associated with metals. The concentrations of As, Pb, Cd, Cu and Zn found in surface water samples fell within the following ranges: 2.03 - 17.19, 1.752 - 13.264, 0.067 - 0.774, 17.44 - 2369.11 and 136.72 - 3669.37 µg/L, respectively and in sediment: 0.69 - 4.60, 2.10 - 11.30, 0.13 - 5.00, 1.70 - 28.20 and 4.10 - 90.30 µg/g, respectively. The results showed high levels of As, Cu, Pb and Zn contamination in places, above WHO limits. The calculation of non-carcinogenic and carcinogenic risk indices revealed that arsenic and copper can present major health risks for humans through the consumption of water. Cd concentrations exceeded geochemical background values. The results suggest moderate to very severe Cd contamination of the sediments by anthropogenic origin at certain sampling points. In general, the results of the ecological risk indices revealed low to moderate levels of contamination for metals, with the exception of heavy cadmium contamination in the river. The highest concentrations of trace metals were observed in water and sediment samples collected from stations with high anthropogenic pressure. The continuing intensification of human activity may in the long term present a major risk to man and his environment, hence the need to set up a system for monitoring river watercourses and to develop a system for remediating trace metals in river water such as phytoremediation.

Sources and transport pathways of trace metals to the outer continental shelf off South Carolina and Georgia, USA revealed from the otoliths of moray eels

Trace metal concentrations in otoliths of spotted moray eels (Gymnothorax moringa), non-migratory residents of hard bottom reefs at depths of ∼30–70m along the outer shelf adjacent to South Carolina and Georgia, were analyzed to determine if results provide insights into trace metal sources and transport processes in this dynamic region of the shelf. Li and Mg appear to reflect exposure to local sea water circulated through adjacent porous rock outcrops where the eels reside. Concentrations of Mn, V, Cu, and Zn in otoliths appear to be associated with deep water upwelled along the shelf break. Based on 30 years of water temperature data from fishery surveys, Scamp Ridge, located at 32.30 N at a depth of ∼50m, has significantly lower summertime bottom temperature than elsewhere along the shelf edge, indicating locally enhanced upwelling at that location. The highest levels of Cu and Zn and the lowest of Mn and V were also found in otoliths of eels collected in the vicinity of Scamp Ridge. These results indicate that otolith chemistry in eels can reveal fine-scale structure of water mass inputs to the outer shelf of the southeastern US coast.

Detangling past and modern zinc anthropogenic source contributions in an urbanized coastal river by combining elemental, isotope and speciation approaches

The accumulation of trace metals in the environmental compartments of coastal rivers is a global and complex environmental issue, requiring multiple tools to constrain the various anthropogenic sources and biogeochemical processes affecting the water quality of these environments. The Valao fluvio-estuarine system (Rio de Janeiro, Brazil) presents a challenging case of a coastal river contaminated by both modern and historical anthropogenic metal sources, located in the land and in the intra-estuary, continuously mixed by tidal cycles. This study employed a combination of spatial distribution analysis of trace metals including gadolinium (Gd), zinc (Zn) isotopic analyses, and X-ray absorption spectroscopy (XAS) to distinguish between these sources. The concentrations of metals in both dissolved (water samples) and surficial sediment compartments (Suspended Particulate Matter and sediment samples) display an overall enrichment trend from upstream to downstream. Multivariate statistical analysis allows to discriminate geogenic elements derived from watershed geology (Ti, K, and Mg) vs anthropogenic contaminants from urban runoff and domestic sewage discharges (Cu, Cr, Pb, Zn, and Gd); and legacy metal contaminants (Zn and Cd) remobilized from ancient metallurgical wastes and transported upstream in the estuary during tidal cycles. The anthropogenic Gd concentration in the dissolved compartment increases along the watercourse, highlighting continuous ongoing sewage discharge. Zinc solid speciation also indicates that Zn contribution from legacy metallurgy waste is primarily associated with sulfide-Zn and Zn-phyllosilicate in the outlet estuary, while in upstream sediments of fluvio-estuarine system, Zn is found bound to organic matter. Zinc isotope systematically reveals a progressive downstream shift to heavier isotope compositions. Upstream, the relatively pristine site and the urbanized section of the river exhibit a relatively uniform δ66/64Zn value (+0.20 ± 0.07 ‰) in suspended particulate matter (SPM) and surficial sediments. These results indicate that domestic sewage discharges contribute to Zn enrichment in sediments of the Valao fluvio-estuarine system but without modifying its isotope signature in sediments. The sediment of the downstream estuarine section shows a heavier δ66/64Zn value (+0.48 ± 0.08 ‰), indicating the strong influence of the intra-estuarine source identified as the historical metallurgic contamination. An integrated view of the geochemical tracers allows thus inferring that the untreated sewage and legacy metallurgical contamination are the primary sources of anthropogenic Zn contamination. It highlights the progressive mixing along the estuarine gradient under tidal dynamics. The influence of the former source continuously expands from the headland towards the estuary.

18 Impacts of supplementing sulfate vs. hydroxychloride sources of Cu, Mn, and Zn on heifer growth performance and physiology during feed restriction and high-starch challenge periods

Abstract This study evaluated the effects of supplementing different sources (sulfate vs. hydroxychloride) of Cu, Mn, and Zn during feed restriction and high-starch challenge periods on heifer growth performance and physiology. On d 0, Nelore heifers (n = 40) were stratified by body weight (BW = 238 ± 38 kg) and age (21 ± 1 mo), and individually allocated into 1 of 40 drylot pens. The study was divided: washout (d 0 to 27), nutrient surplus (d 28 to 55), nutrient restriction (d 56 to 83), and high-starch challenge (d 84 to 112). The washout period consisted of limit-feeding Tifton hay (2.5% of BW; DM basis) and providing free choice access to white salt only. On d 28, heifers were randomly assigned to receive protein DM supplementation (0.10 to 0.20% of BW) added with sulfate (SUL) or hydroxychloride (HYD) sources of Cu, Mn, and Zn (≥ 260, 200, and 960 mg of Cu, Mn, and Zn per kg of supplement DM) from d 28 to 112 (n = 20 heifers/treatment). From d 28 to 55, heifers were offered ad libitum Tifton hay. From d 56 to 83, heifers were limit-fed 50% of average hay DM intake consumed in the last 6 d of the previous phase (d 50 to 55). From d 84 to 112, each respective protein supplement was mixed with a starch-based total mixed ration (TMR). Heifers were gradually adapted to the starch-based TMR by increasing the concentrate DM amount while simultaneously decreasing the hay DM amount by 20% every 7 d (starting with 35% concentrate and 65% hay on d 84 and ending with 80% concentrate and 20% hay from day 106 to 112). Individual heifer shrunk BW were collected on d 0, 28, 56, 84, and 112, following 12 h of feed and water withdrawal. Effects of treatment × day and treatment were not detected (P ≥ 0.37) for heifer BW, average daily gain (ADG), and dry matter (DM) intake, except for ADG from d 28 to 56, which was less (P = 0.05) for SUL vs. HYD heifers (-0.21 ± 0.05 vs. -0.10 ± 0.05 kg/day, respectively). Effects of day, but not treatment × day and treatment (P ≥ 0.43), were detected for fecal pH, which remained relatively constant from d 0 to 84, and then decreased (P < 0.01) from 7.2 on d 84 to 5.8-6.0 on d 110. Overall, protein supplementation added with hydroxychloride sources of Cu, Mn, and Zn had minor positive effects on heifer growth performance immediately following a washout period, but did not improve heifer growth performance and fecal pH during nutrient restriction and high-starch challenge periods, compared with protein supplementation added with sulfate sources of same metals.

Source apportionment and emission projections of heavy metals from traffic sources in India: Insights from elemental and Pb isotopic compositions

The study investigates the sources of metals in urban road dusts using elemental concentration and Pb isotopic ratios. The elemental concentrations are also utilized to determine the present heavy metal emissions as well as projected emissions till 2045. Bayesian mixing model for source apportionment highlights the significant contributions of both exhaust and non-exhaust sources to the metal-enriched urban road dusts, with each contributing approximately 40 %. Emission analysis reveals that India’s projected electric vehicle (EV) penetration may not be sufficient to suppress the metal emissions from vehicular exhausts. Further challenge is posed by high metal concentrations in the non-exhaust sources, that dominates the emission of some metals compared to exhaust sources. If the metal concentrations remain unchanged, the emission analysis predicts alarming increases in total emissions from all the exhaust and non-exhaust sources by 174 %, 176 %, 163 % and 184 % for Ni, Cu, Zn and Pb, respectively, from 2022 to 2045. Thus, it is crucial to reduce the metal concentrations in traffic emission sources and also impose better regulatory measures to improve the urban metal pollution scenario.

New data about the provenance of the Early Eneolithic copper artefacts from western Lesser Poland

Abstract The Early Eneolithic period in Lesser Poland is represented by the Lublin-Volhynian culture and the Wyciąże-Złotniki group. For both of them, the main cultural references were the Middle Copper Age groups from the Carpathian Basin (the Bodrogkeresztúr, the Hunyadihalom-Lažňany, the Balaton-Lasinja cultures, as well as the Ludanice, and the Bajč-Retz-Gajary groups). One of the most important indicators of the Transcarpathian influence was the use of various copper objects by local communities and their deposition in graves. A set of seventeen objects, mostly from well-dated grave contexts, was analysed to establish the provenance of the copper artefacts used in western Lesser Poland. This set included artefacts discovered in Złota Grodzisko I and Grodzisko II, Książnice 2, Koniecmosty, Kraków-Wyciąże 5 and Kraków-Cło 7. Energy dispersive X-ray fluorescence analysis was used to study the chemical compositions, while lead isotope ratios were determined using a inductively coupled plasma mass spectrometer (HR-MC-ICP-MS). In addition, some of the objects were visually inspected under a digital microscope to determine how they were made and used. As a result of this analytical programme, it was possible to establish that both Lesser Poland groups used the same copper distribution networks. Initially (c. 4050–3950 BC), the copper originated from the mines in Serbia that at the time were controlled, as suggested in the literature, by the peoples of the Bodrogkeresztúr culture, and also from the mines in the Slovak ore Mountains, linked to the Ludanice group. It appears, however, that from c. 3950 BC onwards, the only source of metal for the production of copper objects used by the inhabitants of western Lesser Poland were the mines located in the Slovak Ore Mountains. This research also suggested that, while around 3950–3800 BC, there was a marked regression in the production and use of copper artefacts in the Carpathian Basin, in the area of western Lesser Poland there was an increase in the use and, most likely, local production of original copper jewellery.

Co‐Based Metal–Organic Frameworks With Dual Redox Active Centers for Lithium‐Ion Batteries With High Capacity and Excellent Rate Capability

AbstractSmall molecule organic materials are widely used as anode materials for lithium‐ion batteries (LIBs) due to their high reversible capacity, designable structure, and environmental friendliness. However, they suffer from poor intrinsic electronic conductivity, severe dissolution, and low initial coulombic efficiency. Recently, metal–organic frameworks (MOFs) have demonstrated in metal‐ion batteries, outperforming some small molecule organic materials in terms of both cycling stability and rate capability. Herein, the first rational design and synthesis of a new cobalt‐based MOF (CoBPDCA), are reported employing cobalt(II) nitrate as the metal source and small organic molecules (2,2‐bipyridyl‐4,4‐dicarboxylic acid, BPDCA) as the ligands, which shows exceptional chemical stability and impressive electron conductivity. Most importantly, CoBPDCA electrodes deliver a high reversible capacity of 1112.9 mAh g−1 at 0.05 C (1 C = 1000 mA g−1) and outstanding high‐rate durability (166.3 mAh g−1 after 2500 cycles at 10 C). Employing a series of spectroscopic and morphological characterizations and density functional theory (DFT) calculations, it is revealed that these impressively electrochemical performances are contributed to the dual active redox centers of Co cations and BPDCA ligands (CN and CO groups), and the superb electron conductivity. This work might provide a new strategy and a deeper understanding of the other MOFs' development for LIBs.