Release Of Mn Research Articles

Ternary Alloy PtWMn as a Mn Nanoreservoir for High‐Field MRI Monitoring and Highly Selective Ferroptosis Therapy

Ferroptosis exhibits potential to damage drug-resistant cancer cells. However, it is still restricted with the "off-target" toxicity from the undesirable leakage of metal ions from ferroptosis agents, and the lack of reliable imaging for monitoring the ferroptosis process in living systems. Herein, we develop a novel ternary alloy PtWMn nanocube as a Mn reservoir, and further design a microenvironment-triggered nanoplatform that can accurately release Mn ions within the tumor to increase reactive oxygen species (ROS) generation, produce O2 and consume excess glutathione for synergistically enhancing nonferrous ferroptosis. Moreover, this nanoplatform exerts a responsive signal in high-field magnetic resonance imaging (MRI), which enables the real-time report of Mn release and the monitoring of ferroptosis initiation through the signal changes of T1 -/T2 -MRI. Thus, our nanoplatform provides a novel strategy to store, deliver and precisely release Mn ions for MRI-guided high-specificity ferroptosis therapy.

Ternary Alloy PtWMn as a Mn Nanoreservoir for High‐Field MRI Monitoring and Highly Selective Ferroptosis Therapy

AbstractFerroptosis exhibits potential to damage drug‐resistant cancer cells. However, it is still restricted with the “off‐target” toxicity from the undesirable leakage of metal ions from ferroptosis agents, and the lack of reliable imaging for monitoring the ferroptosis process in living systems. Herein, we develop a novel ternary alloy PtWMn nanocube as a Mn reservoir, and further design a microenvironment‐triggered nanoplatform that can accurately release Mn ions within the tumor to increase reactive oxygen species (ROS) generation, produce O2and consume excess glutathione for synergistically enhancing nonferrous ferroptosis. Moreover, this nanoplatform exerts a responsive signal in high‐field magnetic resonance imaging (MRI), which enables the real‐time report of Mn release and the monitoring of ferroptosis initiation through the signal changes of T1‐/T2‐MRI. Thus, our nanoplatform provides a novel strategy to store, deliver and precisely release Mn ions for MRI‐guided high‐specificity ferroptosis therapy.

Tree species identity and mixing ratio affected the release of several metallic elements from mixed litter in coniferous-broadleaf plantations in subtropical China

Planting broadleaf trees in coniferous forests has been shown to promote biogeochemical cycling in plantations; however, how species mixing influences litter decomposition and release of metallic elements from mixed coniferous-broadleaf litter remains unclear. An in situ litter decomposition experiment was conducted to examine the effect of 1) a mixture from coniferous litter (Pinus massoniana) with different individual broadleaved litter (Bretschneidera sinensis, Manglietia chingii, Cercidiphyllum japonicum, Michelia maudiae, Camellia oleifera) and 2) their mixing ratio (mass ratios of coniferous and broadleaf litter of 5:5, 6:4 and 7:3) on the release of metallic elements [calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), manganese (Mn), iron (Fe), copper (Cu) and zinc (Zn)] during litter decomposition. We found that the identity of the broadleaf tree species in the mixed litter and the mixing ratio affected the release rates of metallic elements (p < 0.05). After one year of decomposition, K, Mg, Mn and Zn were released, while Na, Ca, Fe and Cu accumulated in the mixed litter. Mixing increased the release of K, Ca, Na, Mg, Fe, Mn, Cu and Zn in more than one-third of the samples, but inhibited the release of K, Fe and Mn in less than 14% of the samples. Increasing the mixing ratio of coniferous to broadleaf litter enhanced the release of Na, Fe, Mn and Zn but decreased the release of Ca and Mg. Overall, these results highlight that mixed litter, particularly tree species identity and mixing ratio, can alter the release and enrichment of metallic elements during litter decomposition, thereby affecting the cycling of metallic elements in plantations with different species compositions.

Litter decomposition and nutrient release from monospecific and mixed litters: Comparisons of litter quality, fauna and decomposition site effects

Abstract Litter decomposition and nutrient release are key processes for soil C and nutrient cycling. However, the relative importance of the effects of litter quality, fauna and decomposition site on litter decomposition remains poorly understood. Moreover, the macronutrient and micronutrient (C, N, P, K, Ca, Mg, Mn, Cu and Zn) release in the decomposition process are even less well‐known. In this study, we performed 5040 litterbag samplings of monospecific (Larix gmelinii, Acer mono, Quercus mongolica and Juglans mandshurica) and mixed (Larix with each broad‐leaved litter) litter treatments using litterbags with three mesh sizes (for different‐sized fauna) in four paired stands of natural secondary forests compared with adjacent Larix plantations in a temperate forest ecosystem in China. Litter decomposition rate and macronutrient and micronutrient release during decomposition were assessed. We found that variation in litter quality had a considerably greater effect on litter decomposition than fauna and decomposition site. The decomposition constant was significantly related to the initial litter Mg concentration and lignin/P ratio, suggesting the importance of the Mg content and lignin/P ratio in controlling litter decomposition in temperate tree species. We also showed that macrofauna significantly increased monospecific but not mixed litter decomposition. In addition, the decomposition site conditions further influenced monospecific litter decomposition. Furthermore, the litter quality significantly influences N and Mn release in both monospecific and mixed litters. Compared with Larix litter, the average of N and Mn increased 33.9% and 53.8% in three broad‐leaved litters, and 21.4% and 38.0% in three mixed litters respectively. Synthesis. Litter quality is a relatively more important factor than fauna and decomposition site for the decomposition of both monospecific and mixed litters when studied at a local scale in temperate forests. Moreover, litter decomposition enhanced in plantation sites with poor soil nutrient status, which has implications for C and nutrient cycling and long‐term below‐ground forest ecosystem functions.

Developing the large-area manganese-based catalytic ceramic membrane for peroxymonosulfate activation: Applications in degradation of endocrine disrupting compounds in drinking water

Endocrine disrupting compounds (EDCs) in the aquatic systems are of growing concerns that could undermine drinking water safety. In this study, manganese (III) oxide (Mn2O3) based catalytic ceramic membrane (CCM) was developed for the activation of peroxymonosulfate (PMS), and its applicability has been tested in degrading the ten different EDCs (including bisphenol analogs (BPs)) in drinking water. The CCMs were synthesized at different calcination temperatures i.e., 850, 950, and 1150 °C. Optimal performance of CCMs/PMS was achieved at a higher degree of calcination. The CCMs/PMS has shown a potential to effectively degrade the EDCs at higher concentrations (mg/L) to trace levels (ng/L). The CCMs/PMS system adopted a non-radical pathway of degrading the EDCs through the extensive generation of singlet oxygen (1O2), as confirmed using quenching experiments and electron paramagnetic resonance (EPR) spectroscopy. 1O2-based oxidation process showed special selectivity for the decontamination of phenols and bisphenols. The long-term performance of CCMs/PMS showed good stability in degradation of the EDCs in drinking water, also with efficient mineralization (TOC removal >55%) and negligible release of Mn (0.004 wt%Mn/min). CCMs/PMS system also showed high potential in improving water quality by reducing the disinfection byproducts (DBPs) formation potential, highest recorded for bromodichloromethane (CHCl2Br, 100%) and lowest for dichloroacetic acids (TCAA, ∼50%). The study provided a highly efficient catalytic ceramic membrane based advanced oxidation process (AOPs) for effective degradation multiple of EDCs in drinking water, and the findings of this work can be a baseline for full-scale water treatment applications.

Effects of atmosphere and blending ratios on emission characteristics of pollutants from co‐combustion of municipal solid waste and aged refuse

AbstractThe emission of pollutants caused by incineration has imposed a severe burden on the atmospheric environment. In this study, the thermogravimetric thermal analyzer (TGA) was used to study the characteristic behavior of co‐combustion of municipal solid waste (MSW) and aged refuse (AR). And combined with Fourier transform infrared measurement, the emissions of several typical gaseous pollutants (NO, COx, CH4, HCl, HCN, SO2) have been investigated. Also, the release characteristics of heavy metals (As, Cd, Co, Cr, Cu, Ni, Pb, Zn, Ti) during the co‐combustion process were explored using inductively coupled plasma–optical emission spectrometry (ICP‐OES). This research found that both the combustion atmosphere and the mixing ratios impacted the experimental results. As the proportion of AR in the blends increased, the ignition index decreased, the burnout temperature rose, but the burnout efficiency increased. The addition of AR inhibited the generation of CO2, CH4, and HCl and promoted the production of NO and CO. Aerobic environment mainly inhibited the release of Cr and Mn. The research results provided important information for the study of pollutant emission characteristics during the co‐combustion of MSW with AR.

Speciation and release risk of heavy metals bonded on simulated naturally-aged microplastics prepared from artificially broken macroplastics

The negative impact of microplastics (MPs) act as metals vectors to environment and ecosystem have been paid more and more attention, and the accumulation risk of them to human body through the food chains and food webs needs to attract attention. In addition, the MPs bonded with heavy metals transport from river into the sea with high salinity may also have metals release risk. Herein, natural aged microplastics prepared from artificially broken macroplastics adsorbed with heavy metals accumulated from the natural environment were tested for their states and release risk in several simulated solution (NaCl and gastrointestinal solutions) to understand their effects on environment and human health. The adsorption capacity of different heavy metals on MPs was different during natural aging process proved by four-acid digestion method. Metals with high accumulation (including Pb, As, Cr, Mn, Ni, Zn, Co, Cu and Cd) on NAMPs were selected for further study. Results obtained via three-step extraction method showed that these heavy metals were mainly present as acid-extractable and reducible ions, which were characterized by high bioavailability. Release experiments suggested the notable Mn, Zn, As, Cr, Cu and Ni release in NaCl solution, and significant release of Mn, Zn, As, Cr, Cu, Pb and Ni in gastrointestinal solutions. The high metal release ratio in the simulated gastric solution was attributed to the weak binding of metal ions to NAMPs in acidic environment. This study will play a vital rule in assessing the ecological risks associated with MPs in natural environment.

Glutathione-Responsive Chemodynamic Therapy of Manganese(III/IV) Cluster Nanoparticles Enhanced by Electrochemical Stimulation via Oxidative Stress Pathway.

Escalating the level of reactive oxygen species (ROS) in a tumor microenvironment is one of the effective strategies to improve the efficacy of anticancer therapy. In this work, manganese cluster nanoparticles (Mn12) encapsulated with heparin (Mn12-heparin) were developed as a chemodynamic therapeutic agent for cancer treatment by raising ROS levels in tumor cells via cascade reactions. The manganese cluster is a cluster of mixed valence (III/IV) with acetate as the ligand. The cluster is readily subject to reduction by glutathione (GSH) to release Mn(II), which reacts with H2O2 to generate hydroxyl radicals via a Fenton-like pathway. The generation of hydroxyl radicals could be enhanced by the stimulation of an external alternative electric field during which GSH acts as an electron mediator to enhance the release of Mn(II) from the cluster. The relatively high levels of both H2O2 and GSH and the acidic environment in tumor cells strengthen its specificity when the manganese cluster system is employed to suppress or eliminate tumors. Both in vitro and in vivo results suggest that, in addition to the cytotoxicity imposed by the raised ROS level due to the presence of Mn(II) species, the depletion of endogenous GSH leads indirectly to the inhibition of glutathione peroxidase 4 (GPX4), consequently raising the lipid peroxidation (LPO) level to cause ferroptosis. The apoptosis and ferroptosis jointly render the manganese-based agent potent efficacy with tumor-targeting specificity in antitumor treatment under electric stimulation.

Mn(II) complexes of phenylenediamine based macrocyclic ligands as T1-MRI contrast agents

The Mn(II) complexes are emerging as alternative T1-MRI contrast agents (CAs) to the currently available Gd-based CAs. The complexes [Mn(L1)] 1 and [Mn(L2)] 2 of o-phenylenediamine based macrocyclic ligands are reported as T1-CAs for MRI applications. The high spin state of the Mn(II) complexes (S = 5/2) is confirmed by EPR spectra. The complexes showed an irreversible Mn(II)/Mn(III) redox potential at pH 7.28, which became more and less positive at the acidic and alkaline pHs, respectively. The species [MnL], [Mn(LH−1), and [Mn(LH−2) are persisted in solution. Complex 1 is inert towards Ca(II), Mg(II), and Zn(II), whereas complex 2 is inert for Ca(II) and Mg(II) and labile under Zn(II) and Cu(II) ions. Complex 1 showed an r1-relaxivity of 3.27 and 2.32 mM−1 s−1 at 1.41 T, 25, and 37 °C respectively via inner-sphere water relaxation, which is lower than that of 2 (r1, 5.56, and 4.19 mM−1 s−1) at pH 7.28 and 1.41 T. The Mn(II) complexes showed a 2–8% enhancement of r1-relaxivity while lowering the pH to acidic, which corresponds to the release of free Mn(II) ions. In contrast, the r1-relaxivity is dropped to 52% and 20% for 1 and 2 respectively under alkaline pH due to the deprotonation of inner-sphere water. Phantom images obtained on Bruker ‘BIOSPEC’ 47/40 animal research MRI/MRS scanner showed concentration-dependent brightness. The interaction of human serum albumin (HSA) with 1 and 2 exhibited five times higher r1-relaxivities (11.3 and 22.0 mM−1 s−1 at 1.41 T, respectively).

Macrophage Membrane-Camouflaged Responsive Polymer Nanogels Enable Magnetic Resonance Imaging-Guided Chemotherapy/Chemodynamic Therapy of Orthotopic Glioma.

Development of innovative nanomedicine formulations to traverse the blood-brain barrier (BBB) for effective theranostics of glioma remains a great challenge. Herein, we report the creation of macrophage membrane-camouflaged multifunctional polymer nanogels coloaded with manganese dioxide (MnO2) and cisplatin for magnetic resonance (MR) imaging-guided chemotherapy/chemodynamic therapy (CDT) of orthotopic glioma. Redox-responsive poly(N-vinylcaprolactam) (PVCL) nanogels (NGs) formed via precipitation polymerization were in situ loaded with MnO2 and physically encapsulated with cisplatin to have a mean size of 106.3 nm and coated with macrophage membranes to have a good colloidal stability. The generated hybrid NGs display dual pH- and redox-responsive cisplatin and Mn(II) release profiles and can deplete glutathione (GSH) rich in tumor microenvironment through reaction with disulfide-containing cross-linkers within the NGs and MnO2. The thus created Mn(II) enables enhanced CDT through a Fenton-like reaction and T1-weighted MR imaging, while the loaded cisplatin not only exerts its chemotherapy effect but also promotes the reactive oxygen species generation to enhance the CDT efficacy. Importantly, the macrophage membrane coating rendered the hybrid NGs with prolonged blood circulation time and ability to traverse BBB for specific targeted chemotherapy/CDT of orthotopic glioma. Our study demonstrates a promising self-adaptive and cooperative NG-based nanomedicine platform for highly efficient theranostics of glioma, which may be extended to tackle other difficult cancer types.

Study on the Prevention and Control of Fe and Mn Pollution by Resistant Mixed Bacteria in Simulated Mining Area

By simulating the mining environment, the potential of the selected mixed bacteria (Pseudomonas putida, Lysinibacillus xylanilyticus, Lysinibacillus macroides, Bacillus simplex, Brevibacillus agri) to control Fe and Mn pollutants in mining environment were explored. The results showed that the selected bacteria could inhibit the release of Fe and Mn from ore into the aquifer, and the inhibition effect on Mn was significantly stronger than that on Fe. At the same time, these processes also have a certain degree of impact on the external environment, including the gradual increase of pH, the gradual decrease of oxidation-reduction potential, and the decrease of dissolved oxygen concentration. The changes of these external environmental factors will once again directly affect the degradation and immobilization of Fe and Mn. The selected mixed bacteria can also enhance the adsorption of free Fe and Mn, improve the adsorption efficiency and capacity of Fe and Mn, and slow down the desorption of Fe and Mn to water.

Incorporating Kinetic Modeling in the Development Stages of Hard Rock Mine Projects

Weathering cell test, designed specifically to overcome material-limited constraints, yields prompt and efficient experimental assessment during the development stages of mining projects. However, it has barely benefited from geochemical modeling tools despite their ease of use. Accordingly, this paper aims to strengthen the upstream geochemical assessment via parametric analysis that simulates the effect of various mineral assemblages on leachate quality recovered from weathering cells. The main objective is to simulate the pH in presence of silicate neutralizing minerals and Mn release from carbonates based upon minimal characterization data. The public domain code PHREEQC was used for geochemical kinetic modeling of four weathering cells. The kinetic model utilized a water film concept to simulate diffusion of chemical elements from mineral surfaces to the pore water. The obtained results suggest that the presence of the silicate neutralizing minerals slightly affects the Mn release from carbonates. Furthermore, plagioclases could supply a significant neutralization potential when they predominate the mineral assemblage. Finally, coupling weathering cell test and parametric analyses illuminate the pH evolution for various mineral proportion scenarios.

Revisiting the adsorption of antimony on manganese dioxide: The overlooked dissolution of manganese

Manganese dioxide (MnO2) exhibits great potential for the uptake of antimony (Sb) from wastewater. Much research has been dedicated to enhancing the capacity of MnO2 for Sb sequestration. However, the dissolution behavior of Mn has been overlooked, and the underlying relationship between Sb(III) adsorption and Mn dissolution is not clear. In this study, batch experiments evidenced that there was a noticeable dissolution of Mn during the adsorption of Sb(III) on MnO2. A correlation analysis demonstrated that the amount of Mn dissolved was dependent on the Sb(III) adsorption capacity of MnO2, regardless of the crystalline phase of MnO2. Further experimental and theoretical results (taking α-MnO2 as an example) unveiled that Mn dissolution involved the following stages. First, Sb(III) adsorbed onto the (310) crystal plane of α-MnO2 to form a complex via two Mn-O-Sb bonds, which can be proven by the delicate adsorption configuration and corresponding adsorption energy (Ead) of −4.04 eV. Then, three O atoms from the α-MnO2 progressively deprived two H atoms from Sb(OH)3 and one H atom from a water molecule bound to Sb(OH)3, respectively. This process was verified by the configuration of the transition state (transition state #3) and the occurrence of electron transfer (i.e., the net charge changed by + 2 e). Finally, the Mn-O bonds of α-MnO2 were weakened and disrupted, leading to the release of Mn into the aqueous solution. This work advances the fundamental understanding of Sb adsorption onto MnO2, which not only promotes a re-evaluation of the utility of MnO2 for Sb(III) elimination but also provides a theoretical guide for the design of robust MnO2-based adsorbents.

Manganese uptake by red maples in response to mineral dissolution rates in soil

Manganese (Mn) is an essential plant micronutrient that influences photosynthesis, ecosystem productivity, and soil carbon storage. Our objective was to quantify how Mn uptake by forest vegetation relates to Mn release into soil solution through mineral dissolution. A greenhouse pot experiment was conducted to quantify Mn uptake by red maple saplings as a function of mineral solubility to test whether Mn uptake was limited by the supply of Mn to soil solution. Differences in soil microbial community composition between treatments, particularly amongst Mn cycling bacteria and fungi, were also evaluated to assess potential microbial impacts on observed Mn fluxes. Plant Mn uptake was highest in systems supplied with dissolved Mn(II) because it was not kinetically limited by mineral weathering. Mn uptake was also higher in systems supplied with a fast-weathering substrate (shale containing Mn(II)-bearing pyrite) than a slow-weathering substrate (Mn(IV)-oxide). However, vegetation accumulated a decreasing proportion of available Mn with increasing solubility, indicating that uptake was tempered relative to solubility. The presence of bacterial phyla containing known Mn-oxidizing bacteria indicates the potential for Mn-oxidizing bacteria to influence Mn solubility within Mn-oxide and dissolved Mn treatments. A relatively low abundance of these bacteria points to their limited capacity to oxidize and retain Mn in the shale treatments, consistent with substantial Mn leaching. We conclude that Mn uptake was primarily controlled by dissolution rates of Mn-bearing minerals but modified by biological processes. The quantitative framework presented here can guide understanding of how biogeochemical processes control element cycling between plants and soils.

Anthropogenic Organic Pollutants in Groundwater Increase Releases of Fe and Mn from Aquifer Sediments: Impacts of Pollution Degree, Mineral Content, and pH

In many aquifers around the world, there exists the issue of abnormal concentrations of Fe and Mn in groundwater. Although it has been recognized that the main source of this issue is the release of Fe and Mn from aquifer sediments into groundwater under natural environmental conditions, there lacks enough reliable scientific evidence to illustrate whether the pollutants imported from anthropogenic activities, such as organics, can increase this natural release. On the basis of time series analysis and comparative analysis, the existence of an increasing effect was verified through laboratorial leaching test, and the impacts of aquatic chemical environment conditions, such as pH, on the effect were also identified. The results showed that the increase of organics in groundwater made the release of Fe and Mn more thorough, which was favorable for the increase of groundwater concentrations of Fe and Mn. The higher the contents of Fe- and Mn-bearing minerals in aquifer sediments, the higher the concentrations of Fe and Mn in groundwater after the release reaches kinetic equilibrium. Lower pH can make the leaching more thorough, but the neutral environment also increases the amount of Mn. It can be deduced that the pollutants such as organics imported by anthropogenic activities can indeed increase the releases of Fe and Mn from aquifer sediments into groundwater, thus worsening the issue of groundwater Fe and Mn pollution. The findings provide a deeper insight into the geochemical effects of Fe and Mn in the natural environment, especially in the groundwater system.

Migration analysis of Cr, Ni, Al, Fe, Mn, Cu, Zn, and Mo in internet-bought food serving stainless-steel utensils by ICP-MS and XRF

ABSTRACT A total of 120 internet bought stainless-steel utensil samples intended for food serving were analysed for their release of Cr, Ni, Al, Fe, Mn, Cu, Zn, and Mo. Samples were extracted using simulants under continuous and discontinuous test conditions, extracts were analysed by ICP-MS, and metallic compositions of utensils were indicated by XRF analysis. r2 values for all analytes were determined between 0.9982 and 0.9997. RSD and WRm values ranged between 4.5–8.5% and 80–107% for all analytes, respectively, and LOD was in the range of 0.11–25.8 µg/l. Migration results show that 35% of total sample types show non-compliance with the SMLs established by the Nordic guidelines. XRF data show good correlation between the metals’ migration levels and their respective compositions in the utensil, and toxicological exposure estimates no significant adverse health effects from food served with articles exceeding the SMLs for Fe, Al, and Ni.

Passivation of pyrite for reduced rates of acid and metalliferous drainage using readily available mineralogic and organic carbon resources: A laboratory mine waste study

Acid and metalliferous drainage (AMD) is a major environmental issue resulting largely from exposure to weathering of mine wastes containing pyrite (FeS2). At-source strategies to reduce the rate of formation of AMD have potential to be more cost-effective and sustainable than post-generation downstream treatments. The objective of this study was to examine the efficacy of geochemical and microbial treatments for at-source control through pyrite surface passivation. Six kinetic leach columns (KLCs), using a mine waste containing 3.8 wt% pyrite, were subjected to various treatments: 1) untreated, 2) blended calcite, and applications of 3) calcite-saturated water, 4) lime-saturated water followed by calcite-saturated water, 5) biosolids extract water (providing a source of organic carbon to promote microbial growth) and 6) biosolids extract in calcite-saturated water. The untreated KLC leachate pH was on average 5.7 for the first 12 weeks, followed by a gradual decrease to pH 4.5 at week 52. This slow pH decrease is attributed to neutralisation released upon Mg-siderite dissolution. The leachate pH from all treated KLCs was near-neutral at the end of the tests. Pyrite was surface-passivated and leaching supressed by all treatments except for calcite-saturated water. Leaching of Mn and Zn from the untreated waste identified the potential for adverse environmental impact. No evidence was found for surface passivation of Zn- or Mn-containing minerals in the treated KLCs. Blended calcite addition and lime-saturated water followed by calcite-saturated water were most effective at reducing release of Zn and Mn, likely due to precipitation as hydroxides/carbonates.

Impact of CO2 leakage from sub-seabed carbon dioxide storage on sediment and porewater geochemistry

Sub-seabed geological CO2 storage is discussed as a climate mitigation strategy, but the impact of any leakage of stored CO2 into the marine environment is not well known. In this study, leakage from a CO2 storage reservoir through near-surface sediments was mimicked for low leakage rates in the North Sea. Field data were combined with laboratory experiments and transport-reaction modelling to estimate CO2 and mineral dissolution rates, and to assess the mobilization of metals in contact with CO2-rich fluids and their potential impact on the environment. We found that carbonate and silicate minerals reacted quickly with the dissolved CO2, increasing porewater alkalinity and neutralizing about 5% of the injected CO2. The release of Ca, Sr, Ba and Mn was mainly controlled by carbonate dissolution, while Fe, Li, B, Mg, and Si were released from silicate minerals, mainly from deeper sediment layers. No toxic metals were released from the sediments and overall the injected CO2 was only detected up to 1 m away from seabed CO2 bubble streams. Our results suggest that low leakage rates of CO2 over short timescales have minimal impact on the benthic environment. However, porewater composition and temperature are effective indicators for leakage detection, even at low CO2 leakage rates.

Effects of chemical and natural ageing on the release of potentially toxic metal additives in commercial PVC microplastics

Various chemical substances, such as potentially toxic trace metals, are used as plastic additives to improve the performance of polymers and extend the service life of plastic products. However, these added trace metals are likely released from plastic into the environment when the plastic becomes a pollutant, although the process is poorly understood. In this study, chemical ageing of commercial polyvinyl chloride (PVC) microplastics using hydrogen peroxide (H2O2) and natural ageing of PVC that had been added to an alkaline paddy soil were undertaken to evaluate the potential release of trace metals from PVC. Enhanced release of trace metals from PVC with the increasing H2O2 concentrations was observed, in which the released Pb was 1–2 orders of magnitude higher than other metals (p < 0.01). The released Cr, Ni, Pb, Cu, Zn, Cd and Mn accounted for 87.37%, 79.27%, 22.02%, 20.93%, 17.06%, 15.11%, and 11.02% of their total concentrations (0.28 ± 0.03, 0.08 ± 0.01, 13.67 ± 0.18, 1.07 ± 0.02, 2.20 ± 0.18, 0.05 ± 0.00 and 1.26 ± 0.08 mmol kg−1) in PVC after ageing with 30% H2O2, respectively. Compared with the control treatment without PVC addition, the concentrations of CaCl2-extractable Cu, Mn, Ni, Pb, and Zn in the soil treated with 5% PVC are significantly increased after incubation for 60 days (p < 0.01). In conclusion, chemical and natural ageing have the potential to lead to the release of Cu, Mn, Ni, Pb, and Zn from the commercial PVC into aquatic and terrestrial environments.

Manganese Release Kinetics In Some Calcareous Soils From The Sulaimani Governorate In Iraqi Kurdistan Region

This study was carried out in the Sulaimani Governorate, Iraqi Kurdistan Region, to estimate manganese release kinetics in five calcareous soils including (Sharazor, Qaradagh, Bazian, Mawat, and Surdash). The highest amount of Mn release during 48 hours was least in soil Surdash (64.00 mg kg-1), while Soil Mawat exhibited the highest release (541.82 mg kg-1). The value of first order release rate constant (k1) from first order differed from 0.076 to 0.102 with a mean of (0.091 h-1). The mean values of the rate constant (a and b) from the power function model were (2.128 mg Mn kg -1(h-1)b and 0.916 mg Mn kg-1)−1) respectively varied widely with the five soil. The value of second order release constant (k2) from second order model, varied from (-0.012) to (-0.005) with a mean of (-0.008 mg Mn kg-1)-1. The first order, power function, and second order were the best-fitted model used to describe Mn release process very well in the investigated soils.