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[Effect of kerogen oxidation products on the biosynthesis of beta-lactamases by Escherichia coli].

Shale acid concentrate (SAC) and ozonid, the products of water-alkaline oxidation of kerogen stimulated production of beta-lactamases by E. coli. The effect was most pronounced when the SAC was added to the fermentation nutrient medium. Kerogen ozonid was inferior by its activity. Cultivation of the seed material on media containing both the products of kerogen did not influence the enzyme production. Stimulating effect on production of either penicillinases or cephalosporinases was observed. SAC and ozonid had no influence on the culture growth, multiplication and biomass accumulation.

Culture Media↗

Effect of alkaline pH on photosynthetic water oxidation and the association of extrinsic proteins with Photosystem Two.

Incubation of a membrane preparation enriched in Photosystem Two (PSII) at alkaline pH inhibited the water-splitting reactions in two distinct steps. Up to pH 8.5 the inhibition was reversible, whereas at higher alkalinities it was irreversible. It was shown that the reversible phase correlated with loss and rebinding of the 23 kDa extrinsic polypeptide. However, after mild alkaline treatments a partial recovery was possible without the binding of the 23 kDa polypeptide when the assay was at the optimal pH of 6.5 and in a medium containing excess Cl-. The irreversible phase was found to be closely linked with the removal of the 33 kDa extrinsic protein of PSII. Treatments with pH values above 8.5 not only caused the 33 kDa protein to be displaced from the PSII-enriched membranes, but also resulted in an irreversible modification of the binding sites such that the extrinsic 33 kDa protein could not reassociate with PSII when the pH was lowered to 6.5. The results obtained with these more extreme alkaline pH treatments support the notion that the 23 kDa protein cannot bind to PSII unless the 33 kDa protein is already bound. The differential effect of pH on the removal of the 23 kDa and 33 kDa proteins contrasted with the data of Kuwabara & Murata [(1983) Plant Cell Physiol. 24, 741-747], but this discrepancy was accounted for by the use of glycerol in the incubation media.

Electron Transport↗

CeOx-Induced Spatial and Electronic Modulation for General Direct Oxo Coupling in Transition Metal Hydroxides.

Electrochemical water splitting has emerged as a sustainable paradigm for hydrogen generation, where sluggish kinetics of the oxygen evolution reaction (OER) catalyzed by transition metal-based materials remain the critical bottleneck. Herein, we present a strategy that anchors CeOx nanoparticles (∼2 nm) onto two-dimensional Ni(OH)2 nanosheets, enabling dual modulation of spatial configuration and electronic states to accelerate O-O coupling. Spatially, interfacial lattice distortion between CeOx and Ni(OH)2 optimizes Ni-Ni dual-metal sites with reduced interatomic spacing. Electronically, dynamic modulation through reversible Ce3+/Ce4+ redox cycling positions Ce as an electronic regulation hub, stabilizing Ni species at the catalytically favorable +3 oxidation state through Ce─O─Ni interactions. This synergistic effect shifts the pathway from adsorbate evolution mechanism (AEM) to oxide pathway mechanism (OPM). The prepared CeOx@Ni(OH)2 achieves an overpotential of 152 mV at 10 mA cm-2 and operates continuously over 2000 h with limited performance decay. When integrated into an alkaline anion exchange membrane water electrolyzer (AEMWE), it requires 1.91 V to attain 1 A cm-2 and maintains stable operation for 450 h. This OPM activation strategy shows potential applicability across CeOx-loaded transition metal hydroxides, including Ni(OH)2, Co(OH)2, NiCo, and NiFe layered double hydroxides, offering a promising approach for alkaline OER enhancement.

alkaline water oxidation↗

Formation of the paramagnetic complex [Cr(OH)5O2]5- in the reaction between chromium(VI) oxide, and hydrogen peroxide or superoxide anion radicals studied by EPR spectroscopy.

Hydrogen peroxide or superoxide anion radicals form a paramagnetic complex in the reaction with chromium(VI) oxide in an alkaline water solution at room temperature. The complex [Cr(OH)5O2]5- with the g-value equal to 1.9734 is believed to contain hydroxyl groups derived from the alkaline solution and dioxygen derived from hydrogen peroxide or superoxide anion radicals.

Chromium Compounds↗

Efficacy of electrolyzed oxidizing water for the microbial safety and quality of eggs.

During commercial processing, eggs are washed in an alkaline detergent and then rinsed with chlorine to reduce dirt, debris, and microorganism levels. The alkaline and acidic fractions of electrolyzed oxidizing (EO) water have the ability to fit into the 2-step commercial egg washing process easily if proven to be effective. Therefore, the efficacy of EO water to decontaminate Salmonella Enteritidis and Escherichia coli K12 on artificially inoculated shell eggs was investigated. For the in vitro study, eggs were soaked in alkaline EO water followed by soaking in acidic EO water at various temperatures and times. Treated eggs showed a reduction in population between > or = 0.6 to > or =2.6 log10 cfu/g of shell for S. Enteritidis and > or =0.9 and > or =2.6 log10 for E. coli K12. Log10 reductions of 1.7 and 2.0 for S. Enteritidis and E. coli K12, respectively, were observed for typical commercial detergent-sanitizer treatments, whereas log10 reductions of > or =2.1 and > or =2.3 for S. Enteritidis and E. coli K12, respectively, were achieved using the EO water treatment. For the pilot-scale study, both fractions of EO water were compared with the detergent-sanitizer treatment using E. coli K12. Log10 reductions of > or = 2.98 and > or = 2.91 were found using the EO water treatment and the detergent-sanitizer treatment, respectively. The effects of 2 treatments on egg quality were investigated. EO water and the detergent-sanitizer treatments did not significantly affect albumen height or eggshell strength; however, there were significant affects on cuticle presence. These results indicate that EO water has the potential to be used as a sanitizing agent for the egg washing process.

Animals↗

Extremely alkaline (pH > 12) ground water hosts diverse microbial community.

Chemically unusual ground water can provide an environment for novel communities of bacteria to develop. Here, we describe a diverse microbial community that inhabits extremely alkaline (pH > 12) ground water from the Lake Calumet area of Chicago, Illinois, where historic dumping of steel slag has filled in a wetland. Using microbial 16S ribosomal ribonucleic acid gene sequencing and microcosm experiments, we confirmed the presence and growth of a variety of alkaliphilic beta-Proteobacteria, Bacillus, and Clostridium species at pH up to 13.2. Many of the bacterial sequences most closely matched those of other alkaliphiles found in more moderately alkaline water around the world. Oxidation of dihydrogen produced by reaction of water with steel slag is likely a primary energy source to the community. The widespread occurrence of iron-oxidizing bacteria suggests that reduced iron serves as an additional energy source. These results extend upward the known range of pH tolerance for a microbial community by as much as 2 pH units. The community may provide a source of novel microbes and enzymes that can be exploited under alkaline conditions.

Alkalies↗

Characterization of degradation products from alkaline wet oxidation of wheat straw.

Alkaline wet oxidation pre-treatment (water, sodium carbonate, oxygen, high temperature and pressure) of wheat straw was performed as a 2(4-1) fractional factorial design with the process parameters: temperature, reaction time, sodium carbonate and oxygen. Alkaline wet oxidation was an efficient pre-treatment of wheat straw that resulted in solid fractions with high cellulose recovery (96%) and high enzymatic convertibility to glucose (67%). Carbonate and temperature were the most important factors for fractionation of wheat straw by wet oxidation. Optimal conditions were 10 min at 195 degrees C with addition of 12 bar oxygen and 6.5 g l(-1) Na2CO3. At these conditions the hemicellulose fraction from 100 g straw consisted of soluble hemicellulose (16 g), low molecular weight carboxylic acids (11 g), monomeric phenols (0.48 g) and 2-furoic acid (0.01 g). Formic acid and acetic acid constituted the majority of degradation products (8.5 g). The main phenol monomers were 4-hydroxybenzaldehyde, vanillin, syringaldehyde. acetosyringone (4-hydroxy-3,5-dimethoxy-acetophenone), vanillic acid and syringic acid, occurring in 0.04-0.12 g per 100 g straw concentrations. High lignin removal from the solid fraction (62%) did not provide a corresponding increase in the phenol monomer content but was correlated to high carboxylic acid concentrations. The degradation products in the hemicellulose fractions co-varied with the pre-treatment conditions in the principal component analysis according to their chemical structure, e.g. diacids (oxalic and succinic acids), furan aldehydes, phenol aldehydes, phenol ketones and phenol acids. Aromatic aldehyde formation was correlated to severe conditions with high temperatures and low pH. Apart from CO2 and water, carboxylic acids were the main degradation products from hemicellulose and lignin.

Alkalies↗

Potential inhibitors from wet oxidation of wheat straw and their effect on ethanol production of Saccharomyces cerevisiae: wet oxidation and fermentation by yeast.

Alkaline wet oxidation (WO) (using water, 6.5 g/L sodium carbonate and 12 bar oxygen at 195 degrees C) was used as pretreatment method for wheat straw (60 g/L), resulting in a hydrolysate and a cellulosic solid fraction. The hydrolysate consisted of soluble hemicellulose (8 g/L), low-molecular-weight carboxylic acids (3.9 g/L), phenols (0.27 g/L = 1.7 mM) and 2-furoic acid (0.007 g/L). The wet oxidized wheat straw hydrolysate caused no inhibition of ethanol production by Saccharomyces cerevisiae ATCC 96581. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested in concentrations of 50-100 times the concentration found in the hydrolysate for their effect on fermentation by yeast. At these high concentrations (10 mM), 4-hydroxybenzaldehyde, vanillin, 4-hydroxyacetophenone and acetovanillone caused a 53-67% decrease in the volumetric ethanol productivity in S. cerevisiae compared to controls with an ethanol productivity of 3.8 g/L. The phenol acids (4-hydroxy, vanillic and syringic acid), 2-furoic acid, syringaldehyde and acetosyringone were less inhibitory, causing a 5-16% decrease in ethanol productivity. By adding the same aromatic compounds to hydrolysate (10 mM), it was shown that syringaldehyde and acetovanillone interacted negatively with hydrolysate components on the ethanol productivity. Fermentation in WO hydrolysate, that had been concentrated 6 times by freeze-drying, lasted 4 hours longer than in regular hydrolysate; however, the ethanol yield was the same. The longer fermentation time could not be explained by an inhibitory action of phenols alone, but was more likely caused by inhibitory interactions of phenols with carboxylic acids, such as acetic and formic acid.

Cells, Cultured↗

Potential inhibitors from wet oxidation of wheat straw and their effect on growth and ethanol production by Thermoanaerobacter mathranii.

Alkaline wet oxidation (WO) (using water, 6.5 g/l sodium carbonate, and 12 bar oxygen at 195 degrees C) was used for pre-treating wheat straw (60 g/l), resulting in a hemicellulose-rich hydrolysate and a cellulose-rich solid fraction. The hydrolysate consisted of soluble hemicellulose (9 g/l), aliphatic carboxylic acids (6 g/l), phenols (0.27 g/l or 1.7 mM), and 2-furoic acid (0.007 g/l). The wet-oxidized wheat straw hydrolysate caused no inhibition of ethanol yield by the anaerobic thermophilic bacterium Thermoanaerobacter mathranii. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested in concentrations of 10-100x the concentration found in the hydrolysate for their effect on fermentation by T. mathranii. At 2 mM, these aromatic compounds were not inhibitory to growth or ethanol yield in T. mathranii. When the concentration of aromatics was increased to 10 mM, the fermentation was severely inhibited by the phenol aldehydes and to a lesser extent by the phenol ketones. By adding the same aromatic compounds to WO hydrolysate (10 mM), synergistic inhibitory effects of all tested compounds with hydrolysate components were shown. When the hydrolysate was concentrated three- and six-fold, growth and fermentation with T. mathranii were inhibited. At a six-fold hydrolysate concentration, the total concentration of phenolic monomers was 17 mM; hence aromatic monomers are an important co-factor in hydrolysate inhibition.

Bacteria, Anaerobic↗

Improvement in electrokinetic remediation of heavy metal spiked kaolin with the polarity exchange technique.

In the electrokinetic treatment of heavy metal polluted soil, an alkaline environment is generated at the cathode side. It provokes the precipitation of metal ions as hydroxides into the soil and diminishes the capability of the electroremediation to clean the polluted site. In this work the "polarity exchange" technique is presented as a simple way to avoid the negative effect of OH(-) on metal transportation. This technique lies in the operation during short time intervals at inverted polarity, so that the generation of H+ ions from the oxidation of water neutralize in the alkaline zone where the metal is precipitated, favouring its dissolution. Once the metals are redissolved, the polarity is set to the original position to transport them to the desired direction. Kaolin clay contaminated with Mn was used to test the feasibility of the polarity exchange technique. The application of the "conventional technique" dealt with a removal of 14% of the initial Mn in 7.6d. For a similar treatment time the polarity exchange technique resulted in 72% of removed Mn. Successive polarity exchanges will yield with a complete decontamination of the soil with a moderate increment in the electric power consumption.

Electrochemistry↗

Freezing of isolated thylakoid membranes in complex media. VI. The effect of pH.

Thylakoid membranes isolated from spinach leaves (Spinacia oleracea L. cv. Monatol) were used as a model biomembrane system for evaluating the significance of the hydrogen ion activity for cryoprotection. After freeze-thaw treatment in a buffered complex medium adjusted to various pH, light-induced photosynthetic membrane reactions were determined at optimum proton concentration. When thylakoids were suspended at hydrogen ion activities above and below the physiologically important pH range, irreversible inhibition of membrane functions was significantly less distinct after freezing at -15 degrees C than after storage for the same time at 0 degree C. It is suggested that thylakoid preservation at subfreezing temperatures could be due to temperature- and concentration-induced changes of the proton activity in the unfrozen part of the system and retardation of the temperature-dependent aging processes of the isolated membranes. In addition, the increase in the concentration of cryoprotective compounds during freezing could stabilize chloroplast membranes against the deleterious effect of unfavorable high and low proton concentrations. Thylakoid injury brought about by lowering the pH was primarily due to dissociation of the chloroplast coupling factor (CF1), which increased the proton permeability of the membranes and caused inhibition of photophosphorylation. In media adjusted to more alkaline pH, inactivation of the water oxidation system was an initial result of membrane damage. Then, noncyclic photophosphorylation was limited by photosystem II-mediated electron flow. Photosystem I-driven electron transport was substantially more stable over a wide pH range.

Chloroplasts↗

Biodegradability enhancement by wet oxidation in alkaline media: delignification as a case study.

Nowadays many industries are considering the recycling of process waters as a way of improving environmental safety, preventing pollution, and avoiding the loss of valuable production materials. One industry in the forefront of this trend is the pulp and paper industry. Lignin is a pollutant present in the mill process waters and such macromolecules can cause problems during biological treatment of process waters. Wet oxidation (WO) is a process that can be used as a pre-treatment method for lignin fragmentation and improvement of biodegradability. Wet oxidation (WO) under alkaline conditions permits faster lignin fragmentation than the conventional WO process and, therefore, should favour biodegradability improvement. In this study, the experiments were carried out in a high-pressure batch reactor with an alkali lignin solution at temperatures up to 438 K, an alkali concentration of 1.5-3.5 g l(-1) and an oxygen partial pressure of 0.4 to 1.5 MPa. At an alkali concentration of 3.5 g l(-1)1 and 0.4 MPa of oxygen partial pressure, an increase in BOD/COD ratio was achieved from an initial 11% to 71%. The experiments also showed that the amount of small molecules in the solution measured by Immediately Available BOD (IA BOD) depends on the amount of alkali added and the operating temperature.

Biodegradation, Environmental↗

Thioalkalimicrobium cyclicum sp. nov. and Thioalkalivibrio jannaschii sp. nov., novel species of haloalkaliphilic, obligately chemolithoautotrophic sulfur-oxidizing bacteria from hypersaline alkaline Mono Lake (California).

Two strains of haloalkaliphilic, obligately autotrophic, sulfur-oxidizing bacteria were isolated from the oxygen-sulfide interface water layer of stratified alkaline and saline Mono Lake, California, USA. Strain ALM 1T was a dominant species in enrichment on moderate-saline, carbonate-buffered medium (0.6 M total Na+, pH 10) with thiosulfate as an energy source and nitrate as a nitrogen source. Cells of ALM 1T are open ring-shaped and are non-motile. It has a high growth rate and activity of thiosulfate and sulfide oxidation and very low sulfur-oxidizing activity. Genetic comparison and phylogenetic analysis suggested that ALM 1T (= DSM 14477T = JCM 11371T) represents a new species of the genus Thioalkalimicrobium in the gamma-Proteobacteria, for which the name Thioalkalimicrobium cyclicum sp. nov. is proposed. Another Mono Lake isolate, strain ALM 2T, dominated in enrichment on a medium containing 2 M total Na+ (pH 10). It is a motile vibrio which tolerates up to 4 M Na+ and produces a membrane-bound yellow pigment. Phylogenetic analysis placed ALM 2T as a member of genus Thioalkalivibrio in the gamma-Proteobacteria, although its DNA hybridization with the representative strains of this genus was only about 30%. On the basis of genetic and phenotypic properties, strain ALM 2T (= DSM 14478T = JCM 11372T) is proposed as Thioalkalivibrio jannaschii sp. nov..

California↗

PCB destruction in subcritical and supercritical water--evaluation of PCDF formation and initial steps of degradation mechanisms.

The reduction of polychlorinated biphenyl (PCB) emissions to the environment are contemporary issues of global efforts, and possible destruction technologies have to be selected and evaluated for PCB remediation. In this study PCB destruction in subcritical and supercritical water were assessed under oxidative conditions and nonoxidative, alkaline conditions. In both cases PCBs could be destroyed by more than 99%. The formation of polychlorinated dibenzofurans (PCDFs) during PCB destruction was evaluated. Under both oxidative and nonoxidative treatments of sub- and supercritical conditions, the formation of PCDFs was observed. The PCDFs formed in the early stages of PCB destruction resulted in up to 47-fold increase in terms of toxic equivalency (TEQ) compared to the initial PCB mixture. However, the PCDFs were destroyed together with the PCBs under more severe conditions i.e., at higher temperature or prolonged residence time. The mechanism of PCDF formation and the initial step of PCB degradation was evaluated. Our laboratory-scale investigation indicates that PCB destruction under supercritical water conditions is feasible, but because of the PCDF formation potential, in particular the high ratio of toxic 2,3,7,8-substituted congeners, conditions have to be carefully selected.

Benzofurans↗

Pathways of chemical degradation of polypeptide antibiotic bacitracin.

We described the main pathways of bacitracin (Bc) decomposition, chromatographically set the position of its major degradation products and evaluated microbiological activity of isolated components of Bc and its degradation products. All processes of Bc decomposition under stress and accelerated test conditions were monitored with HPLC, performed mainly on a new type reversed-phase (RP-18e) monolithic silica column (Chromolith) enabling fast separation times and some of them also on conventional HPLC columns. Diode array detection, preparative HPLC and FAB mass spectrometry were used for identification of individual Bc components. We found that the major decomposition mechanism in water solutions of Bc is oxidation, and in alkaline solutions, deamidation. In oxidation process the components B1, B2 and B3 and A are oxidized into their corresponding oxidative products H1, H2, H3 and F respectively by the same mechanism. A detailed study of oxidative degradation products revealed that HPLC separation with an acid mobile phase caused splitting of peaks of components H2, H3 and F into two peaks but the peak of component H1 did not split due to its special structural properties. For the component A we confirmed gradual formation of desamido product through an intermediate. We found oxidative degradation products of Bc to be relatively stable, and desamido degradation products to be rather unstable. The estimation of kinetics of Bc decomposition was presented with a semi-quantitative model. Microbiological activity of individual isolated active components of Bc was established and the negligible antimicrobial activity of the degradation products was confirmed.

Amides↗

Ferrate(VI) oxidation of cyanide in water.

Experiments were conducted to test removal of cyanide (free cyanide and several cyanide complexes) in water, under alkaline medium (pH > or = 11), by a new potassium ferrate salt. The removal rate of free cyanide by oxidation with Fe(VI) was greater at pH 11.0 than at pH 12.0. A complete oxidation was obtained with a 2.67 Fe(VI)/CN ratio at pH 11.0. In these conditions, the rate of cyanide oxidation by Fe(VI) was slow, with a reaction rate constant estimated at 0.95 +/- 0.10 s(-1) l mol(-1) at pH 11.0 and 19.6 degrees C in this study. This study revealed that Fe(VI) did not decompose all cyanide complexes. Copper, cadmium and zinc complexes were removed efficiently by Fe(VI). Moreover, these metals were also removed from the solution by coagulation effect of Fe(OH)3, the Fe(VI) product of reaction. A particular behaviour was reported with copper, as a rapid oxidation of cyanide was observed in the presence of this metal. On the contrary, oxidation of nickel and silver complexes was incomplete.

Cyanides↗

Electrochemical alkaline Fe(VI) water purification and remediation.

Fe(VI) is an unusual and strongly oxidizing form of iron, which provides a potentially less hazardous water-purifying agent than chlorine. A novel on-line electrochemical Fe(VI) water purification methodology is introduced. Fe(VI) addition had been a barrier to its effective use in water remediation, because solid Fe(VI) salts require complex (costly) syntheses steps and solutions of Fe(VI) decompose. Online electrochemical Fe(VI) water purification avoids these limitations, in which Fe(VI) is directly prepared in solution from an iron anode as the FeO42- ion, and is added to the contaminant stream. Added FeO42- decomposes, by oxidizing a wide range of water contaminants including sulfides (demonstrated in this study) and other sulfur-containing compounds, cyanides (demonstrated in this study), arsenic (demonstrated in this study), ammonia and other nitrogen-containing compounds (previously demonstrated), a wide range of organics (phenol demonstrated in this study), algae, and viruses (each previously demonstrated).

Electrochemistry↗