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Lithological characteristics interact with other factors of soil formation to define soil genesis. This becomes more interesting as data on the mineral and elemental oxide components of soils developed from limestone are rarely available in the humid tropical environment. The present study investigated the elemental oxide content, forms of sesquioxides, and clay mineral species in some limestone soils. Soil samples were obtained from three (3) crestal soil profile pits and analyzed for elemental content by the use of an X-ray fluorescence spectrometer, and sesquioxide forms by inductively coupled plasma-mass spectrometer. Analyses were done in triplicates. The mineralogy of the clay fraction was determined on the A, B, and C horizon samples using an X-ray diffraction technique. The occurrence of SiO 2 (203-277 g/kg), Al 2 O 3 (65-105 g/kg), and Fe 2 O 3 (14-95 g/kg) in substantial amounts over MnO 2 , ZrO 2 , and TiO 2 with negligible quantities of CaO suggested comparatively more developed soils in the Agoi Ibami and Mfamosing tropical rainforests. Crystalline form of Fe was dominant over amorphous form, with indications of the co-migration of dithionite Fe with clay to the B horizons of the soils. Quartz, kaolinite, montmorillonite, and chlorite-vermiculite-montmorillonite interlayered minerals dominated the clay mineralogy of the studied soils. Mineral transformation places the soils at the transitory stage from the intermediate to the complete stage of soil development. The expanding clay minerals are most likely to increase plant nutrient adsorption and soil fertility status to accommodate the cultivation of a wider range of crops., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

High levels of manganese (Mn) and other heavy metals from electrolytic manganese residue (EMR) stockpiled would be released into the environment under natural conditions. A batch-leaching test was carried out to investigate the release characteristics of heavy metals from EMR with different storage times under simulated environmental conditions such as acid rain with different pH (3.0, 4.5, 5.6, and 7.0) at contact times of 1, 2, 4, 6, and 12 h; liquid to solid ratio (L/S) (5:1, 10:1, 20:1, and 30:1); and temperature (15, 25, 35, and 45 °C). The results showed that low pH (3.0 and 4.5) and high temperature (35 and 45 °C) could significantly promote heavy metal leaching from EMRs and increasing the L/S ratio above 20:1 mL/g significantly decreased heavy metal leachate concentrations due to dilution effect. Cr, Mn, and Pb concentrations in leachate increased almost continuously throughout the leaching process, while Zn decreased slightly at the 12th hour. Meanwhile, heavy metal concentrations in EMR1 (fresh EMR) were higher than in EMR2 (out stockpiled for more than 3 months). The concentrations of Mn, Pb, and Zn in leachates from EMRs at pH 3.0 and 4.5 leaching far exceeded the allowable maximum discharge concentrations for pollutants of the integrated wastewater discharge standard in China (GB8978-1996) by 57.5-59.0, 1.3-4.3, and 1.1-1.8 and 53.5-56.0, 3.04-7.25, and 1.0-1.91 times, respectively. Additionally, the Mn concentrations from both EMR leachates at pH 7.0 were above the national safe emission threshold. The morphological structure of EMRs changed after leaching, and XRD analysis showed the disappearance of MnO 2 , SiO 2 , FeS 2 , and CaSO 4 . The XPS revealed that Cr, Mn, Pb, and Zn existed as Cr 3+ , MnO, PbSO 4 , and ZnSiO 3 , respectively, after leaching. The study concluded that Mn, Pb, and Zn from EMRS leached by acid rain might pose a high potential environmental risk. Therefore, developing appropriate disposal techniques for EMR is necessary to prevent heavy metal pollution., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

The aim of this research was the analysis of the effect of a dam height raise on the water quality of a tropical reservoir used for drinking water purposes in South East Asia. Analyses of iron, manganese, pH and ammonia were performed over a 5-year period from daily water sampling at the reservoir. In addition, high-frequency monitoring data of nitrate, ammonium, pH and blue-green algae were obtained using a monitoring probe. The results showed that due to the raising of the reservoir water level, previously oxic sediments became submerged, triggering an increase in iron and manganese in particular due to the establishment of reducing conditions. Manganese concentrations with values up to 4 mg L -1 are now exceeding guideline values. The analysis strongly indicated that both iron and manganese have a seasonal component with higher iron and manganese concentrations during the wet season. Over a three-year period afterwards, concentrations did not go back to pre-raise levels. The change in water quality was accompanied by a change in pH from previous values of around 5 to pH values of around 6.5. Geochemical simulations confirmed the theory that the increasing concentrations of iron and manganese are due to the dissolution of MnO 2 and ferric oxyhydroxides oxidising organic matter in the process. This study showed that changes in reservoir water levels with the establishment of reducing conditions can have long-term effects on the water quality of a reservoir., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

A novel mesophilic, anaerobic, mixotrophic bacterium, with designated strains EPR-M T and HR-1, was isolated from a semi-extinct hydrothermal vent at the East Pacific Rise and from an Fe-mat at Lō'ihi Seamount, respectively. The cells were Gram-negative, pleomorphic rods of about 2.0 µm in length and 0.5 µm in width. Strain EPR-M T grew between 25 and 45 °C (optimum, 37.5-40 °C), 10 and 50 g l -1 NaCl (optimum, 15-20 g l -1 ) and pH 5.5 and 8.6 (optimum, pH 6.4). Strain HR-1 grew between 20 and 45 °C (optimum, 37.5-40 °C), 10 and 50 g l -1 NaCl (optimum, 15-25 g l -1 ) and pH 5.5 and 8.6 (optimum, pH 6.4). Shortest generation times with H 2 as the primary electron donor, CO 2 as the carbon source and ferric citrate as terminal electron acceptor were 6.7 and 5.5 h for EPR-M T and HR-1, respectively. Fe(OH) 3 , MnO 2 , AsO 4 3- , SO 4 2- , SeO 4 2- , S 2 O 3 2- , S 0 and NO 3 - were also used as terminal electron acceptors. Acetate, yeast extract, formate, lactate, tryptone and Casamino acids also served as both electron donors and carbon sources. G+C content of the genomic DNA was 59.4 mol% for strain EPR-M T and 59.2 mol% for strain HR-1. Phylogenetic and phylogenomic analyses indicated that both strains were closely related to each other and to Geothermobacter ehrlichii , within the class δ- Proteobacteria (now within the class Desulfuromonadia ). Based on phylogenetic and phylogenomic analyses in addition to physiological and biochemical characteristics, both strains were found to represent a novel species within the genus Geothermobacter , for which the name Geothermobacter hydrogeniphilus sp. nov. is proposed. Geothermobacter hydrogeniphilus is represented by type strain EPR-M T (=JCM 32109 T =KCTC 15831 T =ATCC TSD-173 T ) and strain HR-1 (=JCM 32110=KCTC 15832).

Planktonic microorganisms play a key role in the biogeochemical processes of the aquatic system, and they may be affected by many factors. High-throughput sequencing technology was used in this study to investigate and study the bacterioplankton community of water bodies in the upper reaches of the Heihe River Basin in Qinghai Plateau. Results showed that Proteobacteria, Firmicutes, Bacteroidetes and Actinobacteria are the predominant phyla in this river section, while the main genera are Thiomonas, Acidibacillus, Acidocella, Rhodanobacter, Acidithiobacter and Gallionella, which are autochthonous in the acid-mine drainage. Additionally, total nitrogen, total phosphorus, permanganate index and pH are significantly correlated with the bacterioplankton abundance and are the main limiting factors for the spatial distribution of the bacterioplankton. PICRUSt inferred that the mainstream microbial assemblages had a higher abundance of KOs belong to metabolism of terpenoids and polyketides, while the tributary had higher abundance of KOs belong to the immune system. The relationship between bacterioplankton community composition and environmental factors in the Heihe River basin was discussed for the first time in this study, which provides a theoretical basis for the healthy, orderly development of the water environment in the Heihe River Basin., (© 2020 Society for Applied Microbiology and John Wiley & Sons Ltd.)

A one-pot hydrothermal synthesis of manganese-doped carbon dots (Mn-CDs) is reported for fluorescent "on-off-on" determination of Mn(VII) and L-ascorbic acid (L-AA) in aqueous solution and living cells. Mn-CDs were prepared by using sulfanilic acid, tetrakis(hydroxymethyl)phosphonium chloride, and Mn(II) chloride as precursors. Mn-CDs were characterized by several spectroscopic methods and microscopic techniques. Mn-CDs show distinctly long fluorescence lifetime (12.39 ± 0.07 ns) and high absolute fluorescence quantum yield (around 37%) with excitation and emission wavelengths of 362 and 500 nm, respectively. Mn-CDs exhibit no significant cytotoxicity to human cervical carcinoma HeLa cells and human embryonic kidney HEK-293T cells at 200 μg mL -1 level after 48 h incubation. The fluorescence of Mn-CDs at 500 nm (excited at 362 nm) is quenched efficiently by Mn(VII) and can be further recovered after the addition of L-AA, resulting in a fluorescent "on-off-on" assay for the determination of Mn(VII) and L-AA. Under optimal experimental conditions, the linear response covers the 3 to 150 μM Mn(VII) concentration range and the 3 to 140 μM L-AA concentration range. This method offers relatively low detection limits of 0.66 μM for Mn(VII) and 0.90 μM for L-AA. This strategy was applied to visual determination of Mn(VII) and L-AA in living HeLa cells with satisfying results. Graphical abstract Schematic presentation of bright Mn-CD-based fluorescence "on-off-on" assay for both Mn(VII) and L-AA. This fluorescent assay possessed low detection limit of 0.66 μM for Mn(VII) and 0.90 μM for L-AA. This strategy was applied for visual determination of Mn(VII) and L-AA in living HeLa cells with satisfying results.

The objective of this study was to evaluate the relative bioavailability (RB) of manganese (Mn) proteinate compared to Mn sulfate for broilers fed a diet based on corn and soybean meal for 20 d. The diets of 1,350 male Cobb broilers were supplemented with 0, 35, 70, 105, or 140 mg of Mn/kg of feed in the form of Mn sulfate or Mn proteinate. Weight gain, feed intake, feed conversion, bone strength, and Mn concentration in the tibia and liver, as well as the concentration of type I collagen in the tibia, were evaluated. No differences were observed for performance variables (P > 0.05) or for type I collage concentration in broiler tibia (P > 0.05), regardless of the source and level of supplementation used. Relative bioavailability was determined using bone strength values and Mn concentration in the tibia and liver, assuming Mn sulfate as the standard source (100%) by the slope-ratio method. The RB of Mn proteinate based on bone strength was 111%, based on liver Mn concentration was 128%, and based on tibia Mn concentration was 105%. Manganese proteinate was more bioavailable than Mn sulfate; it can be an important source of supplementation to improve bone quality in broilers., (Copyright © 2020. Published by Elsevier Inc.)

Three spectrophotometric methods have been developed and compared for the quantification of low concentrations (0.03-63 μM) of aqueous permanganate in neutral pH conditions. Although permanganate is a widely used oxidant in drinking water and wastewater treatment, no widely accepted method of quantification has been reported to date. While one method presented does not require the need for any reagent chemicals (direct spectrophotometric analysis), it yielded a relatively low molar absorption coefficient of 3340 M -1  cm -1 at 525 nm and a level of detection (LOD) and quantification (LOQ) of 0.45 and 1.51 μM, respectively. Some instability of permanganate species during direct quantification was found to occur over 60 min, with a total decrease of 0.002 (arbitrary units) of absorbance, equivalent to a decrease in concentration of 0.6 μM. Beyond 60 min, no further degradation was observed. Indirect spectrophotometric analyses using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and sodium iodide (NaI) provided a significantly more sensitive method for permanganate quantification, yielding molar absorption coefficients of 140,030 and 61,130 M -1  cm -1 , respectively. The LOD and LOQ were determined to be 0.01 and 0.03 μM for the ABTS method and 0.02 and 0.08 μM for the NaI method, respectively. Although conservative and accurate limits of quantification for both the ABTS and NaI methods are presented, which should be sufficient of most practical applications, lower limits may be possible with further refinement of the methods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

As a new member of the fluorescent carbon nanomaterial family, carbon dots (CDs) not only have outstanding photoluminescence properties and small size characteristics, but also contain favourable low cytotoxicity and biocompatibility, which could be the best choice to detect of ions to replace quantum dots for ions detection. Here, the N,S co-doped carbon dots (N/S-CDs) was synthesized by one-step microwave using 1,6-hexanediamine dihydrochloride and dimethyl sulfoxide as precursors, and their morphology and structure were characterized by TEM, XRD, XPS and FTIR. The optimal emission wavelength of the CDs was 512 nm with green fluorescence, and was red-shifted gradually as the excitation wavelength aggrandized. The synthesized CDs owned a well quantum yield of 24 %. It was further applied for the detection of MnO 4 - and Cr 2 O 7 2- with an excellent detection limit of 0.34 μM and 0.23μM, respectively. Cr 2 O 7 2- did not influence the N/S-CDs PL response of MnO 4 - in the presence of excessive Pb 2+ . Moreover, the obtained N/S-CDs demonstrated preeminent biocompatibility and could be resoundingly applied for cellular imaging., Competing Interests: Declaration of Competing Interest There are no conflicts of interest to declare., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Incorporation of dual functions, i.e., sensing and adsorption, into one single organic-inorganic hybrid material for the detection and removal of toxic permanganate (MnO 4 - ) ions is of great importance, representing a challenging and new task in the design and application of new functional materials. However, most of the reported materials display only one function as either sensing probes or adsorbents. In this work, a fluorescent cuboid mesoporous silica-based hybrid material (SiO 2 @SFNO) is first prepared by the covalent coupling of a new safranin O-based fluorophore (2,8-dimethyl-5-phenyl-3,7-bis(3-(3-(triethoxysilyl)propyl)ureido)phenazin-5-ium chloride) (SFNO) and newly-made cuboid mesoporous silica, which showed selective dual-functional activities towards MnO 4 - and green emission at 575 nm with a long-range excitation wavelength that is suitable for bio-imaging application. The design of this SiO 2 @SFNO material is based on the position of -NHCONH- groups, which are mainly responsible for the strong and selective coordination with MnO 4 - . SiO 2 @SFNO is responsive to MnO 4 - at parts per billion (67 ppb) level; it also displays high adsorption ability (292 mg g -1 ) to MnO 4 - in aqueous solutions. The fluorescence responses of MnO 4 - in vivo (limnodrilus claparedianus and zebrafish) demonstrate the possibility of further application in biology. Interestingly, this SiO 2 @SFNO material is also capable of monitoring trace amounts of Hg 2+ and Cu 2+ in living organisms, holding great potential in bio-related applications.

A novel cellulose microcrystalline-manganese dioxide nanocomposite (CMC-NMO) was synthesized by the redox reaction between potassium permanganate and ethanol based on cellulose microcrystalline. The cellulose microcrystalline (CMC) as support providing growth sites for the manganese dioxide nanowhiskers produced by the redox reaction and its application for Pb(II) and Cd(II) removal from aqueous was investigated. The characterization of as-synthesized material was revealed by various spectroscopic and microscopic techniques. Infrared-transform infrared (FITR) indicates that the incorporation of manganese oxide to CMC does not change the initial structure of it. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) data show that the manganese dioxide nanowhiskers with a few nanometers are uniformly dispersed on the surface of cellulose. Kinetics experiments reveal that Pb(II) and Cd(II) adsorption on CMC-NMO is a fast process and pseudo-second-order model fits the adsorption better. The maximum adsorption capacities of Pb(II) and Cd(II) obtained from the Langmuir model are 290.8 mg/g and 67.4 mg/g, respectively. The mechanism is mainly attributed to surface complexation and electrostatic attraction by energy dispersive analysis of X-rays (EDAX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analysis. In addition, depth removal experiments show that the residual concentrations of Pb(II) and Cd(II) in natural water after adsorption are lower than 0.01 mg/L. The regeneration and cyclic utilizing studies indicate that CMC-NMO has good adsorption stability. Therefore, the results indicate that this material can be employed as a potential adsorbent for current serious Pb(II) and Cd(II) pollution caused by industrial emissions. Graphical abstract.

It is necessary to control the emissions of toluene, which is hazardous to both human health and the atmosphere environment and has been classified as a priority pollutant. Manganese oxide-based (Mn-based) catalysts have received increased attention due to their high catalytic performance, good physicochemical characteristic, availability in various crystal structures and morphologies, and being environmentally friendly and low cost. These catalysts can be classified into five categories, namely single manganese oxide, Mn-based composite oxides, Mn-based special oxides, supported Mn-based oxides, and Mn-based monoliths. This review focused on the recent progress on the five types of Mn-based catalysts for catalytic removal of toluene at low temperature and further systematically summarized the strategies improving catalysts, including improving synthetic methods, incorporating MnO x with other metal oxides, depositing Mn-based oxides on proper supports, and tuning the supports. Moreover, the effect of coexisting components, the reaction kinetics, and the oxidation mechanisms toward the removal of toluene were also discussed. Finally, the future research direction of this field was presented.

Permanganate/bisulfite (PM/BS) is a relatively new advanced oxidation process that can degrade organic micropollutants at extraordinary high rates. In this study, the degradability of PM/BS process towards different representative types of compounds was studied by investigating the kinetics, reaction site specificity and transformation chemistry. Acesulfame (ACE) and carbamazepine (CBZ) were two typical compounds containing olefinic moieties. Sucralose (SUC) was selected as a reference compound, and it is without aromatic and olefinic moieties. The kinetics results indicated that ACE and CBZ were effectively degraded while SUC was not. Preferred reaction sites of Mn 3+ species was elucidated by identification of the ACE-transformation products (TPs) and CBZ-TPs with UHPLC-QTOF-MS. Seventeen ACE-TPs including two new compounds and eleven CBZ-TPs produced during the PM/BS process were identified and characterized. Transformation pathways revealed that cleavage of olefinic double bonds was the main reaction mechanism. Chemical structures containing electron-donating groups preferentially reacted with electrophilic Mn 3+ species during the process. In addition, transformation products of ACE and CBZ during PM/BS process did not induce higher toxicity. This study provides a preliminary interpretation on the selectivity of PM/BS process according to the micropollutants' chemical structures, which hope to shed light on the future development of PM/BS treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study investigated the chemical components of fine urban road dust from seven sampling sites, based on which we could predict potential human health effects. The elemental compositions, including the contents of metals and volatile or semivolatile organic compounds, were determined to establish comprehensive chemical profiles of solid road dust. The chemical profiles, consisting of C: H ratio, metal contents, and relative abundances of organic compounds, provided a chemical signature for road dust. To overall cytotoxicity values ranging between 7 and 58%, water extracts contributed less than 15%, and cell death mainly occurred via direct contact with solid-phase components, which possibly indicates that the selected chemical profile of solid-phase road dust components could serve as a strong predictor for BJ and WI-38 cytotoxicity. Pure metal oxides (Cr 2 O 3 , CuO, Fe 2 O 3 , MnO 2 , NiO, or ZnO) exhibited a positive dose-response, and the corresponding metal contents in solid road dust were well correlated with cell viability. The principal component analysis (PCA) results suggested that the metal contents were stronger predictors of cytotoxicity than the benzene derivative or hydrocarbon contents. The chemical profiles established in this study could be further utilized to identify candidate health hazard factors in road dust., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A hydrothermal strategy for preparing boron and nitrogen codoped carbon quantum dots was studied using the precursors of p -amino salicylic acid, boric acid and ethylene glycol dimethacrylate. The boron and nitrogen codoped carbon quantum dots have high fluorescence intensity, good monodispersity, high stability, superior water solubility, and a fluorescence quantum yield of 19.6%. Their average size is 5 nm. Their maximum excitation and emission wavelengths are 380 and 520 nm, respectively. Permanganate (MnO 4 - ) quenched boron and nitrogen codoped carbon quantum dots fluorescence through inner filter effect and static quenching effects. The linear relation between quenching efficiency and MnO 4 - concentration ranged from 0.05 to 60 μmol/L with a detection limit of 13 nmol/L. In the presence of captopril, MnO 4 - was reduced to Mn 2+ and the fluorescence of boron and nitrogen codoped carbon quantum dots was recovered. The linear range between recovery and captopril concentration was from 0.1 to 60 μmol/L. The limit of detection was 0.03 μmol/L. The developed method can be employed as a sensitive fluorescence sensing platform for MnO 4 - . It has been successfully used for captopril detection in mouse plasma.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The extensive applications of biogenic manganese oxides (BioMnOx) generated by manganese oxidizing bacteria (MOB) have attracted considerable attentions. In this study, we report on a novel MOB that has been isolated from sediments and identified as Aeromonas hydrophila strain DS02. The Mn(II) oxidation activity of strain DS02 under Mn(II) stress and the application of the associated BioMnOx products were investigated. Nearly 90.0% (495 mg L -1 ) of the soluble Mn(II) were removed and 45.6% (240 mg L -1 ) was converted to Mn(III/IV). Fitting the XPS data showed that Mn(IV)-oxide is the major component (82.0%) of the flake-shaped BioMnOx, corresponding to an average Mn oxidation number of 3.71. When the BioMnOx were coupled with the PMS activation, a 99.5% catalytic degradation of 2,4-dimethylaniline was observed after 80 min, revealing a high degradation efficiency., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The detection of nitrofuran antibiotics and toxic inorganic anions is currently necessary and challenging because their abuse and/or residuals have caused severe environmental pollution and illness. A heterometallic two-dimensional (2D) layered complex, {[Eu 2 Na(Hpddb)(pddb) 2 (CH 3 COO) 2 ]·2.5(DMA)} n (1), was solvothermally synthesized and structurally and photophysically characterized. Pairs of acetate aggregated {Eu 2 Na(CH 3 COO) 2 } chains are periodically interconnected by V-shaped 4,4'-(pyridine-2,6-diyl)dibenzolate (pddb) linkers. More interestingly, the layered complex exhibits a bright red emission and can efficiently discriminate nitrofuran antibiotics by luminescent quenching with a strong quenching constant (K sv ) and low detection limit (LOD) of 4.93 × 10 4 M -1 and 0.64 μM for nitrofurazone, 4.42 × 10 4 M -1 and 0.68 μM for nitrofurantoin as well as 2.13 × 10 4 M -1 and 1.06 μM for furazolidone. Additionally, 1 can also probe trace amounts of toxic Cr 2 O 7 2- and MnO 4 - anions with K sv = 6.45 × 10 3 M -1 and LOD = 5.35 μM for Cr 2 O 7 2- and K sv = 2.84 × 10 3 M -1 and LOD = 5.99 μM for MnO 4 - anions. These interesting results indicate that heteromatallic coordination polymers can serve as favorable dual- or even multiple-responsive luminescence sensors to selectively recognize different kinds of contaminants.

In this study, MnO 2 and pyrolusite were used as the catalysts to prepare modified activated carbon, that is, AC-Mn and AC-P, respectively, from coals by blending method and steam activation. The Brunauer-Emmett-Teller (BET) results indicated that the AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The relative contents of basic functional groups (i.e., C = O, π-π*) on AC-P were slightly lower than those on AC-Mn, while both contained the same main metal species, namely, MnO. The desulfurization results showed that with 3 wt% of blending ratio, AC-Mn3 and AC-P3 had higher sulfur capacities at 220 and 205 mg/g, respectively, which were much higher than for the blank one (149.6 mg/g). Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn, which might be attributed to the existence of other metals in pyrolusite. After the desulfurization process, MnO were gradually transferred into MnSO 4 , and the relative contents of basic functional groups decreased evidently for both AC-Mn3 and AC-P3. The results demonstrated that pyrolusite could be one good alternative to MnO 2 to prepare modified activated carbon for desulfurization., Implications: MnO 2 and pyrolusite were used as the additives to prepare modified activated carbon from coals by a blending method and by steam activation, that is, AC-Mn and AC-P, respectively. The AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The AC-Mn and AC-P had higher sulfur capacities than a blank one. Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn. The results demonstrated that pyrolusite could be one good alternative to MnO 2 to prepare modified activated carbon for desulfurizatio.

Current magnetic relaxation switching (MRS) sensors for detection of trace targets in complex samples still suffer from limitations in terms of relatively low sensitivity and poor stability. To meet this challenge, we develop a longitudinal relaxation time (T 1 )-based nanosensor by using Mn 2+ released from the reduction of a MnO 2 nanoassembly that can induce the change of T 1 , and thus can greatly improve the sensitivity and overcome the "hook effect" of conventional MRS. Through the specific interaction between antigen and the antibody-functionalized MnO 2 nanoassembly, the T 1 signal of Mn 2+ released from the nanoassembly is quantitatively determined by the antigen, which allows for highly sensitive and straightforward detection of targets. This approach broadens the applicability of magnetic biosensors and has great potential for applications in early diagnosis of disease biomarkers.

In this study, the double-edge role of permanganate in sulfamethoxazole (SMX) photodegradation with a recyclable catalyst was revealed for the first time. The role of the catalyst under different UV wavelength, the role of permanganate in the treatment process, the effects of permanganate dosage and solution pH on the removal efficiency were investigated. Moreover, the transformation products, TOC reduction and the toxicity of the treated final product to Chlorella vulgaris and Artemia salina were determined. Sole permanganate showed no effect in SMX degradation, while its introduction to the photocatalytic process doubled the reaction rate at the optimal dosage. It is interesting to find that the reaction rate showed a fluctuation trend in terms of permanganate dosage due to the summation of positive effect of permanganate oxidation and the negative effect of the formed MnO 2 at the surface of the catalyst, as well as the light attenuation due to overdosed permanganate. The determined intermediates, the higher inorganic ions release and TOC reduction provided a clue on a higher mineralization compared to SMX degradation in the same process without permanganate. Permanganate above 1 μM may pose a threat to the algae growth, therefore a good monitoring and control of residual permanganate dosage should be incorporated into the process design. A good toxicity reduction to A. salina was observed in the treated effluent; a longer detention is suggested for the complete removal of toxicity., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The temporal and spatial distributions of mercury in different fractions and its potential ecological risk were investigated in sediments from the Yangtze River estuary (YRE) by analyzing data collected from the study area. The results showed that mercury in the organic and residual fractions had dominant proportions, from 15.2% to 48.52% and from 45.96% to 81.59%, respectively. The fractions were more susceptible to seasonal changes than other fractions. Higher proportions of mercury in organic fraction were found in wet seasons; the opposite was true for mercury in residual fraction. With respect to the spatial distribution, the concentration mercury in exchangeable, carbonate and Fe-Mn oxide fractions showed a decreasing trend from the inner estuary to the outer estuary, but no obvious trends were found in the distributions of mercury in the organic and residual fractions. The risk assessment code (RAC) was used to evaluate the potential ecological risk in the study area based on the proportions of exchangeable and carbonate fractions. The average RAC values during the four periods were 6.00%, 2.20%, 2.83%, and 0.61%. Although these values show that the risk in the study area is generally low, the distribution of RAC values indicates that the inner estuary has a medium risk, with a value up to 10%., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A composite catalyst for the selective catalytic reduction (SCR) of NO x with NH 3 is investigated, in which the rare earth (RE, including La, Ce, Pr, and Nd) is doped into manganese oxides supported on activated semi-coke (MnO x /ASC) via hydrothermal method at the molar ratio of Mn:RE = 1:5. It is evidenced that the addition of RE at a rather low molar ratio can enhance the catalytic activity of MnO x /ASC. The catalyst with a Mn:Ce molar ratio of 10:1 yields an over 90% NO x removal efficiency in the temperature range of 150-250 °C. An approximate 100% NO conversion and 95% N 2 selectivity are achieved at about 200 °C. The catalysts are characterized by N 2 physisorption, X-ray powder diffraction (XRD), scanning electron microscope (SEM), hydrogen temperature-programmed reduction (H 2 -TPR) and X-ray photoelectron spectroscopy (XPS). The results indicated that the Ce additive is conducive to the NO x adsorption and then accelerates the SCR reaction due to the formation of more chemisorbed oxygen (O β ), which is favored during the oxidation of NH 3 and NO. Moreover, the in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) results confirm that the Ce additive on MnO x /ASC catalyst could provide more active Brønsted acid sites, which eventually contributes to the SCR reaction. The generation of ad-NH 4 + and nitrite species is proved to play the crucial role in the promotional effect of RE addition.

Background: Podoconiosis, non-filarial elephantiasis, is a non-infectious disease found in tropical regions such as Ethiopia, localized in highland areas with volcanic soils cultivated by barefoot subsistence farmers. It is thought that soil particles can pass through the soles of the feet and taken up by the lymphatic system, leading to the characteristic chronic oedema of the lower legs that becomes disfiguring and disabling over time., Methods: The close association of the disease with volcanic soils led us to investigate the characteristics of soil samples in an endemic area in Ethiopia to identify the potential causal constituents. We used the in vitro haemolysis assay and compared haemolytic activity (HA) with soil samples collected in a non-endemic region of the same area in Ethiopia. We included soil samples that had been previously characterized, in addition we present other data describing the characteristics of the soil and include pure phase mineral standards as comparisons., Results: The bulk chemical composition of the soils were statistically significantly different between the podoconiosis-endemic and non-endemic areas, with the exception of CaO and Cr. Likewise, the soil mineralogy was statistically significant for iron oxide, feldspars, mica and chlorite. Smectite and kaolinite clays were widely present and elicited a strong HA, as did quartz, in comparison to other mineral phases tested, although no strong difference was found in HA between soils from the two areas. The relationship was further investigated with principle component analysis (PCA), which showed that a combination of an increase in Y, Zr and Al2O3, and a concurrent increase Fe2O3, TiO2, MnO and Ba in the soils increased HA., Conclusion: The mineralogy and chemistry of the soils influenced the HA, although the interplay between the components is complex. Further research should consider the variable biopersistance, hygroscopicity and hardness of the minerals and further characterize the nano-scale particles.

A pot experiment was used to investigate arsenic (As) speciation and accumulation in rice, as well as its concentration in both heavily contaminated and moderately contaminated soils amended with manganese oxide-modified biochar composites (MBC) and biochar alone (BC). In heavily As-contaminated soil, application of BC and MBC improved the weight of above-ground part and rice root, whereas in moderately As-contaminated soil, the application of MBC and low rate BC amendment increased rice root, grain weight and the biomass of the plant. Arsenic reduction in different parts of rice grown in MBC-amended soils was greater than that in plants cultivated in BC-amended soils. Such reduction can be attributed to the oxidation of arsenite, As(III), to arsenate, As(V), by Mn-oxides, which also had a strong adsorptive capacity for As(V). MBC amended to As-contaminated soil had a positive effect on amino acids. The Fe and Mn levels in the iron-manganese plaque that formed on the rice root surface differed among the treatments. MBC addition significantly increased Mn content (p < 0.05); the application of 2.0% MBC increased Mn content 36- and 10-fold compared to the control in heavily and moderately As-contaminated soils, respectively. The results indicate that application of Mn oxide-modified biochar to As-contaminated paddy soil could effectively remediate contaminated soil and reduce As accumulation in edible parts of rice., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Manganese contamination has become a serious environmental problem in the world and bacterial removal plays an important role in global cycling of manganese. In this study, microorganism distribution within samples from a manganese mine was analyzed with PCR-DGGE technology. The results suggested that Manganese oxidizing bacteria (such as Bacillus, Hyphomicrobiaceae and Erythrobacter) were dominant in the soil. In addition, a Lysinibacillus sp. Isolate, strain MK-1, revealed robust growth at high Mn(II) concentrations up to 1 mM. At that concentration, 55.94% of added Mn(II) was oxidized and 36.23% of the Mn(II) was adsorbed by MK-1(total manganese removal reached 94.67%) after 7 days of culturing. By measuring its metabolic process, the great role of biological adsorption was found. Additionally, the spectroscopic result demonstrated that Mn(III) was an intermediate during the biological oxidation process. These findings increase the knowledge of biological manganese removal mechanisms and show some potentials to the operation of manganese treatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Total oxidant demand (TOD) is a parameter that is often measured during in situ chemical oxidation (ISCO) treatability studies. The importance of TOD is based on the concept that the oxidant demand created by soil organic matter and other reduced species must be overcome before contaminant oxidation can proceed. TOD testing was originally designed for permanganate ISCO, but has also recently been applied to activated persulfate ISCO. Recent studies have documented that phenoxides activate persulfate; because soil organic matter is rich in phenolic moieties, it may activate persulfate rather than simply exerting TOD. Therefore, the generation of reactive oxygen species was investigated in three soil horizons of varied soil organic carbon content over 5-day TOD testing. Hydroxyl radical may have been generated during TOD exertion, but was likely scavenged by soil organic matter. A high flux of reductants + nucleophiles (e.g. alkyl radicals + superoxide) was generated as TOD was exerted, resulting in the rapid destruction of the probe compound hexachloroethane and the common groundwater contaminant trichloroethylene (TCE). The results of this research document that, unlike permanganate TOD, contaminant destruction does occur as TOD is exerted in persulfate ISCO systems and is promoted by the activation of persulfate by soil organic matter. Future treatability studies for persulfate ISCO should consider contaminant destruction as TOD is exerted, and the potential for persulfate activation by soil organic matter., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The aim of the study is the recovery by thermal treatment of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, on the basis of the different phase change temperatures of the two metal-bearing phases. ASR (Automotive Shredder Residue), containing 68% of carbon, was added to the mixture to act as a reductant to metallic Zn of the zinc-bearing phases. The mixture was subsequently heated in different atmospheres (air, CO2 and N2) and at different temperatures (900°C, 1000°C and 1200°C) and stoichiometric excess of ASR (300%, 600% and 900%). Characterization of the mixture and of the residues of thermal treatment was carried out by chemical analysis, TGA/DTA, SEM and XRD. The results show that recovery of 99% of zinc (grade 97%) is achieved at 1000°C in N2 with a stoichiometric excess of car-fluff of 900%. This product could be suitable for production of new batteries after refining by hydrometallurgical way. Recovery of Mn around 98% in the residue of the treatment is achieved at any temperature and atmosphere tested with a grade of 57% at 900% excess of car-fluff. This residue is enriched in manganese oxide and could be used in the production of iron-manganese alloys., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The formation and reduction of furan using a soy sauce model system were investigated in the present study. The concentration of furan fermented up to 30 days increased by 211% after sterilization compared to without sterilization. Regarding fermentation temperature, furan level after 30 days' fermentation was the highest at 30°C (86.21 ng/mL). The furan levels in the soy sauce fermentation at 20°C and 40°C were reduced by 45% and 88%, respectively compared to 30°C fermentation. Five metal ions (iron sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, and calcium sulfate), sodium sulfite, ascorbic acid, dibutyl hydroxyl toluene (BHT), and butylated hydroxyanisole (BHA) were added in a soy sauce model system. The addition of metal ions such as magnesium sulfate and calcium sulfate reduced the furan concentration significantly by 36-90% and 27-91%, respectively in comparison to furan level in the control sample (p<0.05). Iron sulfate and ascorbic acid increased the furan level at 30 days' fermentation in the soy sauce model system by 278% and 87%, respectively. In the case of the BHT and BHA, furan formation generally was reduced in the soy sauce model system by 84%, 56%, respectively., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Extensive uranium mining in the former German Democratic Republic (GDR) in eastern Thuringia and Saxony took place during the period of 1946-1990. During mining activities, pelitic sediments rich in organic carbon and uranium were processed and exposed to oxygen. Subsequent pyrite oxidation and acidic leaching lead to partial contamination of the area with heavy metals and acid mine drainage (AMD) even few years after completion of remediation. One of those areas is the former heap Gessen (Ronneburg, Germany) were the residual contamination can be found 10 m under the base of the former heap containing partly permeable drainage channels. Actually, in such a system, a rapid but locally restricted mineralization of Mn oxides takes place under acidic conditions. This formation can be classified as a natural attenuation process as certain heavy metals, e.g., Cd (up to 6 μg/g), Ni (up to 311 μg/g), Co (up to 133 μg/g), and Zn (up to 104 μg/g) are bound to this phases. The secondary minerals occur as colored layers close to the shallow aquifer in glacial sediments and could be identified as birnessite and todorokite as Mn phase. The thermodynamic model shows that even small changes in the system are sufficient to shift either the pH or the Eh in the direction of stable Mn oxide phases in this acidic system. As a consequence of 9-15-year-long formation process (or even less), the supergene mineralization provides a cost-efficient contribution for remediation (natural attenuation) strategies of residual with heavy metals (e.g., Cd, Co, Ni, Zn) contaminated substrates.

Cryptomelane is a reactive Mn oxide and has been used in removal of heavy metal from wastewaters. Co-doped cryptomelane was synthesized by refluxing at ambient pressure and characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and extended X-ray absorption fine structure spectroscopy, and its performances for removal of Pb(2+) and Cr(3+) from aqueous solutions were investigated. Co doping has a negligible effect on the structure and morphology of cryptomelane but increases the specific surface area and Mn average oxidation state. Mn and Co K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis shows that Co barely affects the atomic coordination environments of Mn, and distances of edge- and corner-sharing Co-Me (MeCo, Mn) pairs are shorter than those of the corresponding Mn-Me pairs, implying the replacement of framework Mn(III) by Co(III). These Co-doped cryptomelanes can quickly oxidize Cr(3+) to be HCrO4(-) and remove 45%-66% of the total Cr in the reaction systems by adsorption and fixation, and they have enhanced Pb(2+) adsorption capacities. Thus these materials are promising adsorbents for heavy metal remediation. The results demonstrate the design and modification of environmental friendly Mn oxide materials and can help us understand the interaction mechanisms of transition metals with Mn oxides., (Copyright © 2015. Published by Elsevier B.V.)

The deep biosphere of the subseafloor basalts is recognized as a major scientific frontier in disciplines like biology, geology, and oceanography. Recently, the presence of fungi in these environments has involved a change of view regarding diversity and ecology. Here, we describe fossilized fungal communities in vugs in subseafloor basalts from a depth of 936.65 metres below seafloor at the Detroit Seamount, Pacific Ocean. These fungal communities are closely associated with botryoidal Mn oxides composed of todorokite. Analyses of the Mn oxides by Electron Paramagnetic Resonance spectroscopy (EPR) indicate a biogenic signature. We suggest, based on mineralogical, morphological and EPR data, a biological origin of the botryoidal Mn oxides. Our results show that fungi are involved in Mn cycling at great depths in the seafloor and we introduce EPR as a means to easily identify biogenic Mn oxides in these environments.

Citric acid, a widespread soil rhizosphere plant/microbe carboxylic acid exudate can easily form chelates with heavy metals, increasing their availability in the environment. When Cu(II) from algal control in water bodies or reservoirs and fungicides, such as the Bordeaux mixture, and citrate interact, solubilization through chelation is a possible outcome. Manganese (hydr)oxides represent a significant portion of the subsurface environment and can affect the fate and transport of chemical species through adsorption and oxidation. This study explores the possible interaction between MnO2 and Cu-Citrate under ambient oxic conditions. The calculated Mn(II) dissolution rates during the initial 1h of reaction followed the series Cu(II)>Cu-Citrate 1:0.5>Cu-Citrate 1:1(oxic)>Citrate>Cu-Citrate 1:1(Anoxic), reinforcing the central role of (complexed or un-complexed) Cu(II) during the initial surface-coordination instead of following the s-shaped auto-catalytic curves of Mn(II) dissolution in citrate solution. The use of capillary electrophoresis allowed the detection of an intermediate Cu(II)Acetonedicarboxylate complex and the oxidation products acetonedicarboxylate, acetoacetate, acetone and acetic acid. The mass balance analysis of Cu-Citrate 1:1 suggests the partial adsorption of Cu-Citrate(ads) and catalytic degradation of acetonedicarboxylate through a MnO2-Cu surface sorbed complex. Lastly, XPS analysis confirmed the MnO2 surface Cu(II) reduction along with an outer-hydration layer at the MnO2 interface, where electron transfer and aquo ligand exchange may lead to the oxidation of Cu-Citrate., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A simple hydrodynamic chronoamperometric method based on the application of an unmodified carbon paste electrode (CPE) and bulk-modified with different contents of MnO2 was investigated for the determination of H2O2. The optimized method involving the CPE with 5% of MnO2 was applied for the determination of the H2O2 consumption in samples of groundwater from the Central Banat region (Province of Vojvodina, Serbia) treated by the Fenton (Fe(2+) and H2O2) and Fenton-like (Fe(3+) and H2O2) reagents to remove natural organic matter at different initial concentrations of iron species, and of their ratios to the initial concentration of H2O2. Under optimized conditions, with a working potential of 0.40V vs. the saturated calomel electrode and a phosphate buffer solution (pH 7.5) as supporting electrolyte, the method enabled the quantitation of H2O2 in the concentration interval from 1.4 to 65 μg mL(-1) with a relative standard deviation of less than 10%. The results obtained for the H2O2 consumption are in good agreement with those obtained by parallel measurements related to the efficiency of organic matter removal., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Manganese ferrite (MnFe2O4) nanoparticles of identical size (9 nm) and with different inversion degrees were synthesized under solvothermal conditions as a candidate theranostic system. In this facile approach, a long-chain amine, oleylamine, was utilized as a reducing and surface-functionalizing agent. The synthesized nanoparticles were shown to have a cubic-spinel structure as characterized by TEM and XRD patterns. Control over their inversion degree was achieved by a simple change of manganese precursor from Mn(acac)2 to Mn(acac)3. The variation in the inversion degree is ascribed to the partial oxidation of Mn(2+) to Mn(3+), as was evidenced by X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy at both the Fe and Mn K-edges. The reduction of the inversion degree from 0.42 to 0.22 is close to the corresponding bulk value of 0.20 and led to elevated magnetization (65.7 emu g(-1)), in contrast to the Néel temperature, which was decreased owing to the weaker superexchange interactions between the tetrahedral and octahedral sites within the spinel structure. In order to evaluate the performance of these nanoprobes as a possible bifunctional targeting system, the (1)H NMR relaxation of the samples was tested together with their specific loss power under an alternating magnetic field as a function of concentration. The hydrophobic as prepared MnFe2O4 nanoparticles converted to hydrophilic nanoparticles with cetyltrimethylammonium bromide (CTAB). The MnFe2O4 nanoparticles, well-dispersed in aqueous media, were shown to have r2 relaxivity of up to 345.5 mM(-1) s(-1) and heat release of up to 286 W g(-1), demonstrating their potential use for bioapplications.

Manganese is a neurotoxic element that leads to severe neurological disorders when excessive exposure occurs, mainly in occupational settings, but that can also lead to more subtle neurological deficits, especially to the dopaminergic system, under lower exposure conditions. Mn exists in a variety of chemical species in the environment but the influence of Mn speciation on its neurotoxicity has not been fully evaluated yet. In this study we compared the cytotoxicity towards dopamine producing cells of environmental Mn compounds with a diversity of physico-chemical forms: inorganic compounds having distinct oxidation states and solubility (MnCl2, MnSO4, and Mn2O3) and organic compounds such as MMT, a gasoline additive, and maneb, a Mn-dithiocarbamate fungicide. We observed that maneb exhibited the highest toxicity, followed by MnCl2, MnSO4 and MMT which resulted in a similar intermediate toxicity, the less toxic compound being the insoluble compound Mn2O3. We combined micro-SXRF (Synchrotron X-Ray Fluorescence) for imaging and micro-XANES (X-ray Absorption Near Edge Structure) to determine the Mn oxidation state at the single cell level. Mn2O3 readily entered the cell but remained in its initial state as Mn(III) particles within the cytoplasm. The lack of toxicity of Mn2O3 can be explained by its insolubility. For all the other compounds, Mn(II) was observed and was located mainly in the Golgi apparatus, probably for detoxification purposes via exocytosis. Organic compounds MMT and maneb were degraded releasing Mn and behaved similar to the soluble Mn(II) inorganic compounds. Maneb cytotoxicity was higher probably because of the combined toxicity due to both Mn and dithiocarbamate residues. Overall these results raise the concern about environmental exposure to Mn since either inhalation of Mn combustion products or ingestion of contaminated food and drinking water will end up in neurotoxic soluble and bioavailable Mn species.

Distinct layers of iron(III) and manganese(IV) (Fe/Mn) oxides are found buried within the reducing part of the sediments in Lake Baikal and cause considerable complexity and steep vertical gradients with respect to the redox sequence. For the on-site investigation of the responsible biogeochemical processes, we applied filter tube samplers for the extraction of sediment porewater combined with a portable capillary electrophoresis instrument for the analyses of inorganic cations and anions. On the basis of the new results, the sequence of diagenetic processes leading to the formation, transformation, and dissolution of the Fe/Mn layers was investigated. With two exemplary cores we demonstrate that the dissolution of particulate Fe and Mn is coupled to the anaerobic oxidation of CH₄ (AOM) either via the reduction of sulphate (SO₄(2-)) and the subsequent generation of Fe(II) by S(-II) oxidation, or directly coupled to Fe reduction. Dissolved Fe(II) diffuses upwards to reduce particulate Mn(IV) thus forming a sharp mineral boundary. An alternative dissolution pathway is indicated by the occurrence of anaerobic nitrification of NH₄(+) observed at locations with Mn(IV). Furthermore, the reasons and consequences of the non-steady-state sediment pattern and the resulting redox discontinuities are discussed and a suggestion for the burial of active Fe/Mn layers is presented.

Sediment particulates can be ingested by benthic animals, and the bioavailability of associated metals strongly depends on their speciation in the sediments. Different sedimentary components have distinct physiochemical characteristics and result in different biological responses from animals. Therefore, the bioaccumulation of particle-bound trace metals may be different. In the present study, bioaccumulation of cadmium adsorbed on various (hydr)oxide minerals, that is, ferric hydroxide, aluminum hydroxide, and manganese dioxide, in the clam Meretrix meretrix Linnaeus was studied. The results showed that the accumulation rate of cadmium varied for different mineral-adsorbed cadmium. The bioaccumulation of metal (hydr)oxide-adsorbed cadmium in M. meretrix followed the order Cd-MnO2  > Cd-Al(OH)3  > Cd-Fe(OH)3 . The type of mineral determines both the assimilation efficiency and ingestion rate, and consequently controls the bioaccumulation of adsorbed cadmium., (Copyright © 2013 SETAC.)

Manganese (Mn) is an essential element and it acts as a cofactor for a number of enzymatic reactions, including those involved in amino acid, lipid, protein, and carbohydrate metabolism. Excessive exposure to Mn can lead to poisoning, characterized by psychiatric disturbances and an extrapyramidal disorder. Mn-induced neuronal degeneration is associated with alterations in amino acids metabolism. In the present study, we analyzed whole rat brain amino acid content subsequent to four or eight intraperitoneal injections, with 25 mg MnCl₂/kg/day, at 48-h intervals. We noted a significant increase in glycine brain levels after four or eight Mn injections (p < 0.05 and p < 0.01, respectively) and arginine also after four or eight injections (p < 0.001). Significant increases were also noted in brain proline (p < 0.01), cysteine (p < 0.05), phenylalanine (p < 0.01), and tyrosine (p < 0.01) levels after eight Mn injections vs. the control group. These findings suggest that Mn-induced alterations in amino acid levels secondary to Mn affect the neurochemical milieu.

Lascaux Cave in France was discovered in 1940. Since being opened to visitors the cave has suffered three major microbial outbreaks. The current problem is the fast dissemination of black stains which are threatening the Palaeolithic paintings. Previous data pointed to the involvement of new fungal species in the formation of black stains on the rock walls and ceiling. However, it appears that there could be other reasons for the formation of different and extensive black stains coating the surface of the clayey sediments. Our analyses reveal that black stains on clayey sediments are mainly produced by Acremonium nepalense, a manganese oxide-depositing fungus, widely distributed in the cave. Thus, in Lascaux Cave, the black stains have a dual origin: on limestone rocks they are mainly produced by the accumulation of fungal melanins, and on clayey sediments by the biogenic deposition of black manganese oxides., (© 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.)

We describe the case of a 50-year-old man with a fatal intoxication after accidental massive oral ingestion of manganese. The patient presented with lethargy, diffuse abdominal pain, vomiting, and profuse diarrhea after ingesting Epsom salts (magnesium sulfate heptahydrate) during a liver cleansing diet. Despite intensive care management with intubation, prone position ventilation, continuous venovenous hemofiltration, and multiple transfusions, he progressed to refractory shock with multiple organ dysfunction resulting in death within 72 h. Similar patients arrived at several hospitals with identical epidemiology (all had ingested the same salt obtained in the same place). Clinical and forensic investigations (X-ray diffraction) discovered that the supplier had mistakenly prepared the salts with hydrated manganese sulfate instead of magnesium sulfate heptahydrate. The results enabled the other patients to be successfully treated for hydrated manganese sulfate intoxication with life support in the intensive care unit and chelation therapy (EDTA). We describe the clinical presentation of acute manganese poisoning and alert professionals to the risk of an increasingly popular diet. This case demonstrates the importance of collaboration between clinicians, pathologists, and forensic scientists to resolve a difficult-to-diagnose case., (Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.)

This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (δ-MnO(2)) as well as impact of variables including initial MnO(2) loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (δ-MnO(2)) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50 mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0 mg/L of carbamazepine and 130.5 mg/L of MnO(2). Effects of initial MnO(2) loading (0-130.5 mg/L), pH (2.72-8.58) and 0.01 M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5 min, and approximately 95 % of carbamazepine was eliminated within 60 min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO(2) loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn(2+) > Fe(3+) > Ca(2+) ≈ Mg(2+). Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by δ-MnO(2), and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO(2) be a potential alternative to solve carbamazepine pollution.

The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λ(max) 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λ(max) 570 the system 3/barium diphenylamine sulphonate λ(max) 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml(-1)/0.14-1.40 μg ml(-1)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Influence of various disturbance intensities on nitrogen, phosphorus and permanganate index (PI) release of Potamogeton crispus were investigated during the plant soaking in water, and the plant materials were collected in an urban lake of Beijing. Results showed that more rapid release of TP and PI from Potamogeton crispus were caused by disturbance, NH4(+) -N and TN in water were significantly increased (ANOVA, p < 0.05) under the condition of high disturbance (120 r/min) for 240 h. However, PI and TP were significantly decreased (ANOVA, p < 0.05) after 240 h disturbance in all treatments. When the release equilibrium of 2.13 g dry mass Potamogeton crispus in one liter of water was reached, the PI, TN, and TP released from unit mass Potamogeton crispus were 35, 5.1 and 4.1 mg x g(-1), respectively. The release ratio of TP from Potamogeton crispus was the highest, while the release ratio of PI was the lowest. The simulated experiment results showed that the highest pollution load to water released from Potamogeton crispus was the TP among the three nutrients. Phosphorus is one of the key factors which causing water eutrophication in lake, thus after submerged plants declining in lake, the field research of phosphorus release and migration from submerged plants into water is the focus of future research work.

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E(h) ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E(h) range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E(h) range (+50 to -100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E(h) ranges were also proposed., (Published by Elsevier Ltd.)

Mesoporous silica-coated hollow manganese oxide (HMnO@mSiO(2)) nanoparticles were developed as a novel T(1) magnetic resonance imaging (MRI) contrast agent. We hypothesized that the mesoporous structure of the nanoparticle shell enables optimal access of water molecules to the magnetic core, and consequently, an effective longitudinal (R(1)) relaxation enhancement of water protons, which value was measured to be 0.99 (mM(-1)s(-1)) at 11.7 T. Adipose-derived mesenchymal stem cells (MSCs) were efficiently labeled using electroporation, with much shorter T(1) values as compared to direct incubation without electroporation, which was also evidenced by signal enhancement on T(1)-weighted MR images in vitro. Intracranial grafting of HMnO@mSiO(2)-labeled MSCs enabled serial MR monitoring of cell transplants over 14 days. These novel nanoparticles may extend the arsenal of currently available nanoparticle MR contrast agents by providing positive contrast on T(1)-weighted images at high magnetic field strengths.

Arsenic (As) enrichment in groundwater has become a major global environmental disaster. Groundwater samples were collected from 64 sites located in the districts of 24-Parganas (S), and Nadia in West Bengal, India (Bhagirathi sub-basin), and 51 sites located in the districts of Comilla, Noakhali, Magura, Brahman baria, Laxmipur, Munshiganj, Faridpur and Jhenaida in Bangladesh (Padma-Meghna sub-basin). Groundwater samples were also collected from two As-affected areas (Chianan and Lanyang plains) of Taiwan (n = 26). The concentrations of major solutes in groundwater of the Padma-Meghna sub-basin are more variable than the Bhagirathi sub-basin, suggesting variations in the depositional and hydrological settings. Arsenic concentrations in groundwaters of the studied areas showed large variations, with mean As concentrations of 125 μg/L (range: 0.20 to 1,301 μg/L) in Bhagirathi sub-basin, 145 μg/L (range: 0.20 to 891 μg/L) in Padma-Meghna sub-basin, 209 μg/L (range: 1.3 to 575 μg/L) in Chianan plain, and 102 μg/L (range: 2.5 to 348 μg/L) in Lanyang plain groundwater. The concentrations of Fe, and Mn are also highly variable, and are mostly above the WHO-recommended guideline values and local (Indian and Bangladeshi) drinking water standard. Piper plot shows that groundwaters of both Bhagirathi and Padma-Meghna sub-basins are of Ca-HCO(3) type. The Chianan plain groundwaters are of Na-Cl type, suggesting seawater intrusion, whereas Lanyang plain groundwaters are mostly of Na-HCO(3) type. The study shows that reductive dissolution of Fe(III)-oxyhydroxides is the dominant geochemical process releasing As from sediment to groundwater in all studied areas.

Streams below mountaintop removal-valley fill coal mining operations often have elevated Mn concentrations, but it remains unclear if Mn plays a role in biodiversity reduction. We examined various aspects of aqueous Mn interactions with aquatic insects exposed to environmentally relevant Mn concentrations, revealing complex behavior. First, Mn accumulation rates varied widely among 9 species. A significant percentage of total Mn accrued (mean 74%, range 24-95%) was associated with the cuticle, predominantly in the form of Mn-oxides, and to a lesser degree Mn(II). Mn II is also absorbed into tissues, possibly through calcium transporters. Increased ambient calcium concentrations decreased both adsorbed and absorbed Mn accumulation from solution. Though species showed similar Mn efflux rate constants (0.032-0.072 d(-1)), the primary mode of Mn loss was through molting. Both adsorbed and absorbed Mn is lost during the molt. Subcellular compartmentalization studies revealed an overwhelming tendency for internalized Mn to associate with the heat stable cytosolic protein fraction. After short dissolved Mn exposures, intracellular glutathione and cysteine levels were markedly reduced relative to controls. These findings suggest that Mn exposure results in transient physiological stress in aquatic insects which is likely relieved, in part, during the molting process.