Mobility Of Metals Research Articles

Process-Based and Probabilistic Quantification of Co and Ni Mobilization Risks Induced by Managed Aquifer Recharge.

Managed aquifer recharge (MAR) is an increasingly used water management technique that enhances water availability while commonly generating water quality benefits. However, MAR activities may also trigger adverse geochemical reactions, especially during the injection of oxidant-enriched waters into reducing aquifers. Where this occurs, the environmental risks and the viability of mitigating them must be well understood. Here, we develop a rigorous approach for assessing and managing the risks from MAR-induced metal mobilization. First, we develop a process-based reactive transport model to identify and quantify the main hydrogeochemical drivers that control the release of metals and their mobility. We then apply a probabilistic framework to interrogate the inherent uncertainty associated with adjustable model parameters and consider this uncertainty (i) in long-term predictions of groundwater quality changes and (ii) in scenarios that investigate the effectiveness of modifications in the water treatment process to mitigate metal release and mobility. The results suggested that Co, Ni, Zn, and Mn were comobilized during pyrite oxidation and that metal mobility was controlled (i) by the sediment pH buffering capacity and (ii) by the sorption capacity of the native aquifer sediments. Both tested mitigation strategies were shown to be effective at reducing the risk of elevated metal concentrations.

Heavy metal leaching from wood ash before and after hydration and carbonation

AbstractWood ashes can be used, e.g., as soil fertilizer or in construction materials; however, it is important to ensure that such use will not cause spreading of heavy metals and subsequent harm to the environment. Wood fly ashes (WFAs) generally have higher concentrations of heavy metals than wood bottom ashes. This paper focuses on the leaching of heavy metals from WFA, specifically identifying WFA characteristics that influence the leaching and changes in leaching caused by hydration and carbonation in ambient air. Chemometric modeling based on characteristics for eight different WFAs suggested that the leaching of Cr and Zn was associated with the concentration of K and the leaching of SO42−, indicating a connection to the soluble K2(SO4) commonly found in WFAs. During the aging, both pH and conductivity of the WFAs decreased showing the formation of new phases. The leaching of Cd, Cu, Ni, and Pb was low initially and decreased to non-measurable after the aging. So did the leaching of Zn except from one of the WFAs. Thus, the part of the heavy metals, which were leaching originally, was built into the newly formed phases. The Cr leaching also showed a general decrease during the aging, however, not to similarly low levels. This means that the leaching Cr fraction was either not influenced by the aging processes or the formed phases contained water-soluble Cr. The continued leaching of Cr needs more attention as it may be the toxic and carcinogenic Cr(IV). As the chemistry and mineralogy of WFAs, inclusive of the mobility of the heavy metals, are subject to changes, increased knowledge on the chemistry determining these changes is needed to choose environmentally sound recycling options.

From source to sink via a ferronickel smelting process: Chromium, nickel, and mercury in sediments of the Evoikos Gulf, Greece

Ferronickel smelters are highly waste intensive industrial processes. In the Larymna Bay (LB) of the Evoikos Gulf (Greece), the slag produced after the processing of lateritic ores for nickel extraction used to be discharged to an authorized marine area (slag disposal area; SDA). This study assessed the distribution of Cr, Ni, Fe and Mn, largely related to ultramafic parent rocks, laterites, and the slag, as well as Hg as a tracer of combustion processes in the sediments of Evoikos Gulf. A very severe (Cr) and moderate (Ni) enrichment was found both in LB and SDA in relation to local background levels. Mercury was severely enriched in LB. LB becomes enriched with magnetic particles and metals through washout and deposition of dust. Magnetic susceptibility was found to be a good proxy for Cr and Ni distributions, as well as the dispersal of slag because both parent rocks and slag contain magnetite-like magnetic minerals. The strong tidal currents of the area do not cause the dispersal of slag particles southwards, beyond SDA, yet they are responsible for the accumulation and focusing of Hg in the South Evoikos Gulf, close to the Chalkida city. Metals mobilization potential from the slag was higher compared to laterites, but lower compared to SDA's sediments, due to reduction processes in the plant and oxidation after its disposal, respectively. Oxidation processes result in the genesis of Cr(VI) in SDA and LB, through oxidative reactions with Mn oxides. This is the first time (to the best of our knowledge) that the formation of Cr(VI) from slags is reported. This finding is important for settings rich in Mn oxides, receiving Cr-rich wastes from Fe–Ni smelter plants.

Speciation, mobility, and risks of heavy metals in sediment and water of a freshwater Lake in Fujian Province, China

ABSTRACT This study investigated the level of dissolved heavy metals in the water of Longhu Lake and focused on the speciation, mobility, and risks of heavy metals (Cr, Mn, Ni, Cu, Zn, As, Cd, and Pb) in sediment. The levels of heavy metals in the water were found to be below the thresholds set by the Chinese safe drinking water standard. The highest average percentages of Cr, Ni, Zn, and As were bound with residual fractions, while Pb and Cu were bound with reducible fractions. Additionally, the highest percentage of Cd and Mn was bound to the acid-soluble fraction in the sediment. These findings suggest that Cd, Mn, Pb, and Cu likely originated from anthropogenic sources in the lake. There was a strong correlation between total organic carbon (TOC) and metal fractions in the sediment, indicating that TOC may play a role in transporting heavy metal fractions. Risk assessment code values for Cd and Mn indicated higher risks and mobility, while Ni, Cu, and Zn showed medium risks and mobility for aquatic biota. To mitigate heavy metal contamination, it is recommended to improve monitoring and regulation of urban runoff and inlet areas.

Evaluating the effectiveness of sulfidated nano zerovalent iron and sludge co-application for reducing metal mobility in contaminated soil

Sewage sludge has long been applied to soils as a fertilizer yet may be enriched with leachable metal(loid)s and other pollutants. Sulfidated nanoscale zerovalent iron (S-nZVI) has proven effective at metal sorption; however, risks associated with the use of engineered nanoparticles cannot be neglected. This study investigated the effects of the co-application of composted sewage sludge with S-nZVI for the stabilization of Cd, Pb, Fe, Zn. Five treatments (control, Fe grit, composted sludge, S-nZVI, composted sludge and S-nZVI), two leaching fluids; synthetic precipitation leaching procedure (SPLP) and toxicity characteristic leaching procedure (TCLP) fluid were used, samples were incubated at different time intervals of 1 week, 1, 3, and 6 months. Fe grit proved most efficient in reducing the concentration of extractable metals in the batch experiment; the mixture of composted sludge and S-nZVI was the most effective in reducing the leachability of metals in the column systems, while S-nZVI was the most efficient for reducing about 80% of Zn concentration in soil solution. Thus, the combination of two amendments, S-nZVI incorporated with composted sewage sludge and Fe grit proved most effective at reducing metal leaching and possibly lowering the associated risks. Future work should investigate the longer-term efficiency of this combination.

Effect of multiwall carbon nanotubes and surfactants characteristics on immobilization of heavy metals in contaminated soils

Soil is a vital resource to humans and soil health is a concern of modern societies. One of the problems is the existence of heavy metals (HMs) pollution, which can affect food, water sources and biodiversity. This experimental work studies the effect of multiwall carbon nanotubes (MWCNTs) and surfactants characteristics on HMs immobilization in a contaminated soil. The testing program comprises the characterization of the MWCNTs and surfactants, followed by two distinct adsorption tests: suspension tests designed to supply preliminary information regarding the adsorption capacity of soil particles towards the different HMs, and percolation tests to evaluate the HMs immobilization in conditions mimicking a real in-situ scenario. The different HMs exhibit different affinities order to the soil studied: Pb > Cu > Ni > Zn. Results indicated that the inherent soil particles can immobilize significant quantities of HMs (especially Pb and Cu) due to their fine size and the existence of a substantial amount of organic matter content in the soil matrix. Molecular weight and charge density of the surfactant are characteristics with an impact on the MWCNTs dispersion and also on the adsorption capacity of the different HMs, namely in the case of Ni2+ and even in the case of Zn2+ possessing lower electronegativity and higher mobility. The findings of the study allow concluding that MWCNTs possess the potential to reduce the mobility of heavy metals in soil, even when employed at very low concentration (0.01% w/w), which is an important feature considering their cost.

Seawater flooding of calcareous soils: Implications for trace and alkaline metals mobility

Developing management strategies to safeguard public health and environmental sustainability requires a comprehensive understanding of the solubility and mobility of trace and alkaline metals in the event of seawater flooding. This study investigated the effects of seawater flooding, along the duration of flooding, on the release of trace and alkaline metals (Mn, Fe, Cu, Zn, Ca, K, and Mg) in two calcareous soils (Krome and Biscayne) located in southern Florida. Seawater flooding experiments involved two soil types and four flooding durations (1, 7, 14, and 28 days) replicated three times. Freshwater flooding experiments were also conducted for comparison. After each flooding experiment, soil samples were collected at three depths (15, 30, and 45 cm), and analyzed for selected elements. Comparative analysis revealed significant releases of Mn, Fe, and Zn in both soils flooded by seawater compared to freshwater. In most cases, significant increments were evident as early as 1-day exposure to seawater flooding, which further increased with flooding duration. However, the impacts of seawater flooding had notable differences between the two soils. Seawater flooding in Krome soil for 28 days, resulted in higher Mn, Fe, and Zn contents by 58, 340, and 510% compared with freshwater flooding, while corresponding increases in Biscayne soil were 3.3, 130, and 180%, respectively. Comparable marginal increases in Cu content were observed for both soils. Similarly, seawater flooding increased K, Mg, and Na contents from single-day flooding. The interplay between soil type, column depth, flooding duration, and their interactions proved influential factors in determining Mn, Fe, Cu, and Zn releases, with peak levels typically observed on the 28th day of flooding and at bottom depths. Overall, these findings highlight the release of these elements, raising concerns about potential plant toxicity and groundwater or surface water contamination due to leaching and runoff.

Salinity-Induced Changes in Heavy Metal Behavior and Mobility in Semi-Arid Coastal Aquifers: A Comprehensive Review

Semi-arid coastal aquifers face critical challenges characterized by lower rainfall, higher evaporation rates, and looming risk of over-exploitation. These conditions, coupled with climate change, are conducive to seawater intrusion and promote mechanisms associated with it. The understanding of metal behavior in such environments is limited, and hence, an attempt is made through this review to bridge the knowledge gap. A study on the behavior of trace metals within a specific context of semi-arid coastal aquifers was carried out, and 11 aquifers from 6 different countries were included. The review observed that trace metals within semi-arid coastal aquifers exhibit distinctive behaviors influenced by their surrounding environment. The prevalence of evaporation and continuous seawater intrusion played a pivotal role in shaping trace metal dynamics by curtailing groundwater flux. The findings suggest that the formation of stable Cl and organic ligands under increased alkaline conditions (pH > 8) has higher control over Zn, Pb, and Cd toxicity in a highly ionic reactive condition. In addition, dominant control of Fe/Mn-hydroxide association with Pb and high organic affinity of Zn played a pivotal role in controlling its bioavailability in aquifers such as WFB, Saudi Arabia NW-C and India. On the contrary, under prevailing acidic conditions (pH < 6), carbonate and SO4-ligands become more dominant, controlling the bioavailability/desorption of Cu irrespective of its origin. The behavior of Ni is found to be controlled by stable organic ligands increasing salinity. An increase in salinity in the considered aquifers shows an increase in bioavailability of Ni, except UmC, South Africa, where organic ligands act as a sink for the metal, even at low pH conditions (pH < 5.5). This study indicates that factors such as mineral saturation, carbonate complexes, pH variations (pH > 8), and chloride complexes govern the distribution of trace metals further enhanced by prolonged water residence time. Nonetheless, specific conditions, such as a reducing and acidic environment, could potentially elevate the solubility of highly toxic Cr (VI) released from anthropogenic sources.

Geochemical constraints on the Gano karst bauxite deposit, eastern Alborz Mountains, northern Iran: Implications for provenance, elemental mobility, and distribution of critical metals

The Gano karst bauxite deposit is located in the eastern Alborz Mountains, 90 km NE of Semnan city, northern Iran. The layers and lenticular patches of bauxite are hosted in the Triassic karstified carbonate rocks interbedded with calcareous shale of the Elika Formation, unconformably overlain by siliciclastics of the early Jurassic Shemshak Formation. The bauxite ores have a mineral assemblage dominated by diaspore and hematite, with lesser kaolinite, illite, chlorite, goethite, anatase, dolomite, and quartz. In the Gano area, intrusions range from monzonite to quartz monzonite in composition with an alkaline composition that generated in an extensional regime within a plate tectonic setting. Geochemical signatures of the Gano bauxite ores suggest a derivation from the monzonite intrusions at the base of the Elika Formation, although a contribution of interbedded calcareous shale of the Elika Formation cannot be excluded. Based on the variation of Ce anomaly across the studied profile and the integration of petrographic evidence and mineralogical and geochemical data, the Gano deposit formed in an oxidized environment under warm-humid climates, significantly linked to rainfall seasonality and groundwater-level fluctuations. Gallium, Nb, and V median values of the Gano bauxite ores are a bit above the maximum value of these critical metals in the northwestern Iranian and Alborz bauxite data set, making diaspore-, anatase-, and hematite-rich layers and lenses valuable for further exploration of these critical metals.

Enhanced multi-metals stabilization: Synergistic insights from hydroxyapatite and peroxide dosing strategies

Sediment contamination by heavy metals is a pressing environmental concern. While in situ metal stabilization techniques have shown promise, a great challenge remains in the simultaneous immobilization of multi-metals co-existing in contaminated sediments. This study aims to address this challenge by developing a practical method for stabilizing multi-metals by hydroxyapatite and calcium peroxide (HAP/CaO2) dosing strategies. Results showed that dosing 15.12 g of HAP/CaO2 at a ratio of 3:1 effectively transformed labile metals into stable fractions, reaching reaction kinetic equilibrium within one month with a pseudo-second-order kinetic (R2 > 0.98). The stable fractions of Nickel (Ni), Chromium (Cr), and lead (Pb) increased by approximately 16.9 %, 26.7 %, and 21.9 %, respectively, reducing heavy metal mobility and ensuring leachable concentrations complied with the stringent environmental Class I standard. Mechanistic analysis indicated that HAP played a crucial role in Pb stabilization, exhibiting a high rate of 0.0176 d−1, while Cr and Ni stabilization primarily occurred through the formation of hydroxide precipitates, as well as the slowly elevated pH (>8.5). Importantly, the proposed strategy poses a minimal environmental risk to benthic organisms exhibits almost negligible toxicity towards Vibrio fischeri and the Chironomus riparius, and saves about 71 % of costs compared to kaolinite. These advantages suggest the feasibility of HAP/CaO2 dosing strategies in multi-metal stabilization in contaminated sediments.

Mobilization of heavy metals from floodplain sediments of the Yellow River during redox fluctuations

The floodplain of the Yellow River is a typical area characterized by redox fluctuations and heavy metal pollution. However, the mobilization behavior of heavy metals in floodplain sediments during redox fluctuations remains poorly understood. In this study, reductive mobilization of Fe and Mn was observed under reducing environments through reduction and dissolution, leading to the subsequent release of adsorbed As. In contrast, the mobilization of U occurred under oxic conditions, as the oxidative state of U(VI) has higher solubility. Furthermore, insignificant effects on the mobilization of Cd, Cu, Pb, and Hg were noticed during redox fluctuations, indicating higher stability of these heavy metals. Additionally, we demonstrated that carbon sources can play a key role in the mobilization of heavy metals in floodplain sediments, amplifying the reductive mobilization of Fe, Mn, As and the oxidative mobilization of U. Our findings contribute to the understanding of the biogeochemical cycling of heavy metal in floodplain sediments of the Yellow River and the factors that control this cycling.

The use of in situ Gamma-Ray Spectrometry to Assess the Environmental Impacts of Intensive Agriculture in terms of Geochemical Mobility in soil and waters

The concentration and mobility of metals in the lithosphere and hydrosphere are led by many physical-chemical parameters and processes from natural and anthropogenic origins, the last one resulting in impacts over many ecosystems around the World, including wetlands. These transitional zones, often characterized by the presence of hydric soils, adapted vegetation, and seasonal or permanent presence of surface water, are commonly under human pressure in terms of land use conversion and contamination, notably in agricultural production areas, where excess of nutrients/organic matter, pesticides, salts, sediments, heavy metals and radionuclides (originated from inorganic fertilizers) can substantially alter the ecological balance of those ecosystems. Thus, this study aimed to evaluate the agricultural impact over a tropical geographically isolated wetland in the Brazilian Cerrado by the analysis of geochemical mobility and interaction between surface and groundwater through in situ gamma-ray spectrometry and hydraulic conductivity measurements. The results demonstrated that the margins of this diabase-derived soil wetland are one of the most important and critical compartments due to its capacity of metal immobilization and surface water infiltration, indicated especially by uranium concentrations. Thorium, in turn, was most related to colluvial transport from slopes to the center of wetland. It was also corroborated by low hydraulic conductivity zones as a result of soil compaction due to heavy agricultural machinery and increase in runoff fluxes. Thus, this methodology could be used as an initial fast screening method in wetlands under other climatic and geological/pedological contexts to evaluate the local hydrogeochemical dynamics and impacts of agricultura.

A thorough assessment of mineral carbonation of steel slag and refractory waste

Escalating industrial CO2 emissions necessitate innovative carbon capture and utilization strategies. This study explores the potential of mineral-carbonation of steelmaking slags, particularly White Slag (WS) and various Refractory Wastes (RWs), to mitigate CO2 emissions and valorize industrial wastes. Experiments were performed with waste materials from the production lines at CELSA (Barcelona, Spain). We delved into direct aqueous carbonation, evaluating the performance and characteristics of these wastes under different experimental conditions. Our findings reveal that all slags can effectively sequester CO2. This process is effective not only for pure CO2 but also for diluted flue gases under mild conditions (≤ 100 ºC, ≤ 6 bar). Specifically, WS exhibited peak CO2 sequestration capacities (SC) of 359.79 gCO2/kgslag (pure CO2) and 276.65 gCO2/kgslag (diluted flue gas). In contrast, the RWs presented different kinetic, reaching a maximum SC of 311 gCO2/kgslag after prolonged times. Given the large inhomogeneity of RWs, individual analysis of distinct RW fractions revealed significant variations in carbonation performance. Tundish RW exhibited the highest CO2 sequestration capacity, emphasizing the importance of waste source and mineral composition in the carbonation. Chemical and morphological evaluations confirmed the transformation of CaO to CaCO3, with MgO remaining largely inert. Additionally, the process indicated potential environmental benefits by reducing the mobility of toxic metals, particularly Pb, suggesting an ancillary avenue for waste treatment. This study underscores the utility of CO2 mineralization as a dual-benefit approach within the circular economy framework, offering insights into its application for sustainable waste management and CO2 emission reduction in the steel industry.

Nitrogen enrichment does not adversely affect exchangeable bases in rainfed urban arable soils of Kumasi, a tropical West African city

Urbanisation induces nitrogen (N) enrichment in tropical soils. This enhances soil acidification, leading in turn to a decrease in effective cation exchange capacity (CECe) and base saturation (BSe). Here, we investigated if and how these effects of urbanisation-induced N inputs affect the soils of tropical urban agroecosystems. Our aim was to quantify the impact of urbanisation intensity (UI) on total N (TN) contents and stocks, and to detect possible adverse N effects on soil pH, CECe, and exchangeable bases in rainfed urban arable soils of Kumasi, a tropical city in Ghana, West Africa. We analysed 618 topsoil samples (0–10 cm) from arable fields within the urban perimeter, categorised into four classes forming a gradient from low to high UI. For baseline comparison, 9 samples each from both rural arable fields and an urban forest were included. Urban arable soils generally had higher TN levels than their rural counterparts. Among the urban arable soils however, TN levels decreased with increasing UI, possibly as crop production and related N export through harvest intensified. Conversely, increasing UI correlated with increased levels of exchangeable Ca2+, K+, and Na+. No adverse N effect on soil pH, CECe, and BSe was detected. This could be explained with the strong TN-SOC relationship (R2 ≥ 0.9), and an increasingly strong relationship between exchangeable bases and TN and SOC (R2 = 0.5–0.8) with increasing UI. These relationships suggested a major common source of TN, SOC, and exchangeable bases. As the soils are neither chemically fertilised nor limed, these findings supported earlier studies that this source is provided by dumped biodegradable household waste, charred matter, ash, and construction materials. We concluded that soil N enrichment through these materials in Kumasi is accompanied by abundant bases in the same materials, which overcompensate any theoretic acidification. Our findings imply that not only can the fertility of tropical urban arable soils in cities like Kumasi be maintained, but also that the crops and ground water may not be at risk from the mobilisation of trace elements and heavy metals due to the hindered soil acidification.

Changes in coal waste DOM chemodiversity and Fe/Al oxides during weathering drive the fraction conversion of heavy metals

The long-term accumulation of coal waste on the surface during natural weathering leads to the inevitable migration of heavy metals contained in the coal waste, which increases the likelihood of environmental contamination and health risks. Dissolved organic matter (DOM) and Fe/Al oxides play crucial roles in the transformation and bioavailability of heavy metals. Thus, we analyzed the Fe/Al oxide content and DOM molecular composition in coal waste with different degrees of weathering and explored the influence of DOM chemical diversity and Fe/Al oxides on the potential mobility of heavy metals. Results showed that weathering-driven decrease in Fe oxides (Fed, FeO, and Fep decreased from 82.4, 37.5, and 3.6 mg∙L−1 to 41.3, 24.7, and 2.3 mg∙L−1, respectively) led to decreases in the reducible fractions of V and Cr. The potential environmental risks of more toxic metals of Cd and As, also increased as a result of the residual fractions decreased to 32.6 % and 41.3 %, respectively. Weathering caused an increase in oxygen-to‑carbon ratio, double-bond equivalent, modified aromaticity index, nominal oxidation state of carbon, and molecular diversity and a decrease in (m/z)w and (H/C)w, suggesting that the DOM of highly weathered coal waste possessed high unsaturation, aromatic structures, hydrophilicity, and strong oxidative characteristics. Additionally, although VMF and CrMF showed significant negative correlations with O/C ratio, polyphenolic, carbohydrates, and condensed aromatics, pH remained a key environmental factor determining the potential environmental risks of V and Cr by changing the residual fractions. The mobilities of Cd and As were significantly negatively correlated with those of Fe/Al oxides, particularly Fed, FeO, Fep, and Alp. Our findings contribute to the understanding of the impact of weathering on the geochemical cycling of different coal waste components, providing priority options for environmental risk prevention and control in coal mining areas.

Migration of transition metals and potential for carbon mineralization during acid leaching of processed kimberlite from Venetia diamond mine, South Africa

Carbonation of mafic and ultramafic rocks and mineral wastes provides a permanent way to sequester excess atmospheric CO2. Recent research has shown that this method also offers the potential for enhanced recovery of critical metals from mine tailings. In this study, processed kimberlite from the Venetia diamond mine (South Africa) was used in column acid leaching experiments to assess both its carbonation potential and whether critical metals such as nickel could be recovered during mineral carbonation. Processed kimberlite was treated daily with one pore volume of either deionized water or dilute hydrochloric acid (0.04 M, 0.08 M, 0.12 M and 0.16 M) for 28 days. Iron-rich yellow precipitates consistent with yellow ground formed during the experiments both at the top of the residue columns (corresponding to the inlets of the columns) and within the leachates collected from the bases of columns. The carbonation potential and mobility of transition metals were investigated using a combination of quantitative X-ray diffraction (XRD) using Rietveld refinements, inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM) coupled with EDXS, and synchrotron-based X-ray fluorescence microscopy (XFM). Our results show that the high proportion of clay minerals (e.g., lizardite, smectite, talc, chlorite) in the processed kimberlite act as the primary source for Mg and transition metals such as Ni; however, calcite dissolution is the main source for Ca. The amount of Mg and Ca extracted from processed kimberlite increases with HCl concentration. If acid leaching of processed kimberlite were used at Venetia, the amount of Mg leached from clay minerals would provide an estimated CO2 offset potential ranging from 2.1 to 15.8 % of the mine's total annual emissions. The leached Ca from silicate dissolution could also provide an estimated CO2 offset potential ranging from 2.1 to 8.1 % of the mine's total annual emissions. However, the amount of CO2 released by calcite dissolution during this process is equivalent to 2.1–14.3 % of total annual CO2 emissions at Venetia., thus resulting in a net estimated CO2 offset potential of 2.1–9.6 % if the Ca released from calcite could not be recarbonated. If all of the Ca could be reprecipitated as calcite, the acid leaching techniques employed in this study could offset 4.2–23.9 % of the Venetia mine's CO2 emissions. Ultimately, greater concentrations and/or amounts of acid may be used to access more of the offset potential of Mg phyllosilicates in kimberlite, but the CO2 released by calcite dissolution must also be won back by recarbonation.

Nitrate-induced mobilization of trace elements in reduced groundwater environments

Groundwater is an essential source for drinking water production. Nitrate infiltration into groundwater due to over-fertilization can cause a potential risk for groundwater quality. Pyrite and other geogenic minerals can be oxidized and trace metals consequently released into water, e.g., nickel and uranium.To achieve a better understanding of the nitrate-induced mobilization of metals, this study investigated the release of antimony, arsenic, chromium, cobalt, molybdenum, uranium, and vanadium from three different reduced sediments after nitrate addition. The experiments were conducted as batch and soil column tests under oxygen-free conditions. In addition to the ORP, the pH value was a relevant driver for the metal mobilization due to pH dependent adsorption and ion exchange processes. Uranium concentrations in the water increased with increasing redox potential. Also, antimony and, to a lesser extent, molybdenum showed higher mobilization at higher ORP as well as at higher pH values. On the contrary, arsenic and cobalt was immobilized with increasing redox potential. Pourbaix diagrams demonstrated very complex species distributions even in synthetic water. The mobilization of trace metals is expected to be also influenced by the type of surrounding rocks and water quality parameters such as dissolved organic carbon.

Incipient carbonate melting drives metal and sulfur mobilization in the mantle.

We present results from high-pressure, high-temperature experiments that generate incipient carbonate melts at mantle conditions (~90 kilometers depth and temperatures between 750° and 1050°C). We show that these primitive carbonate melts can sequester sulfur in its oxidized form of sulfate, as well as base and precious metals from mantle lithologies of peridotite and pyroxenite. It is proposed that these carbonate sulfur-rich melts may be more widespread than previously thought and that they may play a first-order role in the metallogenic enhancement of localized lithospheric domains. They act as effective agents to dissolve, redistribute, and concentrate metals within discrete domains of the mantle and into shallower regions within Earth, where dynamic physicochemical processes can lead to ore genesis at various crustal depths.

Uranium accumulation in environmentally relevant microplastics and agricultural soil at acidic and circumneutral pH

The co-occurrence of microplastics (MPs) with potentially toxic metals in the environment stresses the need to address their physicochemical interactions and the potential ecological and human health implications. Here, we investigated the reaction of aqueous U with agricultural soil and high-density polyethylene (HDPE) through the integration of batch experiments, microscopy, and spectroscopy. The aqueous initial concentration of U (100 μM) decreased between 98.6 and 99.2 % at pH 5 and between 86.2 and 98.9 % at pH 7.5 following the first half hour of reaction with 10 g of soil. In similar experimental conditions but with added HDPE, aqueous U decreased between 98.6 and 99.7 % at pH 5 and between 76.1 and 95.2 % at pH 7.5, suggesting that HDPE modified the accumulation of U in soil as a function of pH. Uranium-bearing precipitates on the cracked surface of HDPE were identified by SEM/EDS after two weeks of agitation in water at both pH 5 and 7.5. Accumulation of U on the near-surface region of reacted HDPE was confirmed by XPS. Our findings suggest that the precipitation of U was facilitated by the weathering of the surface of HDPE. These results provide insights about surface-mediated reactions of aqueous metals with MPs, contributing relevant information about the mobility of metals and MPs at co-contaminated agricultural sites.

Metal mobility after resuspension of contaminated sediments from a tropical urban bay

Dredging activities are recurrent in coastal cities, however, they can cause the remobilization of contaminants, increasing the risk to the biota. Guanabara Bay is a complex eutrophic estuary that undergoes dredging in several areas during the year. The Meriti River estuary is silted up and highly contaminated by metals, such as Cr, Cu, and Zn, due to the discharge of untreated sewage. In this sense, the present study aims to evaluate the remobilization of metals in the sediment (Cr, Cu, Fe, Mn, Ni, Pb, and Zn) and bioavailability after resuspension. Twelve sampling points were collected along 4 transects. The resuspension experiments were performed at two intervals: 1 h (T1) and 24 h (T2) and followed protocols from previous studies. In general, all metals are remobilized after resuspension. - In addition, the bioavailability change (BC) index was applied., which showed 54% remobilization of Cr after T2. The transects closer to the river showed less remobilization after resuspension, which may be related to the saline gradient. Zn was the only metal that exceeded CONAMA Resolution 454/12 level 2 after resuspension, indicating a significant anthropogenic input to the area. Although organic matter (OM) is one of the main regulators of bioavailability in this study, the results suggest that there is an interference of bacterial activity in the dynamics of OM degradation, which directly impacts the bioavailability of metals after resuspension.