Ferric Iron Reduction in Extreme Acidophiles

Biochemical processes are a key element of natural cycles occurring in the environment and enabling life on earth. With regard to microbially catalyzed iron transformation, research predominantly has focused on iron oxidation in acidophiles, whereas iron reduction played a minor role. Microbial conversion of ferric to ferrous iron has however become more relevant in recent years. While there are several reviews on neutrophilic iron reducers, this article summarizes the research on extreme acidophilic iron reducers. After the first reports of dissimilatory iron reduction by acidophilic, chemolithoautotrophic Acidithiobacillus strains and heterotrophic Acidiphilium species, many other prokaryotes were shown to reduce iron as part of their metabolism. Still, little is known about the exact mechanisms of iron reduction in extreme acidophiles. Initially, hypotheses and postulations for the occurring mechanisms relied on observations of growth behavior or predictions based on the genome. By comparing genomes of well-studied neutrophilic with acidophilic iron reducers (e.g., Ferroglobus placidus and Sulfolobus spp.), it became clear that the electron transport for iron reduction proceeds differently in acidophiles. Moreover, transcriptomic investigations indicated an enzymatically-mediated process in Acidithiobacillus ferrooxidans using respiratory chain components of the iron oxidation in reverse. Depending on the strain of At. ferrooxidans, further mechanisms were postulated, e.g., indirect iron reduction by hydrogen sulfide, which may form by disproportionation of elemental sulfur. Alternative scenarios include Hip, a high potential iron-sulfur protein, and further cytochromes. Apart from the anaerobic iron reduction mechanisms, sulfur-oxidizing acidithiobacilli have been shown to mediate iron reduction at low pH (< 1.3) under aerobic conditions. This presumably non-enzymatic process may be attributed to intermediates formed during sulfur/tetrathionate and/or hydrogen oxidation and has already been successfully applied for the reductive bioleaching of laterites. The aim of this review is to provide an up-to-date overview on ferric iron reduction by acidophiles. The importance of this process in anaerobic habitats will be demonstrated as well as its potential for application.

Chromium (VI) Inhibition of Low pH Bioleaching of Limonitic Nickel-Cobalt Ore

Limonitic layers of the regolith, which are often stockpiled as waste materials at laterite mines, commonly contain significant concentrations of valuable base metals, such as nickel, cobalt, and manganese. There is currently considerable demand for these transition metals, and this is projected to continue to increase (alongside their commodity values) during the next few decades, due in the most part to their use in battery and renewable technologies. Limonite bioprocessing is an emerging technology that often uses acidophilic prokaryotes to catalyse the oxidation of zero-valent sulphur coupled to the reduction of Fe (III) and Mn (IV) minerals, resulting in the release of target metals. Chromium-bearing minerals, such as chromite, where the metal is present as Cr (III), are widespread in laterite deposits. However, there are also reports that the more oxidised and more biotoxic form of this metal [Cr (VI)] may be present in some limonites, formed by the oxidation of Cr (III) by manganese (IV) oxides. Bioleaching experiments carried out in laboratory-scale reactors using limonites from a laterite mine in New Caledonia found that solid densities of ∼10% w/v resulted in complete inhibition of iron reduction by acidophiles, which is a critical reaction in the reductive dissolution process. Further investigations found this to be due to the release of Cr (VI) in the acidic liquors. X-ray absorption near edge structure (XANES) spectroscopy analysis of the limonites used found that between 3.1 and 8.0% of the total chromium in the three limonite samples used in experiments was present in the raw materials as Cr (VI). Microbial inhibition due to Cr (VI) could be eliminated either by adding limonite incrementally or by the addition of ferrous iron, which reduces Cr (VI) to less toxic Cr (III), resulting in rates of extraction of cobalt (the main target metal in the experiments) of >90%.

Antimicrobial and Antioxidant Properties of Total Polyphenols of Anchusa italica Retz

Anchusa italica Retz has been used for a long time in phytotherapy. The aim of the present study was to determine the antioxidant and antibacterial activities of extracts from the leaves and roots of Anchusa italica Retz. We first determined the content of phenolic compounds and flavonoids using Folin–Ciocalteu reagents and aluminum chloride (AlCl3). The antioxidant activity was determined using three methods: reducing power (FRAP), 2.2-diphenyl-1-picrylhydrazyl (DPPH), total antioxidant capacity (TAC). The antimicrobial activity was investigated against four strains of Escherichia coli, two strains of Klebsiella pneumoniae and coagulase-negative Staphylococcus, and one fungal strain of Candida albicans. The results showed that the root extract was rich in polyphenols (43.29 mg GAE/g extract), while the leave extract was rich in flavonoids (28.88 mg QE/g extract). The FRAP assay showed a strong iron reduction capacity for the root extract (IC50 of 0.11 µg/mL) in comparison to ascorbic acid (IC50 of 0.121 µg/mL). The DPPH test determined an IC50 of 0.11 µg/mL for the root extract and an IC50 of 0.14 µg/mL for the leaf extract. These values are low compared to those for ascorbic acid (IC50 of 0.16 µg/mL) and BHT (IC50 0.20 µg/mL). The TAC values of the leaf and root extracts were 0.51 and 0.98 mg AAE/g extract, respectively. In vitro, the extract showed inhibitory activity against all strains studied, with diameters of zones of inhibition in the range of 11.00–16.00 mm for the root extract and 11.67–14.33 mm for the leaf extract. The minimum inhibitory concentration was recorded for the leaf extract against E. coli (ATB:57), corresponding to 5 mg/mL. Overall, this research indicates that the extracts of Anchusa italica Retz roots and leaves exert significant antioxidant and antibacterial activities, probably because of the high content of flavonoids and polyphenols.

Multi-Element Imaging of a 1.4 Ga Authigenic Siderite Crystal

Iron formations (IFs) are traditionally considered to be limited during 1.8−0.8 Ga. However, there are recent reports of siderite-dominated IFs within this time interval, such as the 1.40 Ga Xiamaling IF in North China and the 1.33 Ga Jingtieshan IF in Qilian. To further explore the crystallization and formation mechanisms of siderite, an authigenic siderite crystal from the Xiamaling IF was fully scanned using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Multi-element imaging with a spatial resolution of 5 μm revealed an obvious rim structure of the siderite crystal, which might record the crystallization and growth processes. The Al- and Fe-enriched zone in the core of siderite crystal might be an iron-bearing nucleus, and the formation of rim structure was related to the transition from a closed crystallization environment to a semi-closed growth environment. These results, combined with carbon isotope evidence from the siderites and surrounding shales, suggest that vigorous dissimilatory iron reduction that can provide Fe2+ and HCO3− to the pore water is a key factor to form the siderite-dominated Xiamaling IF.

Nitrogen Removal by an Anaerobic Iron-Dependent Ammonium Oxidation (Feammox) Enrichment: Potential for Wastewater Treatment

Nitrogen pollution in water is a growing concern. Anthropogenic activities have increased the amount of nitrogen released into watercourses, which harms human health and the environment, and causes serious problems, such as eutrophication. Feammox is a recently discovered biological pathway associated with the nitrogen cycle that has gained scientific interest. This process couples anaerobic ammonium oxidation with iron reduction. This work presents a study on the Feammox mechanism from the enrichment of an activated sludge obtained from a sewage treatment plant. The enrichment was carried out at neutral pH to study the N2 pathway, that is, the Feammox process with the oxidation of ammonium (NH4+) directly to N2. In addition, different sources of iron were studied: iron chloride (FeCl3); ferrihydrite; and goethite. The characterization of the sludge showed the genes associated with ammonia monooxygenase, nitrate and nitrite reductases processes, along with relevant microbial species. The enrichment, carried out for 42 days and monitored every 14 days, showed that FeCl3 as a source of Fe was more effective for the coupled process of oxidation of NH4+ and the reduction of Fe(III) to Fe(II). At the end of the enrichment period, a removal of 31% and 32.2% of NH4+, and an increase in Fe(II) concentration by 52.4 and 63.9 times regarding the initial value were achieved in aerobic and anaerobic sludge, respectively. This study provides information on the potential of Feammox in the removal of N from wastewater, and the oxidation/reduction yields in the initial enrichment phase.

Iron reduction from concentrates of hydrometallurgical dressing

The article presents results of theoretical and experimental studies of the processes of iron solid-phase reduction from an iron-containing concentrate obtained as a result of hydrometallurgical dressing of ferromanganese and polymetallic manganese-containing ores with coals of grades D (long-flame) and 2B (brown). The method of thermodynamic modeling using TERRA software complex was used to study the reducing properties of hydrocarbons by calculating equilibrium compositions in the temperature range of 373 - 1873 K. The authors obtained the dependences of compositions and volume of the gas phase formed as a result of the release of volatile components during heating on the temperature for the coals of the grades under consideration. As a result of thermodynamic modeling, the optimal temperatures and consumption are determined, which ensure the complete iron reduction from an iron-containing concentrate. The results of experimental studies were obtained by modern research methods using laboratory and analytical equipment, as well as methods of statistical processing. Results of the coals analysis carried out using the Setaram LabSys Evo thermal analyzer showed that the process of thermal decomposition of coals of the studied grades proceeds according to general laws. The process of thermal decomposition of long-flame coal proceeds less intensively than of brown coal. The results of an experimental study of the processes of thermal decomposition of reducing agents have shown that volumes of the gas phases, formed when coals are heated to a temperature of 1173 K in an argon atmosphere, practically coincide with the calculated values. As a result of thermodynamic modeling and experimental study, the optimal consumption of D and 2B grades of coal is determined at a temperature of 1473 K. The best reducing agent with a minimum specific consumption is long-flame coal of D grade. When determining the optimal amount of reducing agent in charge mixtures during the study of metallization processes, it was found that with an excess of reducing agent, it is possible to achieve almost complete extraction (98 - 99 %) of iron from the concentrate.

Dietary Iron Overload and Hfe−/− Related Hemochromatosis Alter Hepatic Mitochondrial Function

Iron is an essential co-factor for many cellular metabolic processes, and mitochondria are main sites of utilization. Iron accumulation promotes production of reactive oxygen species (ROS) via the catalytic activity of iron species. Herein, we investigated the consequences of dietary and genetic iron overload on mitochondrial function. C57BL/6N wildtype and Hfe−/− mice, the latter a genetic hemochromatosis model, received either normal diet (ND) or high iron diet (HI) for two weeks. Liver mitochondrial respiration was measured using high-resolution respirometry along with analysis of expression of specific proteins and ROS production. HI promoted tissue iron accumulation and slightly affected mitochondrial function in wildtype mice. Hepatic mitochondrial function was impaired in Hfe−/− mice on ND and HI. Compared to wildtype mice, Hfe−/− mice on ND showed increased mitochondrial respiratory capacity. Hfe−/− mice on HI showed very high liver iron levels, decreased mitochondrial respiratory capacity and increased ROS production associated with reduced mitochondrial aconitase activity. Although Hfe−/− resulted in increased mitochondrial iron loading, the concentration of metabolically reactive cytoplasmic iron and mitochondrial density remained unchanged. Our data show multiple effects of dietary and genetic iron loading on mitochondrial function and linked metabolic pathways, providing an explanation for fatigue in iron-overloaded hemochromatosis patients, and suggests iron reduction therapy for improvement of mitochondrial function.

Curcumin Protects against Renal Ischemia/Reperfusion Injury by Regulating Oxidative Stress and Inflammatory Response

Objective. The aim of this study was to explore the pharmacological effects of curcumin on oxidative stress and inflammatory response of renal dysfunction induced by renal ischemia/reperfusion (RIRI). Methods. Fifty male SD rats (Sprague Dawley) were randomly divided into the sham group, RIRI group, and curcumin group (low, medium, and high). The RIRI model was established by clipping the left renal artery for 45 min and then reperfusion for 24 h and resection of the contralateral kidney. In the curcumin group, curcumin was intraperitoneally injected once a day for 3 consecutive days using different dosage regimens. The RIRI group was intraperitoneally administered with normal saline. Renal injury was evaluated by measuring the concentration of creatinine (Cr) and urea nitrogen (BUN) in serum. Oxidative stress was assessed by assessing the level of malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione (GSH), and iron reduction/antioxidant capacity (FRAP) in tissues. In addition, the protective effect of RIRI was investigated by measuring Paller scores, the level of serum inflammatory factors and caspase-3, and the number of apoptotic cells. Results. Ischemia/reperfusion resulted in increased levels of Cr and BUN in serum and MDA in tissues and decreased levels of SOD, CAT, GPx, GSH, and FRAP. Curcumin pretreatment strikingly increased the level of SOD, CAT, GPx, GSH, IL-10, IFN-γ, and FRAP and significantly decreased MDA, Cr, BUN, IL-8, TNF-α, IL-6, and myeloperoxidase (MPO) expressions in tissues. Conclusion. Curcumin can relieve the degree of renal injury and improve renal function in ischemia-reperfusion, which may be related to the fact that curcumin can increase SOD content in serum and reduce MDA and FRAP levels in the rat model.

Thymus algeriensis and Artemisia herba-alba Essential Oils: Chemical Analysis, Antioxidant Potential and In Vivo Anti-Inflammatory, Analgesic Activities, and Acute Toxicity

The study of bioactive molecules of natural origin is a focus of current research. Thymus algeriensis and Artemisia herba-alba are two medicinal plants widely used by the Moroccan population in the traditional treatment of several pathologies linked to inflammation. This study aimed to evaluate the single and combined antioxidant, anti-inflammatory and analgesic effects of the essential oils extracted from these two medicinal plants, and also their potential toxicity. Essential oils were extracted using hydro-distillation in a Clevenger-type apparatus. The antioxidant activity was evaluated by two methods: the scavenging of the free radical DPPH, and the reduction in iron. Anti-inflammatory activity was evaluated by evaluating the edema development induced by carrageenan injecting, while the analgesic power was evaluated according to the number of abdominal contortions induced by the intraperitoneal injection of acetic acid (0.7%). The acute oral toxicity was performed to assess the potential toxicity of the studied EOs, followed by an analysis of the blood biochemical parameters. The results of the two antioxidant tests indicated that our extract mixture exhibits good iron reduction capacity and very interesting DPPH free radical scavenging power, with an IC50 of around 4.38 ± 0.98 μg/mL higher than that of the benchmark antioxidant, BHT. The anti-inflammatory test demonstrated that the mixture administered orally at a dose of 150 mg/kg has a better activity, exceeding that of 1% Diclofenac, with a percentage of maximum inhibition of the edema of 89.99 ± 4.08. The number of cramps in the mice treated with the mixture at a dose of 150 mg/kg is significantly lower (29.80 ± 1.92) than those of the group treated with Tramadol (42.00 ± 2.70), respectively. The toxicity results show no signs of toxicity with an LD50 greater than 150 mg/Kg. These interesting results show that the two plants’ EOs had an important anti-inflammatory, analgesic, and antioxidant activity, and also a powerful synergistic effect, which encourages further in-depth investigations on their pharmacological proprieties.