Cancer Influences the Elemental Composition of the Myocardium More Strongly than Conjugated Linoleic Acids-Chemometric Approach to Cardio-Oncological Studies.

The aim of the study was to verify in a cardio-oncological model experiment if conjugated linoleic acids (CLA) fed to rats with mammary tumors affect the content of selected macro- and microelements in their myocardium. The diet of Sprague-Dawley females was supplemented either with CLA isomers or with safflower oil. In hearts of rats suffering from breast cancer, selected elements were analyzed with a quadrupole mass spectrometer with inductively coupled plasma ionization (ICP-MS). In order to better understand the data trends, cluster analysis, principal component analysis and linear discriminant analysis were applied. Mammary tumors influenced macro- and microelements content in the myocardium to a greater extent than applied diet supplementation. Significant influences of diet (p = 0.0192), mammary tumors (p = 0.0200) and interactions of both factors (p = 0.0151) were documented in terms of Fe content. CLA significantly decreased the contents of Cu and Mn (p = 0.0158 and p = 0.0265, respectively). The level of Ni was significantly higher (p = 0.0073), which was more pronounced in groups supplemented with CLA. The obtained results confirmed antioxidant properties of CLA and the relationship with Se deposition. Chemometric techniques distinctly showed that the coexisting pathological process induced differences to the greater extent than diet supplementation in the elemental content in the myocardium, which may impinge on cardiac tissue's susceptibility to injuries.

Poly(styrene)-co-2-vinylpyridine copolymer as a novel solid-phase adsorbent for determination of manganese and zinc in foods and vegetables by FAAS.

The aim of this study is to extract zinc and manganese from foods and vegetables using an amphiphilic copolymer adsorbent, poly(styrene)-co-2-vinylpyridine which was synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization from styrene and 2-vinyl pyridine in the presence of a trithiocarbonate and 2,2'-azo-bis isobutyro nitrile (AIBN) in toluene solution under argon at 80 °C. Fourier Transform Infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) spectroscopy were used in the characterization of the obtained copolymer. Under the optimum conditions, several validation variables such as uncertainty measurement, selectivity, robustness, precisions, matrix effects and accuracy were investigated. Taking an adsorption time of 15 min, detection limits of 0.04 µg L -1 and 0.2 µg L-1and 7.9 µg L-1and enrichment factors of 145 and 110 were obtained for Mn(II) and Zn(II), respectively.The method was successfully applied to the analysis of Mn(II) and Zn(II) in foods and vegetables.

Subcritical Water Extraction of Valuable Metals from Spent Lithium-Ion Batteries.

The leaching of valuable metals (Co, Li, and Mn) from spent lithium-ion batteries (LIBs) was studied using subcritical water extraction (SWE). Two types of leaching agents, hydrochloric acid (HCl) and ascorbic acid, were used, and the effects of acid concentration and temperature were investigated. Leaching efficiency of metals increased with increasing acid concentration and temperature. Ascorbic acid performed better than HCl, which was attributed to ascorbic acid's dual functions as an acidic leaching agent and a reducing agent that facilitates leaching reactions, while HCl mainly provides acidity. The chemical analysis of leaching residue by X-ray photoelectron spectroscopy (XPS) revealed that Co(III) oxide could be totally leached out in ascorbic acid but not in HCl. More than 95% of Co, Li, and Mn were leached out from spent LIBs' cathode powder by SWE using 0.2 M of ascorbic acid within 30 min at 100 °C, initial pressure of 10 bar, and solid-to-liquid ratio of 10 g/L. The application of SWE with a mild concentration of ascorbic acid at 100 °C could be an alternative process for the recovery of valuable metal in spent LIBs. The process has the advantages of rapid reaction rate and energy efficiency that may benefit development of a circular economy.

Analysis and Optimization of Mn Removal from Contaminated Solid Matrixes by Electrokinetic Remediation.

Electrokinetic remediation is a useful technique for the removal of ionic contaminants in soils, sediments, sludges, and other solid porous matrixes. The efficiency of metal removal and the electricity consumption in the electrokinetic treatment of soils largely depend on electric and physicochemical conditions. This study analyzes the electrokinetic treatment of Mn contaminated kaolinite clay specimen and the influence of voltage, current intensity, moisture content, pH, and facilitating agents on metal removal and energy consumption. The objective of this study is to identify the influence of the typical variables used in electrokinetic remediation. The results showed that the operation at constant voltage or constant current intensity were equivalent in terms of metal removal and energy consumption, as long as the electric field intensity was kept low to minimize the consumption in parallel electrochemical reactions, especially the electrolysis of water. The moisture content had a significant influence on the Mn removal. Moisture content higher that 50 percent resulted in very effective Mn removal as compared with kaolinite specimens with lower moisture. The control of pH in the electrolyte solutions and the addition of facilitating agents (organic acids) enhanced the removal of Mn but increased the electric energy cost. Overall, the best conditions for Mn removal involved low to moderate electric potential difference (10 to 30 V), the use of citric acid as the facilitating agent, and the pH control in the cathode at a slightly acid pH. The electrokinetic treatment of a sludge from a water treatment plant contaminated with Mn was effective when pH control on the cathode was used. Mn and various metals (66% of Mn, 30% of Cu, 56% of Zn, 21% Sr, and 21% of Fe) were removed with moderate electricity and acid consumption.

Ultrasound-assisted extraction of Pb, Cd, Cr, Mn, Fe, Cu, Zn from edible oils with tetramethylammonium hydroxide and EDTA followed by determination using graphite furnace atomic absorption spectrometer.

A new method for extraction and determination of trace and ultratrace impurities from edible oils via an ultrasound-assisted extraction using tetramethylammonium hydroxide (TMAH) and ethylenediaminetetraacetic acid (EDTA) has been described. Method is simple and sensitive. Extraction variables like pH, concentrations of TMAH and EDTA, ultrasonication and centrifugation times were all optimised for analytes using engine-oil. Under optimised conditions, extraction of spiked analytes from all the edible oils into aqueous-medium were investigated and found to be quantitative (89-101%). Using this method, concentrations of impurities in edible-oils were determined by graphite furnace atomic absorption spectrometer (GFAAS) using standard-addition calibration method and validated with microwave-digestion method. The method was successfully applied to edible oils extracted from various seeds such as mustard oil, sun flower oil, sesame oil, ground nut oil, coconut oil, rice bran oil and corn oil containing ultratrace impurities. Accuracy of developed method for edible-oils was checked with corresponding results obtained by microwave digestion method.

Start-Up of a Biofilter in a Full-Scale Groundwater Treatment Plant for Iron and Manganese Removal.

In recent years, biological purification technology has been widely developed in the process of iron and manganese removal from groundwater. The cultivation and maturation of the biological filter layer are key for biological iron and manganese removal processes. The time needed for maturation varies significantly with the water quality, filter and filter media conditions and operation parameters; sometimes it takes only one or two months, sometime more than half a year. In this paper, the feasibility of adopting an intermittent operation for the cultivation of biofilter was investigated with productive filters in a groundwater treatment plant, and the comparative test of the filter column was conducted. The results showed that the intermittent operation had little effect on the cultivation of the biofilter because dissolved oxygen would be gradually exhausted during the filter-suspension process, making the filter layer anaerobic, thus possibly inhibiting the growth and reproduction of IMOB (Iron and Manganese Oxidizing Bacteria). At the same time, the test shows that when the mature biological filter needs the suspension operation, the emptying method should be considered to avoid the destruction of the biological layer.

Long-term operation and autotrophic nitrogen conversion process analysis in a biofilter that simultaneously removes Fe, Mn and ammonia from low-temperature groundwater.

One lab-scale biofilter that simultaneously removes Fe, Mn and ammonia from 4 °C groundwater was established to investigate the nitrogen conversion process. The results showed that 333 days were needed to achieve the required standards for Fe, Mn and ammonia under a filtration rate of 3 m/h. Effluent nitrite concentration was the key factor determining the final operation parameters. Both nitrification and anaerobic ammonium oxidation (ANAMMOX) contributed to nitrogen conversion. The calculation results demonstrated that autotrophic nitrogen removal proportion was about 15.92% in steady operation period. Meanwhile, 7 genera of Mn oxidizing bacteria (MnOB) were detected; Candidatus Brocadia was the only detected ANAMMOX genera. The corresponding functional oxidizing bacteria could be acclimated sufficiently in biofilter treating low-temperature groundwater.

[Mechanism of Removing Iron and Manganese from Drinking Water Using Manganese Ore Sand and Quartz Sand as Filtering Material].

Two lab-scale biofilters packed with manganese ore sand and quartz sand were constructed to reveal the behavior in removing iron and manganese during the start-up period. Meanwhile, the removal mechanism of the two sands was also investigated by means of EDS, XPS, and SEM. With the influent iron (2-3 mg·L-1) and manganese (0.3-0.6 mg·L-1), the start-up operational results indicated that the quartz sand biofilter needed 15 and 30 d to achieve the removal of iron and manganese, respectively. The manganese ore sand only required 10 d to remove iron, while the effluent manganese was always below of 0.1 mg·L-1. The results confirmed that the natural iron and manganese oxides coated on the manganese ore sand surface could explain its better removal behavior as compared to quartz sand. However, the generated iron oxide could also act as the adsorbent and catalyst like natural iron oxide, only when iron removal occurred in the quartz sand biofilter. The final product of iron removal was a complex consisting of divalent and trivalent iron, with a specific value of 1:1.44-1:1.54. Moreover, during the start-up period, manganese ore sand transformed manganese from divalent to trivalent by the catalytic effect, while the latter tended to be converted to the quadrivalent state under the bioactivity. The quartz sand could adsorb manganese but easily became saturated, and then the removal was dominated by bioactivity. The product generated by the manganese removal process was also a complex with the three valences. Moreover, the two complexes could coat onto the surface of the sands, but most of the iron complex was easily washed out of the filtering layer. Conversely, the manganese complex tended to coat onto the manganese ore sand surface or accumulate between the pores of quartz sand.

Arsenite removal from groundwater by iron-manganese oxides filter media: Behavior and mechanism.

Arsenic, a common contaminant in groundwater environments, usually coexists with other contaminants, for example, ammonium, iron, and manganese. In our previous studies, an iron-manganese (Fe-Mn) oxides filter media was developed for catalytic oxidation removal of ammonium, iron, and manganese. In this study, batch oxidation/adsorption kinetic experiments revealed that the filter media could easily oxidize arsenite (As(III)) to arsenate (As(V)). And the sorption kinetics was found to follow the pseudo-second-order kinetic model. X-ray powder diffraction (XRD) and Fourier transform infrared spectra (FTIR) along with X-ray photoelectron spectroscopy (XPS) were used to analyze the surface change in the Fe-Mn oxides. Based on sorption and spectroscopic measurements, the mechanism of As(III) removal by the Fe-Mn oxides filter media was found to be an oxidation coupled with sorption approach. As(III) in the aqueous solution was firstly oxidized to As(V) on the surfaces of the Fe-Mn oxides filter media. Then the converted As(V) was attracted to the Fe-Mn oxides filter media surfaces and bounded with the active sites (-OH groups), through weak intermolecular H-bondings. Our results indicated that the novel Fe-Mn oxides filter media could be applied for the simultaneous removal of ammonium, iron, manganese, and As(III) in drinking water treatment and environmental remediation. PRACTITIONER POINTS: A novel iron-manganese oxides filter for efficient As(III) removal was established. The exhausted filter media could be easily regenerated by NaHCO3 solution. Mn(III) related to surface lattice oxygen species was responsible for As(III) oxidation. The oxidation and adsorption processes were involved in As(III) removal. The filter media could be successfully applied to simultaneous removal of ammonium, manganese, iron, and arsenic.

A review of the implications and challenges of manganese removal from mine drainage.

Manganese (Mn) is the third most abundant transition metal in the Earth's crust. Decades of increasing worldwide mining activities have inevitably led to the release of large amounts of this metal into the environment. Mine drainage, either acidic or neutral, often contains high levels of Mn, which have potentially detrimental effects on ecosystems and receiving water bodies. This review provides a comprehensive assessment of the main implications and challenges of Mn treatment in mine drainage. With this aim, the beneficial and adverse effects of Mn on ecosystems and human health are presented first. A comparison of background and mine effluents Mn contents is also provided, further stressing the need for Mn removal from mine drainage. Several technical options to address Mn contamination in acid and neutral mine drainage, and the challenges associated with Mn removal, are subsequently discussed. Thus, this paper presents up-to-date knowledge on the available physicochemical and biological processes deemed operative in Mn removal during mine drainage treatment and their limitations considering the distinctive behavior of Mn. The discussion is further extended to passive treatment systems, which are the most commonly implemented systems for mine drainage treatment on abandoned or closed mine sites, and highlights both their design criteria and operation requirements, as well as the factors that influence Mn removal efficiency. Finally, new perspectives on future research and development needs are identified to address the challenges in Mn removal during mine drainage treatment.

The simultaneous removal of ammonium and manganese from surface water by MeOx: Side effect of ammonium presence on manganese removal.

Manganese and ammonium pollution in surface water sources has become a serious issue. In this study, a pilot-scale filtration system was used to investigate the effect of ammonium on manganese removal during the simultaneous removal of ammonium and manganese from surface water using a manganese co-oxide filter film (MeOx). The results showed that the manganese removal efficiency of MeOx in the absence of ammonium was high and stable, and the removal efficiency could reach 70% even at 5.5 °C. When the influent ammonium concentration was lower than 0.7 mg/L, ammonium and manganese could be removed simultaneously. However, at an ammonium concentration of 1.5 mg/L, the manganese removal efficiency of the filter gradually decreased with time (from 96% to 46.20%). Nevertheless, there was no impact of manganese on ammonium removal. The mechanism by which ammonium negatively affected manganese removal was investigated, demonstrating that ammonium affected manganese removal mainly through two possible mechanisms. On one hand, the decreased pH caused by ammonium oxidation was unfavorable for the oxidation of manganese by MeOx; on the other hand, the presence of ammonium slowed the growth of new MeOx and retarded the increase in the specific surface area of the MeOx-coated sand, and induced changes in the morphology and crystal structure of MeOx. Consequently, the manganese removal efficiency of the filter decreased when ammonium was present in the inlet water.

Study on the Factors Affecting the Start-Up of Iron-Manganese Co-Oxide Filters for Ammonium and Manganese Removal from Groundwater.

The high concentration of ammonium (NH4⁺-N) and manganese (Mn2+) in underground water poses a major problem for drinking water treatment plants. Effective catalytic oxidative removal of NH4⁺-N and Mn2+ by iron-manganese co-oxide film (MeOx) filters was first developed by our group in a previous study. In this study, several identical pilot-scale filters were employed to optimize the start-up process for simultaneous removal of NH4⁺-N and Mn2+ from potable water supplies. Experiments were conducted to assess the influence of Mn2+ concentration, Fe2+ concentration, filtration rate and dosing time on the start-up period of the filter. Results demonstrated that the ability of the filter to remove completely 1.5 mg/L NH4⁺-N could be achieved on the sixth day at the soonest and the removal of Mn2+ could reach 1 mg/L by the 18th day. Filter R3 feeding with 1 mg/L Fe2+, 2 mg/L Mn2+ and 3.5 mg/L MnO4- during the start-up period exhibited the optimum NH4⁺-N and Mn2+ removal effect. Short dosing time was not conducive to attaining full NH4⁺-N removal in filters, especially the activity of NO2--N conversion to NO3--N. The compositional analysis and element distribution analysis results demonstrated that there was an abundance of C, O, Mn, Mg, Fe, Ca and Si across the entire area of the surface of the filter media and the elemental distribution was homogeneous, which was different from the biofilter media. Knowledge-guided performance optimization of the active iron-manganese co-oxide could pave the way for its future technological use.

Electrochemical effect on bioleaching of arsenic and manganese from tungsten mine wastes using Acidithiobacillus spp.

Mine wastes from tungsten mine which contain a high concentration of arsenic (As) may expose many environmental problems because As is very toxic. This study aimed to evaluate bioleaching efficiency of As and manganese (Mn) from tungsten mine wastes using the pure and mixed culture of Acidithiobacillus ferrooxidans and A. thiooxidans. The electrochemical effect of the electrode through externally applied voltage on bacterial growth and bioleaching efficiency was also clarified. The obtained results indicated that both the highest As extraction efficiency (96.7%) and the highest Mn extraction efficiency (100%) were obtained in the mixed culture. A. ferrooxidans played a more important role than A. thiooxidans in the extraction of As whereas A. thiooxidans was more significant than A. ferrooxidans in the extraction of Mn. Unexpectedly, the external voltage applied to the bioleaching did not enhance metal extraction rate but inhibited bacterial growth, resulting in a reverse effect on bioleaching efficiency. This could be due to the low electrical tolerance of bioleaching bacteria. However, this study asserted that As and Mn could be successfully removed from tungsten mine waste by the normal bioleaching using the mixed culture of A. ferrooxidans and A. thiooxidans.

[Start-up and Operation of Biofilter Coupled Nitrification and CANON for the Removal of Iron, Manganese and Ammonia Nitrogen].

A pilot-scale bio-filter coupled nitrification and CANON was started up to remove iron, manganese and ammonia nitrogen from groundwater in a plant, and the main removal route of ammonia nitrogen was analyzed. The experiment showed that the bio-filter could be started up successfully and achieved stable operation after 164 days of culture development. The value of △NH4+-N/△NO3--N was 1.49, and the oxidation and removal of Fe(Ⅱ), Mn(Ⅱ), and NH4+-N were (9.87±1.17), (2.25±0.06), and (1.51±0.06) mg·L-1, respectively. The calculation based on the quantitative relationship between nitrogen conservation and dissolved oxygen (DO) measurement indicated that the contribution of CANON to NH4+-N removal was 33.48%-38.87%, and the average ratio of ammonia nitrogen removal amount to DO was 1:3.79-1:3.94. The removal ratio of ammonia nitrogen was lower with lower temperature.

Manganese and iron recovery from groundwater treatment sludge by reductive acid leaching and hydroxide precipitation.

In this study, the recovery of manganese (Mn) and iron (Fe) from groundwater treatment sludge through reductive acid leaching and hydroxide precipitation was investigated. Maximum leached Mn (100%) was obtained using sulfuric acid and hydrogen peroxide at 25 °C. Leached Mn and Fe decreased with the increase in the solid-liquid ratio. Leaching time had minimal effect on Mn and Fe leaching beyond 5 min, while agitation rate had minimal effect beyond 150 rpm. At 25 °C, the rate-limiting step of Mn leaching was diffusion through inert solid components of the sludge, composed mainly of insoluble sand particles. Fe leaching was governed by diffusion through the insoluble components of the sludge, including the unreacted manganese dioxide (MnO2). Maximum precipitation of Fe and separation from Mn in the leachate through addition of potassium hydroxide occurred at pH 4.0. The results demonstrated that reductive acid leaching and hydroxide precipitation is an effective means of recovering Mn and Fe from groundwater treatment sludge. The applicability of the recovered Mn for nickel ion removal from aqueous solution was also explored in the study. Highest nickel ion uptake by the MnO2 synthesized from the recovered Mn was at 111.67 mg g-1, even exceeding the adsorption capacities of previously studied nickel adsorbents.

Manganese porphyrin decorated on DNA networks as quencher and mimicking enzyme for construction of ultrasensitive photoelectrochemistry aptasensor.

In this work, the manganese porphyrin (MnPP) decorated on DNA networks could serve as quencher and mimicking enzyme to efficiently reduce the photocurrent of photoactive material 3,4,9,10-perylene tetracarboxylic acid (PTCA), which was elaborately used to construct a novel label-free aptasensor for ultrasensitive detection of thrombin (TB) in a signal-off manner. The Au-doped PTCA (PTCA-PEI-Au) with outstanding membrane-forming and photoelectric property was modified on electrode to acquire a strong initial photoelectrochemistry (PEC) signal. Afterward, target binding aptamer Ι (TBAΙ) was modified on electrode to specially recognize target TB, which could further combine with TBAII and single-stranded DNA P1-modified platinum nanoparticles (TBAII-PtNPs-P1) for immobilizing DNA networks with abundant MnPP. Ingeniously, the MnPP could not only directly quench the photocurrent of PTCA, but also acted as hydrogen peroxide (HRP) mimicking enzyme to remarkably stimulate the deposition of benzo-4-chlorhexidine (4-CD) on electrode for further decreasing the photocurrent of PTCA, thereby obtaining a definitely low photocurrent for detection of TB. As a result, the proposed PEC aptasensor illustrated excellent sensitivity with a low detection limit down to 3 fM, exploiting a new avenue about intergrating two functions in one substance for ultrasensitive biological monitoring.

Sequential Extraction as Novel Approach to Compare 12 Medicinal Plants From Kenya Regarding Their Potential to Release Chromium, Manganese, Copper, and Zinc.

This study is focusing on a novel approach to screen a large number of medicinal plants from Kenya regarding their contents and availability of selected metals potentially relevant for treatment of diabetes patients. For this purpose, total levels of zinc, chromium, manganese, and copper were determined by flame atomic absorption spectrometry and inductively coupled plasma mass spectrometry as well as BCR sequential extraction to fractionate the elemental species in anti-diabetic medicinal plants collected from five natural locations in two sub counties in Nyamira County, Kenya. Solanum mauense had the highest zinc level of 123.0 ± 3.1 mg/kg while Warburgia ugandensis had the lowest level of 13.9 ± 0.4 mg/kg. The highest level of copper was in Bidens pilosa (29.0 ± 0.6 mg/kg) while the lowest was in Aloe vera (3.0 ± 0.1 mg/kg). Croton macrostachyus had the highest manganese level of 1630 ± 40 mg/kg while Clerodendrum myricoides had the lowest (80.2 ± 1.2 mg/kg). The highest level of chromium was in Solanum mauense (3.20 ± 0.06 mg/kg) while the lowest (0.04 ± 0.01 mg/kg) were in Clerodendrum myricoides and Warburgia ugandesis among the medicinal plants from Nyamira and Borabu, respectively. The levels of the elements were statistically different from that of other elements while the level of a given element was not statistically different in the medicinal plants from the different sub counties. Sequential extraction was performed to determine the solubility and thus estimate the bioavailability of the four investigated essential and potentially therapeutically relevant metals. The results showed that the easily bioavailable fraction (EBF) of chromium, manganese, zinc, and copper ranged from 6.7 to 13.8%, 4.1 to 10%, 2.4 to 10.2%, and 3.2 to 12.0% while the potentially bioavailable fraction (PBF) ranged from 50.1 to 67.6%, 32.2 to 48.7%, 23.0 to 41.1%, and 34.6 to 53.1%, respectively. Bidens pilosa, Croton macrostachyus, Ultrica dioica, and Solanum mauense medicinal plants used to treat diabetes by 80 % of the herbalists in Nyamira County were found to be rich in chromium, manganese, copper, and zinc. The EBF of zinc, manganese, and chromium constitutes adequate amounts recommended for daily intake not exceeding the ADI and delivered a low percentage of RDA when estimating daily intake during therapy from typically applied doses. The plants did not show any significant differences at p < 0.05 in terms of concentrations of the elements between the two study areas though the levels of the different elements were statistically significant. Another major observation was that high total levels of the metals in a given plant did not necessarily translate to high bioavailable levels, and hence the need to determine bioavailable form as it is the one accessible to the patient.