Elevated Concentrations Of Mn Research Articles

Effects of wind-driven current and thermal dynamics in a temperate monomictic reservoir: Implications for manganese transport and treatment in water supply systems

Increasing manganese (Mn) concentrations in source water contribute to aesthetic and health-related concerns in drinking water. The challenges with Mn in drinking water primarily arise from elevated Mn concentrations in the water supply reservoir, with the inefficacy of Mn treatment largely attributed to fluctuating Mn levels in the water source. A three-dimensional Mn cycle model in a temperate monomictic reservoir, Tarago Reservoir, and a decision support system reflecting Mn variations in the local water treatment plant have been established in previous research. This study aimed to examine Mn variations from the reservoir to raw water and treated water under the influence of wind conditions during different stages of thermal structure, and discover valuable recommendations for Mn treatment in the local water supply system. We crafted 12 scenarios to scrutinize the impact of varying intensities of offshore and onshore winds on hydrodynamic processes and Mn transport during strong thermal stratification, weak thermal stratification, and turnover. The scenario analysis revealed that, during the gradual weakening of thermal stratification, offshore wind induced a substantial amount of Mn to the upper layers near the water intake point. Conversely, onshore wind hindered the upward transport of Mn. The simulated Mn in the raw water under the 12 scenarios indicated that the timing of turnover in the Tarago Reservoir is the primary concern for Mn treatment in the water treatment plant. Additionally, close attention should be given to the frequency and intensity of offshore winds during the weakening of thermal stratification.

Assessing benthic ecological status of Kaduvaiyar estuary, southeast coast of India – Biotic indices approach

The Kaduvaiyar estuary located on the Southeast coast of India in Nagapattinam is facing various human-induced pressures, making it highly affected by human intervention. To evaluate the ecological quality of the Kaduvaiyar estuary and its coastal region, an extensive survey was conducted. The assessment employed different statistical analyses, specifically the AMBI and M-AMBI biotic indices. Through PCA analysis, it was confirmed that St-1 exhibited a higher similarity level of Clay and TOC. Furthermore, the CCA analysis demonstrated the presence of pollution-tolerant and opportunistic polychaetes species, such as Capitella capitata, Cossura coasta, Prionospio pinnata, and Notomastus sp., in St-1 and St-2. These areas showed elevated concentrations of heavy metals, including Fe, Pb, and Mn. This trend was also evident in the w-statistics, where the negative values (−0.08 and −0.105) indicated the highly polluted nature of St-1 and St-2. Substantiating this, the AMBI values (ranging from 1.86 to 4.17) suggested that the stations (St-1 to St-3) were slightly to moderately disturbed. The M-AMBI result (ranging from 0.43 to 0.44) indicated a clear signal of the disturbed nature and moderate ecological condition of stations (St-1, St-2). These stations are located near urban and harbor activities, which likely contribute to their altered state. However, it is essential to subject the reference conditions proposed for the Kaduvaiyar estuary to further evaluation in upcoming studies. Additional research will help gain a more comprehensive understanding of the estuary's ecological health and establish a solid basis for comparison with future assessments.

Effects of Different Soil Amendments on Growth, Yield and Nutrients Uptake of Stem Amaranth in Acidic Alluvial-and-Hill Soils in a Subtropical Area

ABSTRACT Sandy and acidic soil conditions are the major factors limiting the production of some vegetable crops in acidic soils. This study aims to examine the effect of various amendments on the growth, yield and mineral nutrients uptake of stem amaranth. Two pot experiments were conducted separately in two generic soils. Six treatments viz. T0 = control (without amendment), T1= lime, T2 = lime + wetland bottom sediment, T3 = lime + vermicompost, T4 = lime + rice straw biochar (RSB) and T5 = RSB were used for both experiments following CRD with four replications. Results revealed that plant heights (45.96 and 50.33 cm) of amaranth grown in alluvial and hill soils, respectively, were the highest in T4 treatment. Similarly, treatment T4 showed the highest fresh (118.53 and 116.11 g pot−1, respectively) and dry biomasses (16.98 and 19.54 g pot−1, respectively) for both soils. For both soils, treatment T4 resulted better nutrient uptake of N, P, K, S, Zn, Fe and Mn by edible stem, while non-amended soil gave the lowest result at all parameters. Analytical values of post-harvest soils indicated that T4 and/or T5 treatments resulted in an improvement in soil pH, organic carbon, total N, exchangeable K and extractable P, S and Zn. Treatment T3 showed elevated concentrations of extractable soils Fe and Mn. The amendment RSB combined with lime can be preferably used in strong acidic soils for cultivation of stem amaranth.

Geochemistry and mineralogy of legacy tailings under a composite cover

Remediation by a composite cover was implemented on partly oxidized sulfide-rich tailings in northern Ontario, Canada to reduce the production and release of acid mine drainage (AMD). The impact of the cover on sulfide oxidation rates and trace element mobility was initiated a decade after cover installation via multi-year measurements of pore-gas concentrations, pore-water and groundwater sampling and analysis, mineralogical studies of the tailings, selective chemical extractions, and synchrotron-based X-ray absorption experiments. Depleted pore-gas O2 concentrations, circumneutral pH, and improvement in water quality were observed at one detailed sampling location, suggesting that the cover decreased AMD generation and transport. Carbon and sulfur isotope ratios indicate sulfate reduction occurred at the base of the tailings. In contrast, near-atmospheric pore-gas O2 concentrations, low pH, and elevated aqueous concentrations of Fe, sulfate, Zn, Cu, As, and Pb were observed at another location, suggesting localized sulfide oxidation. Trace elements in the tailings are associated with secondary crystalline and amorphous Fe(III) oxyhydroxides, covellite, and Fe(III) hydroxysulfate phases, formed prior to cover installation. Substantial reductive dissolution of Fe(III) oxyhydroxides due to the isolation of the tailings from the atmosphere by the cover was not observed. Concentrations of Zn and Mn remained elevated due to limited sequestration under the current acidic to circumneutral pH. Although secondary Fe(III) oxyhydroxides contain As(V) and As(III), which were released by arsenopyrite oxidation, dissolved As persists. Due to localized sulfide oxidation, element remobilization, and limited capacity for sulfate reduction, diminished water quality, with elevated aqueous concentrations of sulfate, Zn, As, and Mn, may endure.

Interstitial carbonates in pillowed metabasaltic rocks from the Pilbara Craton, Western Australia: A vestige of Archean seawater chemistry and seawater-rock interactions

Calcites hosted in the interpillow void spaces of extremely well preserved, 3.47–3.12 Ga pillow lavas of the Archean Pilbara Craton, Australia, provide new geochemical insights into the composition of Archean seawater and its interaction with basaltic crust. We present a comprehensive dataset of major and trace elements, radiogenic 147Sm-143Nd, 87Rb-87Sr, and stable C-O isotopes for these calcites.Based on their elemental composition and Post-Archean Australian Shale-normalized rare earth element and yttrium (REYPAAS) patterns, two types of calcites can be distinguished. Type I (n = 9) are coarse-grained calcites with elevated Mn concentrations (478–14,790 ppm) and high REY concentrations that match the basaltic host rock compositions. Petrographic textures in combination with geochemical data indicate precipitation from boiling seawater trapped between pillows during basalt eruption. Small light-REYPAAS depletions, only slightly super-chondritic Y/Ho (34.5–39.1), and low δ18O(VSMOW2) (9.25–16.66 ‰) suggest relatively high fluid-rock interactions of boiling seawater with the basaltic host rock. These characteristics are similar to those of interstitial carbonates found in modern mid-ocean ridge basalts. Type II carbonates (n = 6) are fine-grained, low-Mn (13.7–420 ppm) calcites that exhibit comparably high Sr concentrations (825–2,516 ppm) and anoxic modern seawater-like REYPAAS patterns, strong super-chondritic Y/Ho (39.1–55.8) and δ18O(VSMOW2) values of 9.10–13.18 ‰. These features hint to direct calcite precipitation from seawater within the degassing space with little fluid-rock interaction.Almost all (Type I and Type II) of the calcites investigated here, combined with their respective host rocks, yield well-defined Sm-Nd isochron ages for the Apex (3,466 ± 23 Ma), Euro (3,365 ± 43 Ma), Honeyeater (3,187 ± 33 Ma), and Bradley (3,131 ± 24 Ma) formations. Only calcites from the Mt. Ada Basalt and their associated host rocks show a ∼ 100 Ma younger Sm-Nd isochron age (3,361 ± 22 Ma) compared to the U-Pb zircon age of formation.Highly radiogenic initial Sr isotope compositions of the high-Mn calcites (Type I) and low Sr concentrations, suggest Sr remobilization for these calcites. In contrast, the low-Mn calcite (Type II) exhibit higher Sr concentrations and lower 87Sr/86Sr(i) of 0.7010–0.7011 at 3.34 Ga and 0.70137 at 3.12 Ga, suggesting increasing influence of crustal weathering on the composition of Paleoarchean seawater through time, and progressive decoupling from the Archean mantle (87Sr/86Sr(i) = 0.7003–0.7007).

A halophilic Chromohalobacter species from estuarine coastal waters as a detoxifier of manganese, as well as a novel bio-catalyst for synthesis of n-butyl acetate.

Anthropogenic pollution due to ferro-manganese ore transport by barges through the Mandovi estuary in Goa, India is a major environmental concern. In this study a manganese (Mn) tolerant, moderately halophilic Chromohalobacter sp. belonging to the family Halomonadaceae was isolated from the sediments of a solar saltern adjacent to this Mandovi estuary. Using techniques of Atomic absorption spectroscopy, Scanning electron microscopy-Energy dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy and Atomic Force Microscopy, the Chromohalobacter sp. was explored for its ability to tolerate and immobilize Mn in amended and unamended media with 20% natural salt concentration (w/v). In aqueous media supplemented with 0.1 mM Mn, the Chromohalobacter sp. was capable of sequestering up to 76% Mn with an average immobilization rate of 8 mg Mn /g /day. Growth rate kinetic analysis using Gompertz mathematical functions was found to model the experimental data well. The model inferred that the maximum growth rate of Chromohalobacter sp. was at 10% natural salt concentration (w/v). The Chromohalobacter sp. was further found to be multimetal tolerant showing high tolerance to Iron (Fe), Nickel (Ni) and Cobalt (Co), (each at 4 mM), and tolerated Manganese (Mn) up to 6 mM. Morphologically, the Chromohalobacter sp. was a non-spore forming, Gram negative motile rod (0.726 μ× 1.33 μ). The adaptative mechanism of Chromohalobacter sp. to elevated Mn concentrations (1 mM) resulted in the reduction of its cell size to 0.339 μ× 0.997 μ and the synthesis of an extracellular slime, immobilizing Mn from the liquid phase forming Manganese oxide, as confirmed by Scanning Electron Microscopy. The expression of Mnx genes for manganese oxidation further substantiated the finding. This bacterial synthesized manganese oxide also displayed catalytic activity (∼50% conversion) for the esterification of butan-1-ol with CH3COOH to yield n-butyl acetate. This Chromohalobacter sp. being indigenous to marine salterns, has adapted to high concentrations of heavy metals and high salinities and can withstand this extremely stressed environment, and thus holds a tremendous potential as an environmentally friendly "green bioremediator" of Mn from euryhaline environments. The study also adds to the limited knowledge about metal-microbe interactions in extreme environments. Further, since Chromohalobacter sp. exhibits commendable catalytic activity for the synthesis of n-butyl acetate, it would have several potential industrial applications.

Geochemical conditions regulating chromium preservation in marine sediments

In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records.

Impact of past mining activities on water quality in a karst area in the Cévennes region, Southern France

Sampling and analysis of groundwater and surface water were conducted to assess the potential impacts of abandoned mines on water quality in a karst area in Southern France. The results of multivariate statistical analysis and geochemical mapping revealed that water quality is affected by contaminated drainage from abandoned mine sites. Acid mine drainage with very high concentrations of Fe, Mn, Al, Pb and Zn was identified in a few samples collected from mine openings and near waste dumps. In general, neutral drainage with elevated concentrations of Fe, Mn, Zn, As, Ni and Cd was observed due to buffering by carbonate dissolution. The contamination is spatially limited around abandoned mine sites, suggesting that metal(oid)s are sequestered in secondary phases that form under near-neutral and oxidizing conditions. However, the analysis of seasonal variations in trace metal concentrations showed that the transport of metal contaminants in water is highly variable according to hydrological conditions. During low flow conditions, trace metals are likely to be rapidly sequestered in Fe-oxyhydroxides and carbonate minerals in the karst aquifer and the river sediments, while low or no surface runoff in intermittent rivers limits the transport of contaminants in the environment. On the other hand, significant amounts of metal(loid)s can be transported under high flow conditions, primarily in dissolved form. Dissolved metal(loid) concentrations in groundwater remained elevated despite dilution by uncontaminated water, likely as a result of the increased leaching of mine wastes and the flushing of contaminated waters from mine workings. This work shows that groundwater is the main source of contamination to the environment and highlights the need to better understand the fate of trace metals in karst water systems.

A novel homozygous SLC39A14 variant in an infant with hypermanganesemia and a review of the literature.

Manganese (Mn) is an essential trace metal necessary for good health; however, excessive amounts in the body are neurotoxic. To date, three genes (SLC30A10, SLC39A8, and SLC39A14) have been discovered to cause inborn errors in Mn metabolism in humans. As very rare diseases, the clinical features require further clarification. A male Chinese patient who mainly presented with hypermanganesemia and progressive parkinsonism-dystonia was recruited for this study. We collected and analyzed clinical information, performed whole-exome sequencing (WES), and reviewed the relevant literature. The motor-developmental milestones of the patient were delayed at the age of 4 months, followed by rapidly progressive dystonia. The patient displayed elevated Mn concentrations in blood and urine, and brain magnetic resonance imaging (MRI) showed symmetrical hyperintensity on T1-weighted images and hypointensity on T2-weighted images in multiple regions. A novel homozygous variant of the SLC39A14 gene (c.1058T > G, p.L353R) was identified. The patient was treated with disodium calcium edetate chelation (Na2CaEDTA). Three months later, mild improvement in clinical manifestation, blood Mn levels, and brain MRI was observed. To date, 15 patients from 10 families have been reported with homozygous mutations of SLC39A14, with a mean age of onset of 14.9 months. The common initial symptom is motor regression or developmental milestone delay, with a disease course for nearly all patients involving development of progressive generalized dystonia and loss of ambulation before treatment. Additionally, hypermanganesemia manifests as Mn values ranging from 4- to 25-fold higher than normal baseline levels, along with brain MRI results similar to those observed in the recruited patient. Nine SLC39A14 variants have been identified. Seven patients have been treated with Na2CaEDTA, and only one patient achieved obvious clinical improvement. We identified a novel SLC39A14 mutation related to autosomal recessive hypermanganesemia with dystonia-2, which is a very rare disease. Patients present motor regression or delay of developmental milestones and develop progressive generalized dystonia. Chelation therapy with Na2CaEDTA appears to effectively chelate Mn and increase urinary Mn excretion in some cases; however, clinical response varies. The outcome of the disease was unsatisfactory. This study expands the genetic spectrum of this disease.

Subcellular Localization of Manganese in Two Green Microalgae Species with Different Tolerance to Elevated Mn Concentrations

Subcellular Localization of Manganese in Two Green Microalgae Species with Different Tolerance to Elevated Mn Concentrations

Improving remineralization and manganese-removal of soft waters using a mixed CaCO3/MgO contactor

The aim of this study was to investigate the role of MgO on the long-term operation of a mixed media contactor. Specifically, the simultaneous removal of aqueous manganese and the remineralization of soft waters using pure calcite are limited by a remineralization breakthrough after 600 h of operation in the presence of high Mn concentrations (5 mg Mn/L). The introduction of as little as 5 % (m/m) MgO was able to improve the Mn removal kinetic, while maintaining remineralization objectives over 720 h of operation. After treating elevated concentrations of Mn, both media exhibited a Mn-coated layer which contributed to limiting the mass transfer from the media core to the liquid phase. X-ray photoelectron spectroscopy (XPS) identified this superficial layer as 10 % Mn oxides (MnOx) on MgO media compared to 1.4 % MnOx on calcite, suggesting the MgO acts as the preferred reaction surface during Mn removal. Therefore, it is postulated that in the presence of MgO, Mn removal is impacted by high pH conditions (pH = 10.5) which introduces a significant precipitation mechanism as Mn2+ is oxidized. For all the examined conditions, the formation of this coating improved Mn removal due to the autocatalytic nature of the adsorption/oxidation of dissolved manganese by MnOx. MgO is therefore thought to contribute to a complex sorption-coprecipitation process in the operation of a mixed media contactor.

Geogenic manganese and iron in groundwater of Southeast Asia and Bangladesh – Machine learning spatial prediction modeling and comparison with arsenic

Naturally occurring, geogenic manganese (Mn) and iron (Fe) are frequently found dissolved in groundwater at concentrations that make the water difficult to use (deposits, unpleasant taste) or, in the case of Mn, a potential health hazard. Over 6000 groundwater measurements of Mn and Fe in Southeast Asia and Bangladesh were assembled and statistically examined with other physicochemical parameters. The machine learning methods random forest and generalized boosted regression modeling were used with spatially continuous environmental parameters (climate, geology, soil, topography) to model and map the probability of groundwater Mn > 400 μg/L and Fe > 0.3 mg/L for Southeast Asia and Bangladesh. The modeling indicated that drier climatic conditions are associated with a tendency of elevated Mn concentrations, whereas high Fe concentrations tend to be found in a more humid climate with elevated levels of soil organic carbon. The spatial distribution of Mn > 400 μg/L and Fe > 0.3 mg/L was compared and contrasted with that of the critical geogenic contaminant arsenic (As), confirming that high Fe concentrations are often associated with high As concentrations, whereas areas of high concentrations of Mn and As are frequently found adjacent to each other. The probability maps draw attention to areas prone to elevated concentrations of geogenic Mn and Fe in groundwater and can help direct efforts to mitigate their negative effects. The greatest Mn hazard is found in densely populated northwest Bangladesh and the Mekong, Red and Ma River Deltas of Cambodia and Vietnam. Widespread elevated Fe concentrations and their associated negative effects on water infrastructure pose challenges to water supply. The Mn and Fe prediction maps demonstrate the value of machine learning for the geospatial prediction modeling and mapping of groundwater contaminants as well as the potential for further constituents to be targeted by this novel approach.

Manganese uptake and partitioning between the tissue of the anemone host Exaiptasia pallida and Symbiodinium spp., including assessment of stress and recovery

Manganese (Mn) is essential for global steel and Mn-iron (Fe) alloy production. The human health effects of elevated Mn concentrations have been well established, but studies on its impact on marine invertebrates are limited. This study is the first to investigate Mn uptake in the sea anemone Exaiptasia pallida after chronic exposure (0.5, 1, 10, and 100 mg/L) for 24-d. Following exposure, E. pallida were transferred to ambient seawater for 6-d to assess Mn depuration. Mn accumulation and partitioning in host tissue and symbionts (Symbiodinium spp.), tentacle retraction, and symbiont cell density were measured during exposure and depuration. Mn concentrations were substantially higher in symbionts than tissue in all treatments after 24-d. No significant difference was observed for symbiont cell density after Mn exposure. Tentacle retractions were significantly higher in all Mn exposed treatments than controls at all time points. Mn depuration was observed for both tissue and symbionts but was more rapid in symbionts. This study reveals that Symbiodinium spp. can play a role in Mn uptake and depuration in anemones, but Mn loading does not affect cell density. These results help understand metal uptake and depuration in complex relationships between Symbiodinium spp. and other host taxa like corals.

Variations of arsenic in groundwater from a transect in Van Phuc village, Hanoi

In this study, the author report detailed results of the variation of arsenic in groundwater along a transect in an area near the Hanoi city centre. The results showed that 64% of collected samples exceeded the WHO guideline value for arsenic concentration in drinking water. The arsenic concentration varied in a wide range, strongly depending on the sediment characteristics of each zone along the transect. Aside from As, groundwater in this area also was contaminated by elevated concentrations of Fe, Mn, and ammonium. The study also pointed out a positive correlation between As and reductive chemical species, namely DOC, NH4+, and CH4 in groundwater. Although there is no clear trend in the correlation between As and Fe, Mn, it can be concluded that the formation of arsenic in groundwater in the study area was due to the reductive dissolution of As-bearing iron minerals under the presence of organic matter.

Basin scale distributions of dissolved manganese, nickel, zinc and cadmium in the Mediterranean Sea

Samples for dissolved trace metal concentrations were collected during GEOTRACES expedition GA04-N in summer/spring in the Mediterranean Sea, starting in the Atlantic Ocean and sampling both deep basins of the Mediterranean Sea. Outflow of Mediterranean Outflow Water leads to elevated concentrations of Mn, Ni and Zn in the Atlantic Ocean, but a concentration minimum in the Atlantic distribution of Cd. Nevertheless, when comparing the in- and outflow, the Mediterranean is a net source of Cd to the Atlantic Ocean. Surface concentrations of Mn, Ni, Zn and Cd are elevated in the Mediterranean relative to the Atlantic Ocean where Ni and Cd gradually increased along the eastward surface water flow path, Zn reached a homogenous concentration in the order of 1 to 1.5 nM, and Mn displayed a patchy surface distribution. The observed differences are attributable to the different dynamics of their biogeochemical cycling, notably the partitioning between the dissolved and particulate phases due to biological uptake, scavenging and possibly organic complexation. The elevated surface concentrations of Mn, Ni, Zn and Cd in the Mediterranean are derived from atmospheric deposition, where most likely Zn and Cd are mainly sourced from anthropogenic origin, Mn mostly from lithogenic origin and Ni from both anthropogenic and lithogenic origin. Dissolved Zn and Cd, as well as phosphate and nitrate, display striking inter-basin fractionations with elevated concentrations in the deep water of the western basin compared to the deep eastern basin, without a coinciding increase in the apparent oxygen utilization. Given that physical circulation or contribution from biogenic particulate metals cannot explain the elevated dissolved concentrations, an external non-biological source is required. This source is most likely a vertical flux of metal laden particles dissolving through the water column of the western Mediterranean where these particles, most likely from anthropogenic origin, are derived from either atmospheric deposition or particulate material deposited on the continental shelves that makes its way into the deep basin. To confirm or detect trends in dissolved metal concentrations in the deep basin, regular basin wide assessments of the trace metal distributions in the Mediterranean are needed. The distributions of Mn, Ni, Zn and Cd in the Sea of Marmara illustrate that all of these metals can be affected by anthropogenic surface sources and highlight the different susceptibilities of the dissolved metal distributions to supply from remineralization, and to removal through scavenging. This study provides a first baseline to assess future changes and underlines that the Mediterranean marine environment is susceptible to anthropogenic disturbances, with varying effects for different metals due to differing source strengths and biogeochemical cycles.

Redox dependence of manganese controls cadmium isotope fractionation in a paddy soil-rice system under unsteady pe + pH conditions

Flooding in paddy soils alters the soil redox of manganese (Mn) and produces elevated concentrations of soluble Mn that can reduce cadmium (Cd) uptake by rice. To better understand the fates of Mn and Cd, along with changes in soil redox conditions, we conducted microcosm incubations in paddy soil covering the reduction to oxidation to re-reduction phases. The extractable Cd concentration decreased rapidly during the reduction phases but increased upon oxidation, and Cd availability largely depended on soil pH, Eh, pe + pH, and the extractable Mn concentration. Exogenous Mn can promote Cd binding with Fe–Mn(oxyhydro)oxides. A trade-off effect between the soil-extractable Cd and Mn concentrations across changes in pH, Eh, pe + pH was identified, and attaining an optimal pe + pH value of 6.8 was targeted. Furthermore, to provide insights into how the redox status of Mn changes to alter Cd mobilization in a paddy soil-rice system, Cd isotope ratios across the paddy soil-rice tissue continuum were investigated using planted rhizobox experiments under different irrigation regimes. The heavy Cd isotopes from the soil to liquid-phase (Δ114/110Cdextract-soil = 0.40–0.82‰) and from the soil to rice grain (Δ114/110Cdgrain-soil = 0.84–0.89‰) were preferentially enriched. Light isotopes were likely to be enriched in Cd bound to Fe/Mn-oxides, a process that was promoted by increased Mn availability. These results suggest that Cd isotopes are systematically fractionated within the paddy soil–rice system, which is caused by the unsteady soil redox, and the stabilization of Cd in the bound soil pool such as Fe–Mn(oxyhydro)oxides-Cd under reducing conditions could be developed as a Cd retention mechanism in paddy soils.

Behavioral and neurochemical studies of inherited manganese-induced dystonia-parkinsonism in Slc39a14-knockout mice

Inherited autosomal recessive mutations of the manganese (Mn) transporter gene SLC39A14 in humans, results in elevated blood and brain Mn concentrations and childhood-onset dystonia-parkinsonism. The pathophysiology of this disease is unknown, but the nigrostriatal dopaminergic system of the basal ganglia has been implicated. Here, we describe pathophysiological studies in Slc39a14-knockout (KO) mice as a preclinical model of dystonia-parkinsonism in SLC39A14 mutation carriers. Blood and brain metal concentrations in Slc39a14-KO mice exhibited a pattern similar to the human disease with highly elevated Mn concentrations. We observed an early-onset backward-walking behavior at postnatal day (PN) 21 which was also noted in PN60 Slc39a14-KO mice as well as dystonia-like movements. Locomotor activity and motor coordination were also impaired in Slc39a14-KO relative to wildtype (WT) mice. From a neurochemical perspective, striatal dopamine (DA) and metabolite concentrations and their ratio in Slc39a14-KO mice did not differ from WT. Striatal tyrosine hydroxylase (TH) immunohistochemistry did not change in Slc39a14-KO mice relative to WT. Unbiased stereological cell quantification of TH-positive and Nissl-stained estimated neuron number, neuron density, and soma volume in the substantia nigra pars compacta (SNc) was the same in Slc39a14-KO mice as in WT. However, we measured a marked inhibition (85–90%) of potassium-stimulated DA release in the striatum of Slc39a14-KO mice relative to WT. Our findings indicate that the dystonia-parkinsonism observed in this genetic animal model of the human disease is associated with a dysfunctional but structurally intact nigrostriatal dopaminergic system. The presynaptic deficit in DA release is unlikely to explain the totality of the behavioral phenotype and points to the involvement of other neuronal systems and brain regions in the pathophysiology of the disease.

Geochemistry of fracture coatings in Athabasca Group sandstones as records of elemental dispersion from the McArthur River Uranium deposit

A mineralogical and geochemical study of minerals on seven types of fracture fillings from near and above the McArthur River unconformity-related uranium deposit has been carried out to determine if fracture filling materials and wall rocks record evidence of primary and secondary dispersion of elements from the deposit. This study shows that Pb extracted by weak acid leaching (2% HNO3) provides Pb-Pb model ages near 1100 Ma for fractures with any of the three REE patterns: 1) LREE-enriched patterns, 2) REE patterns that are concave and similar to uraninite in the deposit, and 3) fractures with flat REE patterns. The REE patterns and ages indicate the fractures are an open system to post-mineralization dispersion of radiogenic Pb from a U-rich source, with a major mobilization of Pb from the uranium deposit at ca. 1100 Ma.Brown (Type 1) fractures, which host Mn-Fe oxides and clay minerals, provide the best evidence of U mineralization through post-mineralization dispersion, containing elevated concentrations of pathfinder elements Co, Ba, Tl, Mn and radiogenic Pb near the surface and at depth. Post-mineralization dispersion is also observed within brown (Type 1) and pink (Type 7; clay minerals + hematite) fractures and wall rock, showing low 207Pb/206Pb values of 0.29–0.50 that were subsequently overprinted by fluids with more common Pb, as recorded in fractures with higher 207Pb/206Pb values of 0.51–0.84.Fracture fillings were analyzed by continuous leach inductively coupled plasma mass spectrometry (CL-ICP-MS) to determine the relationship between trace elements and elemental release from specific mineral phases. CL-ICP-MS results indicate that common Pb (with 207Pb/206Pb values > 0.7) and anomalous Co (360 ppm) and V (220 ppm) contents are resident in organic phases that are dissolved during the 10% H2O2 leach phase. CL-ICP-MS also indicates that radiogenic Pb, as well as Ni and V, are resident in clay minerals and Fe-Mn oxy-hydroxides that break down during leaching with 30% HNO3. Uranium contents are low in the leachate during release of Fe, Al, Mn, and Pb using the 10% and 30% HNO3 leaches, reflecting post-mineralization dispersion of radiogenic Pb, but not U. Thus, secondary dispersion of elements into fractures enhances the size of the deposit footprint, particularly in deep fractures near the P2 fault, but also in some fractures near the surface. The results of this study strongly suggest that fractures did indeed act as conduits for dispersion of elements from the deposit, reaching all the way from deposit to the surface, providing viable exploration targets for U mineralization in sedimentary basins.

Origin, fate and ecotoxicity of manganese from legacy metallurgical wastes

Over the course of history, mining and metallurgical activities have influenced the socioeconomic development of human populations. However, these past and current activities can also lead to substantial environmental contamination by various metals. Here, we used an interdisciplinary approach (incorporating archaeology, mineralogy, environmental chemistry and ecotoxicology) to investigate the origin, fate and potential ecotoxicity of anomalous manganese (Mn) concentrations detected in the ancient mining district of Berthelange (medieval period, eastern France). Mineralogical investigations of slag samples showed that smelting temperature conditions in medieval bloomeries led to the production of slags mainly composed of Fe- and Mn-rich olivine, i.e., fayalites. Further mineralogical analyses of bulk soil and clay fractions allowed us to identify the presence of serpentine. This evidence of olivine weathering can account for the release of Mn from slags into the soil. In addition, chemical analyses of total and available (exchangeable and reducible) Mn concentrations in soil samples clearly showed the contribution of slags deposited 1000 years ago to soil contamination. A complementary ecotoxicity bioassay performed on soils from a slag heap using the land snail Cantareus aspersus confirmed that a significant fraction of the Mn detected in soils remains available for partitioning with the soil solution and transfer to soil organisms. Although no growth inhibition of snails was observed after 28 days of exposure, the animals accumulated quite elevated Mn concentrations in their tissues. Our study emphasizes the environmental availability and bioavailability of Mn from ancient metallurgical wastes to soil-dwelling invertebrates, i.e., snails, even one millennium after their deposition. Hence, as for more recent industrial sites, past mining ecosystems must be a cause of concern for the scientific community and public authorities.

Previously unrecognized potential threat to children from manganese in groundwater in rohingya refugee camps in Cox’s Bazar, Bangladesh

The forced displacement of over 700,000 Rohingyas from Myanmar to Bangladesh since the crackdown in August 2017 has resulted in a critical humanitarian and environmental crisis. Groundwater is the primary source of drinking water in the camps that were constructed to provide shelter for the refugee population. The current study explores occurrence of Mn in groundwater in the Rohingya camps and adjacent areas. A total of 52 groundwater samples were collected between August and October 2018 from different camps sites and the adjacent host area. It was found that 64% exceeded the Bangladesh standard (100 μg/L) suggesting the presence of elevated concentrations of Mn in some groundwater aquifers in the camp sites. Mn is a neurotoxicant and previous studies have reported intellectual impairment in children exposed to Mn levels similar to those detected in groundwater in the camp sites. Nearly 450,000 migrant and new-born children live in the camps in already stressed conditions. The occurrence of elevated Mn concentrations in groundwater in the camps and their adjacent areas is likely an additional stressor exposing these children to an increased risk of neurotoxicity. Based on the results of this small-scale study, we recommend undertaking an in-depth study on the occurrence of Mn in groundwater in the camps to come up with appropriate strategies to minimise exposure. In addition, we recommend conducting a systematic epidemiological study on potential impacts of manganese in drinking water on neurological development of the Rohingya children in the camps.