Thermodynamic controls on rates of iron oxide reduction by extracellular electron shuttles

Anaerobic microbial respiration in suboxic and anoxic environments often involves particulate ferric iron (oxyhydr-)oxides as terminal electron acceptors. To ensure efficient respiration, a widespread strategy among iron-reducing microorganisms is the use of extracellular electron shuttles (EES) that transfer two electrons from the microbial cell to the iron oxide surface. Yet, a fundamental understanding of how EES–oxide redox thermodynamics affect rates of iron oxide reduction remains elusive. Attempts to rationalize these rates for different EES, solution pH, and iron oxides on the basis of the underlying reaction free energy of the two-electron transfer were unsuccessful. Here, we demonstrate that broadly varying reduction rates determined in this work for different iron oxides and EES at varying solution chemistry as well as previously published data can be reconciled when these rates are instead related to the free energy of the less exergonic (or even endergonic) first of the two electron transfers from the fully, two-electron reduced EES to ferric iron oxide. We show how free energy relationships aid in identifying controls on microbial iron oxide reduction by EES, thereby advancing a more fundamental understanding of anaerobic respiration using iron oxides.

Mechanochemical Activation Effect on Technogenic Iron Oxide Reduction Kinetics

Understanding the reaction kinetics of iron oxide reduction by carbon is a key task of the theory of metallurgical processes. One of the understudied features of the reaction kinetics of iron oxide solid-phase reduction by carbon is the discrepancy between the reacting substances’ small contact area and the process’s high rate. A convincing theoretical and experimental explanation of this effect has not yet been obtained. The data obtained earlier show that an increase in the scale of the briquetting pressure from 0 to 300 MPa increases the degree of its metallization during heating two-fold, and the metallization temperature decreases by more than 40 °C. Therefore, it was assumed that these effects during heating are a consequence of the mechanochemical activation (MCA) of iron oxides in the scale during its pressing. This paper presents the results of experimental studies on the influence of two types of scale MCA (grinding and pressing) on iron oxide reduction. The study of the MCA effect on the reaction kinetics of scale iron oxide reduction by carbon is a promising way to assess the criteria for scale phase composition changes under external factors. The presented results indicate a decrease in the amount of trivalent iron oxide (Fe2O3) after the MCA and an increase in the amount of one-and-a-half oxide (Fe3O4) and bivalent iron oxide (FeO). The obtained experimental data show that the initial stage of iron oxide reduction, consisting in the transition from higher iron oxides to lower ones, is possible at room temperature without carbon presence.

Diversity and evolution of nitric oxide reduction

Nitrogen is an essential element for life, with the availability of fixed nitrogen limiting productivity in many ecosystems. The return of oxidized nitrogen species to the atmospheric N2 pool is predominately catalyzed by microbial denitrification (NO3- → NO2- → NO → N2O → N2). Incomplete denitrification can produce N2O as a terminal product, leading to an increase in atmospheric N2O, a potent greenhouse and ozone depleting gas2. The production of N2O is catalyzed by nitric oxide reductase (NOR) members of the heme-copper oxidoreductase (HCO) superfamily3. Here we propose that a number of uncharacterized HCO families perform nitric oxide reduction and demonstrate that an enzyme from Rhodothermus marinus, belonging to one of these families does perform nitric oxide reduction. These families have novel active-site structures and several have conserved proton channels, suggesting that they might be able to couple nitric oxide reduction to energy conservation. They also exhibit broad phylogenetic and environmental distributions, expanding the diversity of microbes that can perform denitrification. Phylogenetic analyses of the HCO superfamily demonstrate that nitric oxide reductases evolved multiple times independently from oxygen reductases, suggesting that complete denitrification evolved after aerobic respiration.

Modificarea activiății peroxidazei și a polifenoloxidazei în fructele de prun în dependență de varianta de tratare în perioada de vegetație și metodele de păstrare aplicate

The plum fruits of the President variety were preserved by three methods. I- keeping fruits in the ordinary atmosphere (AO). II - the fruits before being stored for a long time in AO were treated with the synthetic inhibitor of ethylene Fitomag and III - the fruits were kept in a controlled atmosphere (CA). Du-ring the storage of the fruits of the respective variety, the activity of some antioxidant enzymes was de-termined by the mentioned methods. As a result, results were obtained regarding the modification of the activity of the enzymes peroxidase and polyphenol oxidase. Their activity changed depending on the me-tabolic processes that took place when the fruits maturation, as well as the conditions, duration and stora-ge methods. It also depended on the biological peculiarities of the variety and the influence of the sub-stances with which the plum trees were treated during the vegetation period. The highest activity of these enzymes was in the fruits kept in the usual atmosphere, then followed by their activity in the fruits kept with Fitomag and their lowest activity was in the fruits kept in CA. In the fruits preserved by the last two methods, the metabolic processes and those of oxide reduction went slower and the fruits were kept 10, 16 days longer than in AO. There were also significant differences in the activity of these enzymes, being higher in the variant treated with SBA Reglalg and microelements than in the control variant.