Fenton-like system of UV/Glucose-oxidase@Kaolin coupled with organic green rust: UV-enhanced enzyme activity and the mechanism of UV synergistic degradation of photosensitive pollutants.

This study introduces the UV/glucose-oxidase@Kaolin (GOD@Kaolin) coupled organic green rust (OGR) system (UV/OGR/GOD@Kaolin) to investigate the promotion of glucose oxidase activity by UV light and its synergistic degradation mechanism for photosensitive pollutants, specifically targeting the efficient degradation of 4-chlorophenol (4-CP). The enzyme system demonstrates its ability to overcome drawbacks associated with traditional Fenton systems, including a narrow pH range and high localized concentration of H2O2, by gradually releasing hydrogen peroxide in situ within a neutral environment. In the presence of UV radiation under specific conditions, enhanced enzyme activity is observed, resulting in increased efficiency in pollutant removal. The gradual release of hydrogen peroxide plays a crucial role in preventing unwanted reactions among active substances. These unique features facilitate the generation of highly reactive species, such as Fe(IV)O, •OH, and •O2-, tailored to efficiently target the organic components of interest. Additionally, the system establishes a positive iron cycle, ensuring a sustained reactive capability throughout the degradation process. The results highlight the UV/OGR/GOD@Kaolin system as an effective and environmentally friendly approach for the degradation of 4-CP, and the resilience of the enzyme extends the system's applicability to a broader range of scenarios.

Sustainable and Reagentless Fenton Treatment of Complex Wastewater.

Conventional Fenton treatment is fundamentally impractical for large-scale applications, as the consumption of Fe(II), H2O2, and pH regulators and the accumulation of iron hydroxide sludge are very costly. This paper describes a new method for Fenton treatment of complex wastewater without additional dosing of Fe(II) and H2O2, without iron-sludge accumulation, and with less consumption of pH regulators, using a novel bioelectrode system. Our new system includes a novel three-chamber microbial electrolysis unit and Fenton reaction unit, where Fenton reagents are generated by biotic and abiotic cathodes, while the bioanode simultaneously degrades biodegradable organics from the wastewater. The system's self-alkalinity buffering also waives the need for pH regulators. Dissolved organic carbon and 22 specific recalcitrant organics were removed by 99% and between 78 and 100%, respectively. The bioelectrode system generated 13 ± 3 mg/L dissolved Fe(II) and 5 ± 0.4 mg/L H2O2 for the Fenton reaction unit. The closed iron cycle avoided iron loss and iron sludge accumulation during operation. The pH regulator dosage and operating costs were just 9.7 and 1.4%, respectively, of what is required by classic Fenton. The low operating cost and reduction in chemical usage make it an efficient, sustainable alternative to the conventional treatment processes currently used for complex wastewater.

Iron Vacancy Accelerates Fe(II)-Induced Anoxic As(III) Oxidation Coupled to Iron Reduction.

Chemical oxidation of As(III) by iron (Fe) oxyhydroxides has been proposed to occur under anoxic conditions and may play an important role in stabilization and detoxification of As in subsurface environments. However, this reaction remains controversial due to lack of direct evidence and poorly understood mechanisms. In this study, we show that As(III) oxidation can be facilitated by Fe oxyhydroxides (i.e., goethite) under anoxic conditions coupled with the reduction of structural Fe(III). An excellent electron balance between As(V) production and Fe(III) reduction is obtained. The formation of an active metastable Fe(III) phase at the defective surface of goethite due to atom exchange is responsible for the oxidation of As(III). Furthermore, the presence of defects (i.e., Fe vacancies) in goethite can noticeably enhance the electron transfer (ET) and atom exchange between the surface-bound Fe(II) and the structural Fe(III) resulting in a two time increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites is likely to facilitate As(III) coordination and ET with structural Fe(III) based on electrochemical analysis and theoretical calculations showing that this reaction pathway is thermodynamically and kinetically favorable. Our findings highlight the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation, shedding a new light on As risk management in soils and subsurface environments.

Anaerobic Ammonium Removal Pathway Driven by the Fe(II)/Fe(III) Cycle through Intermittent Aeration.

Feammox, that is, Fe(III) reduction coupled to anaerobic ammonium oxidation, has been reported to play an important role in the nitrogen cycle in natural environments. However, the application of Feammox in wastewater treatment is limited because continuous Fe(III) supplementation is required for achieving continuous nitrogen removal, which is not feasible in practice. In this study, air was aerated intermittently into the Feammox system containing iron and high-content ammonium for oxidizing Fe(II) generated from Feammox to Fe(III), then, the produced Fe(III) participated in the next round of Feammox, leading to continuous nitrogen removal through the Fe(II)/Fe(III) cycle. The results showed that after each 10 min of aeration (150 mL/min), every 6-7 days, dissolved oxygen (DO) increased from 0 to about 0.4 mg/L, accompanied by a decrease in Fe(II) and an increase in Fe(III). One day after the aeration, DO was undetectable, and then, Fe(II) content increased and Fe(III) content decreased. On day 90, NH4+-N content in the aerated reactor was only 10.2 mg/L, while it remained at around 288.3 mg/L in the aeration-free group. X-ray diffraction showed that the generated Fe(III) through air aeration was Fe(OH)3. Microbial analysis showed that anammox and nitrification/denitrification could be excluded in the system. This NH4+ removal process, driven by the Fe(II)/Fe(III) cycle with O2 as the terminal electron acceptor, might be used as an in situ remediation method for treating high-content NH4+.

Northern High-Latitude Organic Soils As a Vital Source of River-Borne Dissolved Iron to the Ocean.

Organic soils in the Arctic-boreal region produce small aquatic humic ligands (SAHLs), a category of naturally occurring complexing agents for iron. Every year, large amounts of SAHLs-loaded with iron mobilized in river basins-reach the oceans via river runoff. Recent studies have shown that a fraction of SAHLs belong to the group of strong iron-binding ligands in the ocean. That means, their Fe(III) complexes withstand dissociation even under the conditions of extremely high dilution in the open ocean. Fe(III)-loaded SAHLs are prone to UV-photoinduced ligand-to-metal charge-transfer which leads to disintegration of the complex and, as a consequence, to enhanced concentrations of bioavailable dissolved Fe(II) in sunlit upper water layers. On the other hand, in water depths below the penetration depth of UV, the Fe(III)-loaded SAHLs are fairly resistant to degradation which makes them ideally suited as long-lived molecular transport vehicles for river-derived iron in ocean currents. At locations where SAHLs are present in excess, they can bind to iron originating from various sources. For example, SAHLs were proposed to contribute substantially to the stabilization of hydrothermal iron in deep North Atlantic waters. Recent discoveries have shown that SAHLs, supplied by the Arctic Great Rivers, greatly improve dissolved iron concentrations in the Arctic Ocean and the North Atlantic Ocean. In these regions, SAHLs play a critical role in relieving iron limitation of phytoplankton, thereby supporting the oceanic sink for anthropogenic CO2. The present Critical Review describes the most recent findings and highlights future research directions.

Anaerobic ammonium oxidation linked to sulfate and ferric iron reduction fuels nitrogen loss in marine sediments.

Availability of fixed nitrogen is a pivotal driver on primary productivity in the oceans, thus the identification of key processes triggering nitrogen losses from these ecosystems is of major importance as they affect ecosystems function and consequently global biogeochemical cycles. Denitrification and anaerobic ammonium oxidation coupled to nitrite reduction (Anammox) are the only identified marine sinks for fixed nitrogen. The present study provides evidence indicating that anaerobic ammonium oxidation coupled to the reduction of sulfate, the most abundant electron acceptor present in the oceans, prevails in marine sediments. Tracer analysis with 15N-ammonium revealed that this microbial process, here introduced as Sulfammox, accounts for up to 5 µg 15N2 produced g-1 day-1 in sediments collected from the eastern tropical North Pacific coast. Raman and X-ray diffraction spectroscopies revealed that elemental sulfur and sphalerite (ZnFeS) were produced, besides free sulfide, during the course of Sulfammox. Anaerobic ammonium oxidation linked to Fe(III) reduction (Feammox) was also observed in the same marine sediments accounting for up to 2 µg 15N2 produced g-1 day-1. Taxonomic characterization, based on 16S rRNA gene sequencing, of marine sediments performing the Sulfammox and Feammox processes revealed the microbial members potentially involved. These novel nitrogen sinks may significantly fuel nitrogen loss in marine environments. These findings suggest that the interconnections among the oceanic biogeochemical cycles of N, S and Fe are much more complex than previously considered.

Impact of hydrothermalism on the ocean iron cycle.

As the iron supplied from hydrothermalism is ultimately ventilated in the iron-limited Southern Ocean, it plays an important role in the ocean biological carbon pump. We deploy a set of focused sensitivity experiments with a state of the art global model of the ocean to examine the processes that regulate the lifetime of hydrothermal iron and the role of different ridge systems in governing the hydrothermal impact on the Southern Ocean biological carbon pump. Using GEOTRACES section data, we find that stabilization of hydrothermal iron is important in some, but not all regions. The impact on the Southern Ocean biological carbon pump is dominated by poorly explored southern ridge systems, highlighting the need for future exploration in this region. We find inter-basin differences in the isopycnal layer onto which hydrothermal Fe is supplied between the Atlantic and Pacific basins, which when combined with the inter-basin contrasts in oxidation kinetics suggests a muted influence of Atlantic ridges on the Southern Ocean biological carbon pump. Ultimately, we present a range of processes, operating at distinct scales, that must be better constrained to improve our understanding of how hydrothermalism affects the ocean cycling of iron and carbon.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides.

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth's history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth.

Amino acid promoted oxidation of atrazine by Fe3O4/persulfate.

In the present study, we demonstrated that the presence of cysteine could remarkably enhance the degradation of atrazine by Fe3O4/persulfate system. The results of electron paramagnetic resonance (EPR) spectra confirmed the combination of cysteine and Fe3O4 exhibited much higher activity on activation of persulfate to generate more SO4•- and •OH than Fe3O4 alone. At pH of 3.0, SO4•- and •OH contributed to about 58.2 % and 41.8 % of atrazine removal respectively, while •OH gradually dominated the oxidation of atrazine from neutral condition to alkaline condition. The co-existing Cl- and HCO3- could quench SO4•-, resulting in the inhibition of atrazine degradation. The presence of low natural organic matters (NOM) concentration (0-2 mg L-1) could enhance the atrazine removal, and high concentration (>5 mg L-1) of NOM restrained the atrazine degradation. During the Cysteine/Fe3O4/Persulfate process, cysteine served as a complexing reagent and reductant. Through acidolysis and complexation, Fe3O4 could release dissolved and surface bound Fe2+, both of which contributed to the activation of persulfate together. Meanwhile, cysteine was not rapidly consumed due to a regeneration process, which was beneficial for maintaining Fe2+/Fe3+ cycle and constantly accelerating the activation of persulfate for atrazine degradation. The reused Fe3O4 and cysteine in the Cysteine/Fe3O4/Persulfate process exhibited high stability for the atrazine degradation after three cycles. The degradation pathway of atrazine included alkylic-oxidation, dealkylation, dechlorination-hydroxylation processes. The present study indicates the novel Cysteine/Fe3O4/Persulfate process might be a high potential for treatment of organic polluted water.

Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).

Sulfidation-reoxidation enhances heavy metal immobilization by vivianite.

Iron minerals in nature are pivotal hosts for heavy metals, significantly influencing their geochemical cycling and eventual fate. It is generally accepted that, vivianite, a prevalent iron phosphate mineral in aquatic and terrestrial environments, exhibits a limited capacity for adsorbing cationic heavy metals. However, our study unveils a remarkable phenomenon that the synergistic interaction between sulfide (S2-) and vivianite triggers an unexpected sulfidation-reoxidation process, enhancing the immobilization of heavy metals such as cadmium (Cd), copper (Cu), and zinc (Zn). For instance, the combination of vivianite and S2- boosted the removal of Cd2+ from the aqueous phase under anaerobic conditions, and ensured the retention of Cd stabilized in the solid phase when shifted to aerobic conditions. It is intriguing to note that no discrete FeS formation was detected in the sulfidation phase, and the primary crystal structure of vivianite largely retained its integrity throughout the whole process. Detailed molecular-level investigations indicate that sulfidation predominantly targets the Fe(II) sites at the corners of the PO4 tetrahedron in vivianite. With the transition to aerobic conditions, the exothermic oxidation of CdS and the S sites in vivianite initiates, rendering it thermodynamically favorable for Cd to form multidentate coordination structures, predominantly through the Cd-O-P and Cd-O-Fe bonds. This mechanism elucidates how Cd is incorporated into the vivianite structure, highlighting a novel pathway for heavy metal immobilization via the sulfidation-reoxidation dynamics in iron phosphate minerals.

Iron cycle-enhanced anaerobic ammonium oxidation in microaerobic granular sludge.

Granule-based partial nitritation and anaerobic ammonium oxidation (PN/A) is an energy-efficient approach for treating ammonia wastewater. When treating low-strength ammonia wastewater, the stable synergy between PN and anammox is however difficult to establish due to unstable dissolved oxygen control. Here, we proposed, the PN/A granular sludge formed by a micro-oxygen-driven iron redox cycle with continuous aeration (0.42 ± 0.10 mg-O2/L) as a novel strategy to achieve stable and efficient nitrogen (N) removal. 240-day bioreactor operation showed that the iron-involved reactor had 37 % higher N removal efficiency than the iron-free reactor. Due to the formation of the microaerobic granular sludge (MGS), the bio(chemistry)-driven iron cycle could be formed with the support of anaerobic ammonium oxidation coupled to Fe3+ reduction. Both ammonia-oxidizing bacteria and generated Fe2+ could scavenge the oxygen as a defensive shield for oxygen-sensitive anammox bacteria in the MGS. Moreover, the iron minerals derived from iron oxidation and Fe-P precipitates were also deposited on the MGS surface and/or embedded in the internal channels, thus reducing the size of the channels that could limit oxygen mass transfer inside the MGS. The spatiotemporal assembly of diverse functional microorganisms in the MGS for the realization of stable PN/A could be achieved with the support of the iron redox cycle. In contrast, the iron-free MGS could not optimize oxygen mass transfer, which led to an unstable and inefficient PN/A. This work provides an alternative iron-related autotrophic N removal for low-strength ammonia wastewater.

The First Description of the Microbial Diversity in the Amarillo River (La Rioja, Argentina), a Natural Extreme Environment Where the Whole Microbial Community Paints the Landscape Yellow.

The Amarillo River in Famatina, La Rioja, Argentina, is a natural acidic river with distinctive yellow-ochreous iron precipitates along its course. While mining activities have occurred in the area, the river's natural acidity is influenced by environmental factors beyond mineralogy, where microbial species have a crucial role. Although iron-oxidising bacteria have been identified, a comprehensive analysis of the entire microbial community in this extreme environment has not yet been conducted. In this study, we employ high-throughput sequencing to explore the bacterial and fungal diversity in the Amarillo River and Cueva de Pérez terraces, considered prehistoric analogues of the current river basin. Fe(II)-enrichment cultures mimicking different environmental conditions of the river were also analysed to better understand the roles of prokaryotes and fungi in iron oxidation processes. Additionally, we investigate the ecological relationships between bacteria and fungi using co-occurrence and network analysis. Our findings reveal a diverse bacterial community in the river and terraces, including uncultured species affiliated with Acidimicrobiia, part of an uncharacterised universal microbial acidic diversity. Acidophiles such as Acidithiobacillus ferrivorans, the main iron oxidiser of the system, and Acidiphilium, which is unable to catalyse Fe(II) oxidation but has a great metabolic flexibility,, are part of the core of the microbial community, showing significant involvement in intraspecies interactions. Alicyclobacillus, which is the main Fe(II) oxidiser in the enrichment culture at 30 °C and is detected all over the system, highlights its flexibility towards the iron cycle. The prevalence of key microorganisms in both rivers and terraces implies their enduring contribution to the iron cycle as well as in shaping the iconic yellow landscape of the Amarillo River. In conclusion, this study enhances our understanding of microbial involvement in iron mineral precipitation, emphasising the collaborative efforts of bacteria and fungi as fundamental geological agents in the Amarillo River.

Amorphous Fe substrate enhances nitrogen and phosphorus removal in sulfur autotrophic process.

The autotrophic denitrification of coupled sulfur and natural iron ore can remove nitrogen and phosphorus from wastewater with low C/N ratios. However, the low solubility of crystalline Fe limits its bioavailability and P absorption capacity. This study investigated the effects of amorphous Fe in drinking water treatment residue (DWTR) and crystalline Fe in red mud (RM) on nitrogen and phosphorus removal during sulfur autotrophic processes. Two types of S-Fe cross-linked filler particles with three-dimensional mesh structures were obtained by combining sulfur with the DWTR/RM using the hydrogel encapsulation method. Two fixed-bed reactors, sulfur-DWTR autotrophic denitrification (SDAD) and sulfur-RM autotrophic denitrification (SRAD), were constructed and stably operated for 236 d Under a 5-8-h hydraulic retention time, the average NO3--N, TN, and phosphate removal rates of SDAD and SRAD were 99.04 %, 96.29 %, 94.03 % (SDAD) and 97.33 %, 69.97 %, 82.26 % (SRAD), respectively. It is important to note that fermentative iron-reducing bacteria, specifically Clostridium_sensu_stricto_1, were present in SDAD at an abundance of 58.17 %, but were absent from SRAD. The presence of these bacteria facilitated the reduction of Fe (III) to Fe (II), which led to the complete denitrification of the S-Fe (II) co-electron donor to produce Fe (III), completing the iron cycle in the system. This study proposes an enhancement method for sulfur autotrophic denitrification using an amorphous Fe substrate, providing a new option for the efficient treatment of low-C/N wastewater.

Anaerobic ammonium oxidation coupled to iron(III) reduction catalyzed by a lithoautotrophic nitrate-reducing iron(II) oxidizing enrichment culture.

The last two decades have seen nitrogen/iron-transforming bacteria at the forefront of new biogeochemical discoveries, such as anaerobic ammonium oxidation coupled to ferric iron reduction (feammox) and lithoautotrophic nitrate-reducing ferrous iron-oxidation (NRFeOx). These emerging findings continue to expand our knowledge of the nitrogen/iron cycle in nature and also highlight the need to re-understand the functional traits of the microorganisms involved. Here, as a proof-of-principle, we report compelling evidence for the capability of an NRFeOx enrichment culture to catalyze the feammox process. Our results demonstrate that the NRFeOx culture predominantly oxidizes NH4+ to nitrogen gas, by reducing both chelated nitrilotriacetic acid (NTA)-Fe(III) and poorly soluble Fe(III)-bearing minerals (γ-FeOOH) at pH 4.0 and 8.0, respectively. In the NRFeOx culture, Fe(II)-oxidizing bacteria of Rhodanobacter and Fe(III)-reducing bacteria of unclassified_Acidobacteriota coexisted. Their relative abundances were dynamically regulated by the supplemented iron sources. Metagenomic analysis revealed that the NRFeOx culture contained a complete set of denitrifying genes along with hao genes for ammonium oxidation. Additionally, numerous genes encoding extracellular electron transport-associated proteins or their homologs were identified, which facilitated the reduction of extracellular iron by this culture. More broadly, this work lightens the unexplored potential of specific microbial groups in driving nitrogen transformation through multiple pathways and highlights the essential role of microbial iron metabolism in the integral biogeochemical nitrogen cycle.

Mechanistic insights into sulfadimethoxine degradation via microbially driven Fenton reactions.

Biodegradation, while cost-effective, is hindered by the requirement for specialized microorganisms and co-contaminants. Innovative biological technologies like the microbially driven Fenton reaction, hold promise for enhancing degradation efficiency. However, the intricate biochemical processes and essential steps for effective degradation in such systems have remained unclear. In this study, we harnessed the potential of the microbially driven Fenton reaction by employing Shewanella oneidensis MR-1 (MR-1). Our approach showcased remarkable efficacy in degrading a range of contaminants, including sulfadimethoxine (SDM), 4,4'-dibromodiphenyl ether (BDE-15) and atrazine (ATZ). Using SDM as a model contaminant of emergent contaminants (ECs), we unveiled that biodegradation relied on the generation of hydroxyl radicals (•OH) and involvement of oxidoreductases. Transcriptomic analysis shed light on the pivotal components of extracellular electron transfer (EET) during both anaerobic and aerobic periods. The presence of reactive oxidizing species induced cellular damage and impeded DNA repair, thereby affecting the Mtr pathway of EET. Moreover, the formation of vivianite hindered SDM degradation, underscoring the necessity of maintaining iron ions in the solution to ensure sustainable and efficient degradation. Overall, this study offers valuable insights into microbial technique for ECs degradation, providing a comprehensive understanding of degradation mechanisms during aerobic/anaerobic cycling.

Iron cycle disruption by heme oxygenase-1 activation leads to a reduced breast cancer cell survival.

Heme oxygenase-1 (HO-1), which catalyzes heme degradation releasing iron, regulates several processes related to breast cancer. Iron metabolism deregulation is also connected with several tumor processes. However the regulatory relationship between HO-1 and iron proteins in breast cancer remains unclear. Using human breast cancer biopsies, we found that high HO-1 levels significantly correlated with low DMT1 levels. Contrariwise, high HO-1 levels significantly correlated with high ZIP14 and prohepcidin expression, as well as hemosiderin storage. At mRNA level, we found that high HO-1 expression significantly correlated with low DMT1 expression but high ZIP14, L-ferritin and hepcidin expression. In in vivo experiments in mice with genetic overexpression or pharmacological activation of HO-1, we detected the same expression pattern observed in human biopsies. In in vitro experiments, HO-1 activation induced changes in iron proteins expression leading to an increase of hemosiderin, ROS levels, lipid peroxidation and a decrease of the growth rate. Such low growth rate induced by HO-1 activation was reversed when iron levels or ROS levels were reduced. Our findings demonstrate an important role of HO-1 on iron homeostasis in breast cancer. The changes in iron proteins expression when HO-1 is modulated led to the iron accumulation deregulating the iron cell cycle, and consequently, generating oxidative stress and low viability, all contributing to impair breast cancer progression.

Evaluation of the distribution and mobility of labile phosphorus in sediment profiles of Lake Nansi, the largest eutrophic freshwater lake in northern China.

Understanding various biogeochemical processes, especially in eutrophic sediments, necessitates fine-scale phosphorus (P) measurements in pore waters. To the best of our knowledge, the fine-scale distributions of P across the sediment profiles of Lake Nansi have rarely been investigated. Herein we evaluated the dynamic distributions of labile P and Fe across the sediment-water interface (SWI) of Lake Nansi at two-dimensional (2D) and sub-millimeter resolution, using well-established colorimetric diffusive gradients in thin films (DGT) methodology. The concentrations of labile P in all investigated sediment profiles exhibited strong spatial variations, ranging from 0 to 1.50 mg/L with a considerable number of hotspots. Lake Nanyang (0.55 ± 0.21 mg/L) had the highest mean concentration of labile P, followed by Lake Dushan (0.38 ± 0.19 mg/L), Lake Weishan (0.28 ± 0.21 mg/L), and Lake Zhaoyang (0.18 ± 0.09 mg/L). The highest concentrations of labile P were always detected in Lake Dushan, which had been subjected to excessive exogenous P pollution. The co-distributions of labile P and Fe in the majority of the sediment of Lake Nansi confirmed highly positive correlations (P < 0.01), suggesting that the mobility of labile P throughout the SWI was likely governed by iron redox processes. The apparent diffusion fluxes of P across the SWI ranged from -7.7 to 33.6 µg/m2·d, with a mean value of 5.26 ± 7.80 µg/m2·d. Positive apparent fluxes for labile P were recorded in most sediment cores, demonstrating the strong upward mobility of P from the sediment to the overlying water. Our results provided accurate and extensive information regarding the micro-distribution and dynamic exchange of labile P across the SWI. This allows for a better understanding of eutrophication processes and the implementation of P management strategies in Lake Nansi.

Tracing Fe cycle isotopically in soils based on different land uses: Insight from a typical karst catchment, Southwest China.

Iron (Fe) isotopes can effectively unveil the Fe cycle mechanisms under redox and biological conditions during the weathering and pedogenic processes. Fe contents and Fe isotope compositions (defined as δ56Fe) in the soil profiles under secondary forest land, abandoned cropland and shrubland were investigated in a typical karst area in Southwest China. The results showed that the Fe content ranged from 23.92 to 38.56 g/kg, 21.92 to 33.02 g/kg and 12.98 to 27.93 g/kg, and the δ56Fe levels varied from -0.48 ‰ to 0.21 ‰, -0.24 ‰ to 0.11 ‰ and - 0.11 ‰ to 0.16 ‰ from the secondary forest land, abandoned cropland and shrubland, respectively. The correlation analysis results showed that Fe transportation and isotopic fractionation were regulated by the redox processes through soil pH and soil organic matter (SOM) in the abandoned cropland and shrubland. Heavier Fe isotope may be accumulated in the deeper soil of secondary forest land due to Fe-oxide precipitation. The Fe isotope fractionations were greatly altered by soil organic carbon (SOC) in surface soils due to negative surface charges. Soil pH also plays a key role in enriching lighter Fe in a medium-acidic environment (shrubland) by ligand-controlled dissolution and reductive dissolution. Long-term cultivation in abandoned cropland and grazing in shrubland reshaped the Fe cycle in soil profiles by changing soil pH and SOC contents. However, the similar values of δ56Fe in different land use soils indicated that the agricultural activities have no significant impact on the Fe transformation in karst soil ecosystems. The land utilization is reasonable in the Yinjiang County. This study provided effective data and insightful analysis to understand the Fe cycle processes in the karst soils under varied land uses.

One advantageous reflection of iron metabolism in context of normal physiology and pathological phases.

PURPOSE (BACKGROUND): The presented review is an updating of Iron metabolism in context of normal physiology and pathological phases. Iron is one of the vital elements in humans and associated into proteins as a component of heme (e.g. hemoglobin, myoglobin, cytochromes proteins, myeloperoxidase, nitric oxide synthetases), iron sulfur clusters (e.g. respiratory complexes I-III, coenzyme Q10, mitochondrial aconitase, DNA primase), or other functional groups (e.g. hypoxia inducible factor prolyl hydroxylases). All these entire iron-containing proteins ar e needed for vital cellular and organismal functions together with oxygen transport, mitochondrial respiration, intermediary and xenobiotic metabolism, nucleic acid replication and repair, host defense, and cell signaling. METHODS (METABOLIC STRATEGIES): Cells have developed metabolic strategies to import and employ iron safely. Regulatory process of iron uptake, storage, intracellular trafficking and utilization is vital for the maintenance of cellular iron homeostasis. Cellular iron utilization and intracellular iron trafficking pathways are not well established and very little knowledge about this. The predominant organs, which are associated in the metabolism of iron, are intestine, liver, bone marrow and spleen. Iron is conserved, recycled and stored. The reduced bioavailability of iron in humans has developed extremely efficient mechanisms for iron conservation. Prominently, the losses of iron cannot considerably enhance through physiologic mechanisms, even if iron intake and stores become excessive. Loss of iron is balanced or maintained from dietary sources. RESULTS (OUTCOMES): Numerous physiological abnormalities are associated with impaired iron metabolism. These abnormalities are appeared in the form of several diseases. There are duodenal ulcer, inflammatory bowel disease, sideroblastic anaemia, congenital dyserythropoietic anemias and low-grade myelodysplastic syndromes. Hereditary hemochromatosis and anaemia are two chronic diseases, which are responsible for disturbing the iron metabolism in various tissues, including the spleen and the intestine. Impairment in hepatic hepcidin synthesis is responsible for chronic liver disease, which is grounding from alcoholism or viral hepatitis. This condition directs to iron overload that can cause further hepatic damage. Iron has important role in several infectious diseases are tuberculosis, malaria trypanosomatid diseases and acquired immunodeficiency syndrome (AIDS). Iron is also associated with Systemic lupus erythematosus [SLE], cancer, Alzheimer's disease (AD) and post-traumatic epilepsy. CONCLUSION: Recently, numerous research studies are gradually more dedicated in the field of iron metabolism, but a number of burning questions are still waiting for answer. Cellular iron utilization and intracellular iron trafficking pathways are not well established and very little knowledge about this. Increased information of the physiology of iron homeostasis will support considerate of the pathology of iron disorders and also make available the support to advance treatment.