Circumneutral pH Research Articles

Novel Pt/COF Janus micromotor with bowl-like structure as an effective catalyst in extremely acidic environments

To effectively enhance the catalytic activity and stability of the heterogeneous catalysts in extremely acidic environments, a novel Pt/COF Janus micromotor catalyst with bowl shape (BSJP) was prepared. The as-synthesized BSJP exhibited excellent catalytic degradation efficiency against methylene blue (MB) as the model substrate, owing to self-propelling motion caused by the unique bowl shape and the concentration effect of pollutants in the bowl-shaped structure. The catalyst has excellent catalytic efficiency. At circumneutral pH, the reaction rate constant of BSJP micromotor was 3.35 times of that of non-propellant particles. At pH = 2, Pt/COF-LZU1 BSJP exhibits the best activity with a maximum removal rate of 98.61 %. Moreover, even under extreme pH conditions (pH < 2), the catalytic degradation efficiency of MB remained high, and the structure and morphology of the catalyst remained unchanged. Importantly, the catalyst exhibited remarkable stability and recyclability. The degradation rate of MB and the removal rate of TOC remained above 90 % during the four cycles. This excellent catalytic performance under extremely acidic conditions was attributed to the physical confinement of Pt nanoparticles by stable COF-LZU1. This work confirms the broad application prospects of COF-carrier materials in water purification.

Formation of mineral-associated organic matter in temperate soils is primarily controlled by mineral type and modified by land use and management intensity.

Formation of mineral-associated organic matter (MAOM) supports the accumulation and stabilization of carbon (C) in soil, and thus, is a key factor in the global C cycle. Little is known about the interplay of mineral type, land use and management intensity in MAOM formation, especially on subdecadal time scales. We exposed mineral containers with goethite or illite, the most abundant iron oxide and phyllosilicate clay in temperate soils, for 5 years in topsoils of 150 forest and 150 grassland sites in three regions across Germany. Results show that irrespective of land use and management intensity, more C accumulated on goethite than illite (on average 0.23 ± 0.10 and 0.06 ± 0.03 mg m-2 mineral surface respectively). Carbon accumulation across regions was consistently higher in coniferous forests than in deciduous forests and grasslands. Structural equation models further showed that thinning and harvesting reduced MAOM formation in forests. Formation of MAOM in grasslands was not affected by grazing. Fertilization had opposite effects on MAOM formation, with the positive effect being mediated by enhanced plant productivity and the negative effect by reduced plant species richness. This highlights the caveat of applying fertilizers as a strategy to increase soil C stocks in temperate grasslands. Overall, we demonstrate that the rate and amount of MAOM formation in soil is primarily driven by mineral type, and can be modulated by land use and management intensity even on subdecadal time scales. Our results suggest that temperate soils dominated by oxides have a higher capacity to accumulate and store C than those dominated by phyllosilicate clays, even under circumneutral pH conditions. Therefore, adopting land use and management practices that increase C inputs into oxide-rich soils that are under their capacity to store C may offer great potential to enhance near-term soil C sequestration.

Stability of Coumarins and Determination of the Net Iron Oxidation State of Iron-Coumarin Complexes: Implications for Examining Plant Iron Acquisition Mechanisms.

Coumarins are exuded into the soil environment by plant roots in response to iron (Fe) deficiency. Previous studies have shown that coumarins can increase the Fe solubility upon interaction with sparsely soluble Fe(III) (hydr)oxide. However, the chemical mechanisms of Fe(III) (hydr)oxide dissolution by coumarins remain unclear. The high redox instability of dissolved coumarins and the interference of coumarins in determining the Fe redox state hinder the quantitative and mechanistic investigation of coumarin-induced Fe mobilization. In this study, we investigated the oxidative stability of three coumarins that have been found in root exudates, esculetin, scopoletin, and fraxetin, over a broad pH range under oxic and anoxic conditions. Our results show that the oxidation of coumarins is irreversible under oxic conditions and that oxidative degradation rates increased with increasing pH under both oxic and anoxic conditions. However, the complexation of Fe protects coumarins from degradation in the circumneutral pH range even under oxic conditions. Furthermore, we observed that Ferrozine, which is commonly used for establishing Fe redox speciation, can facilitate the reduction of Fe(III) complexed by coumarins, even at circumneutral pH. Reduction rates increased with decreasing pH and were larger for fraxetin than for scopoletin and esculetin. Based on these observations, we optimized the Ferrozine method for determining the redox state of Fe complexed by coumarins. Understanding the stability of dissolved coumarins and using a precise analytical method to determine the redox state of Fe in the presence of coumarins are critical for investigating the mechanisms by which coumarins enhance the availability of Fe in the rhizosphere.

Kinetic constraints for the formation of microniches for microaerophilic Fe(II) oxidation

Oxidation of Fe(II) by oxygen (O2) at circumneutral pH occurs abiotically or is mediated by microaerophilic Fe(II)-oxidizing bacteria. Abiotic Fe(II) oxidation(s) compete with microbial processes and the relative contribution of abiotic reactions depend on the chemical conditions, e.g. PO2, pH and the presence and identity of ferric (oxyhydr)oxide mineral surfaces, catalyzing the heterogeneous reaction. At circumneutral pH, abiotic Fe(II) oxidation proceeds rapidly, which raises the question how and to which extent neutrophilic microaerophilic Fe(II)-oxidizing bacteria can compete with chemical reactions and gain metabolic energy from microbial Fe(II) oxidation. In this study, we have investigated the environmental constraints for microaerophilic Fe(II) oxidation in a film layer characterized by diffusive supply of both atmospheric O2 (from the top) and dissolved Fe(II) (from the bottom) by use of a numerical model. A coupled diffusion–reaction model was tested at different chemical (pH and alkalinity gradients) and physical (film layer thickness) parameters to investigate their effects on the relative contributions of different reactions (abiotic homogeneous, heterogeneous and biological Fe(II) oxidation) to the overall (net) Fe(II) oxidation. A first order rate constant for biological oxidation was derived from experimental data from simplifcation of a Monod rate law to be 0.06 h−1. The simulations demonstrate distinct spatial oxidation rate patterns for all of the considered reactions. Microaerophilic Fe(II) oxidation is predominant at a uniform pH 6 and a film thickness z of 1 mm with minor importance at pH 7. Maximum biological rates were on the order of 7∙10-10 mol L−1 s−1 and are in the range of experimentally observed values. Minimum rates were close to the thermodynamic limit. In the presence of a pH gradient and z ≤ 1 mm, two distinct zones were observed: an upper zone dominated by abiotic Fe(II) oxidation (pH ∼ 7) and a lower zone dominated by microaerophilic Fe(II) oxidation (pH < 6.3), while the position and extent of the zones depend on the alkalinity. Such separation is strongly amplified for thinner films (z = 0.2 mm). The importance of heterogenous oxidation depends both on the pH and the amount of ferric (oxyhydr)oxides formed which increases with decreasing diffusive O2 supply at z > 1 mm. In combination with high resolution imaging of pH values in a biofilm, our simulations underpin the importance of pH gradients in allowing for the formation of microniches. The conditions suitable for microaerophilic Fe(II) oxidation can be predicted based on reaction time scales and three factors were identified to be especially important: i) a pH low enough (<6.3) to outcompete abiotic processes; ii) sufficiently fast diffusive supply of Fe(II) (e.g. by Fe(III)-reducing bacteria or chemical processes) with O2 concentrations below 150 μmol L−1; iii) sufficient energy gain from Fe(II) oxidation reaction considering the thermodynamic factor FT. We end by discussing strategies that Fe(II)-oxidizing microorganisms can employ to enhance their competitiveness against abiotic reactions.

Impact of Solution {Ba2+}:{SO42-} on Charge Evolution of Forming and Growing Barite (BaSO4) Crystals: A ζ-Potential Measurement Investigation.

The impact of solution stoichiometry on formation of BaSO4 (barite) crystals and the development of surface charge was investigated at various predefined stoichiometries (raq = 0.01, 0.1, 1, 10, and 100, where raq = {Ba2+}:{SO42-}). Synthesis experiments and zeta potential (ζ-potential) measurements were conducted at a fixed initial degree of supersaturation (Ωbarite = 1000, where Ωbarite = {Ba2+}{SO42-}/Ksp), at circumneutral pH of ∼6, 0.02 M NaCl, and ambient temperature and pressure. Mixed-mode measurement-phase analysis light scattering (M3-PALS) showed that the particles stayed negative for raq < 1 during barite crystal formation and positive for raq > 1. At raq = 1, two populations with a positive or negative ζ-potential prevailed for ∼2.5 h before a population with a circumneutral ζ-potential (-10 to +10 mV) remained. We relate the observations of particle charge evolution to particle size and morphology evolution under the experimental conditions. Furthermore, we showed that the ζ-potential became more negative when the pH was increased for every raq. In addition, our results demonstrated that the type of monovalent background electrolyte did not influence the ζ-potential of barite crystals significantly, although NaCl showed slightly different behavior compared to KCl and NaNO3. Our results show the important role of surface charge (evolution) during ionic crystal formation under nonstoichiometric conditions. Moreover, our combined scanning electron microscopy and ζ-potential results imply that the surface charge during particle formation can be influenced by solution stoichiometry, besides the pH and ionic strength, and may aid in predicting the fate of barite in environmental settings and in understanding and improving industrial barite (surface chemistry) processes.

Assessment of Modified Culture Conditions for Fungal Bio-Oxidation of Sulfidic Gold Ores Performed at Circumneutral pH

The significant neutralization of waste streams required after the acidic bio-oxidation of sulfidic gold ores could be avoided by performing a novel treatment at circumneutral pH with an in situ neutralization. For the first time, the white-rot fungus Phanerochaete chrysosporium was incubated in a modified culture medium containing corn steep, an industrial waste product, to support microbial activity and, subsequently, the oxidation of a sulfidic ore at an initial circumneutral pH environment. In this investigation, the concentration of the native culture medium ingredients was first evaluated with response surface methodology to attain maximum sulfide oxidation. The statistical analysis proposed a modified culture medium composed of 12.86 g/L glucose, 2.20 g/L malt extract, 1.67 g/L yeast extract, and 0.49 g/L MgSO4·7H2O to reach a maximum of 28.7% sulfide oxidation after 14 d-bio-oxidation. pH-controlled batch cultures showed that an increase in initial pH in the range of 5.8 to 7.0 reduced the microbial activity, affecting sulfide oxidation. In addition, the modified culture medium at which yeast extract was substituted with 1.67 g/L corn steep produced comparable microbial activity and sulfide oxidation after 14 d, attaining 21.6% at 5% w/v with a maximum 39 U/L lignin peroxidase and 116 U/L manganese peroxidase. A 40.6% sulfide oxidation and 43.8% gold recovery were obtained after 42 d three-cycle replenishing bio-oxidation and 24 h cyanidation, respectively. Overall, corn steep waste showed the potential to substitute more expensive culture medium ingredients, supporting microbial activity and oxidation of sulfidic gold ores at an initial circumneutral pH and contributing to circularity of waste management.

Geochemistry and mineralogy of legacy tailings under a composite cover

Remediation by a composite cover was implemented on partly oxidized sulfide-rich tailings in northern Ontario, Canada to reduce the production and release of acid mine drainage (AMD). The impact of the cover on sulfide oxidation rates and trace element mobility was initiated a decade after cover installation via multi-year measurements of pore-gas concentrations, pore-water and groundwater sampling and analysis, mineralogical studies of the tailings, selective chemical extractions, and synchrotron-based X-ray absorption experiments. Depleted pore-gas O2 concentrations, circumneutral pH, and improvement in water quality were observed at one detailed sampling location, suggesting that the cover decreased AMD generation and transport. Carbon and sulfur isotope ratios indicate sulfate reduction occurred at the base of the tailings. In contrast, near-atmospheric pore-gas O2 concentrations, low pH, and elevated aqueous concentrations of Fe, sulfate, Zn, Cu, As, and Pb were observed at another location, suggesting localized sulfide oxidation. Trace elements in the tailings are associated with secondary crystalline and amorphous Fe(III) oxyhydroxides, covellite, and Fe(III) hydroxysulfate phases, formed prior to cover installation. Substantial reductive dissolution of Fe(III) oxyhydroxides due to the isolation of the tailings from the atmosphere by the cover was not observed. Concentrations of Zn and Mn remained elevated due to limited sequestration under the current acidic to circumneutral pH. Although secondary Fe(III) oxyhydroxides contain As(V) and As(III), which were released by arsenopyrite oxidation, dissolved As persists. Due to localized sulfide oxidation, element remobilization, and limited capacity for sulfate reduction, diminished water quality, with elevated aqueous concentrations of sulfate, Zn, As, and Mn, may endure.

Initial Limnology of Laguna Pozo Verde, Costa Rica: Bathymetry, Water, Sediments, and Diatoms

Introducción : Costa Rica tiene cientos de lagos, muchos de los cuales nunca han sido estudiados científicamente. Objetivo: Conocer limnológia de la Laguna Pozo Verde en el Parque Nacional Juan Castro Blanco, Costa Rica (~1935 m de elevación), para proporcionar datos de referencia para estudiar cambios futuros. Métodos: Medimos la profundidad y temperatura del agua y la profundidad de Secchi; sedimentos superficiales analizados; y examinó mapas e imágenes de satélite. Resultados: Aunque algunos la describen como formada por procesos volcánicos, la Laguna Pozo Verde probablemente se formó en un deslizamiento de tierra, que ocurre con frecuencia en esta zona lluviosa en la empinada ladera sur del inactivo volcán Porvenir. Nuestros sondeos mostraron una profundidad máxima de 9,25 m cerca del centro del lago. El agua era moderadamente transparente (profundidad de Secchi 2,6 m), con pH circunneutro y temperaturas de 15,9 a 18,1 °C, con estratificación débil a 0,5 m. Los sedimentos superficiales contenían 27% de materia orgánica y tenían relaciones C/N y valores de isótopos de carbono estables consistentes con algas lacustres y plantas C 3 ; Surirella angusta compuso más del 90% de las diatomeas. Conclusión: La laguna es significativamente más omera de lo informado y los sedimentos superficiales albergar una combinación de diatomeas única entre los 88 lagos examinados en Costa Rica.

Surface reactivity of the iron and manganese-oxidizing bacterium Leptothrix cholodnii SP-6

Surfaces of prokaryotic cells play a significant role in the adsorption of metals from aqueous solution and the formation of authigenic minerals (Konhauser 2006). Although most studies focus on the cell wall, it is known that many bacteria synthesise an extracellular layer of polysaccharides and proteins, including what are known as sheaths. It has been shown that the cyanobacterium Calothrix sp. produces as sheath which is neutrally charged at circumneutral pH values, and it was hypothesized that such a sheath might allow the cyanobacterium to survive in geothermal settings with high silicification rates (Phoenix et al. 2002). Specifically, the dominance of hydroxyl sites on Calothrix’s sheath surface facilitates hydrogen bonding with aqueous silica species, inducing the precipitation of amorphous silica on the sheath and thus protecting the underlying cell (Phoenix et al. 2002). Leptothrix cholodnii is a sheathed, iron and manganese-oxidizing bacterium that frequently inhabits minerals seeps, where Fe2+ and Mn2+ discharge into oxygenated surface waters (Spring et al. 1996). As a result, the sheath becomes encrusted with Fe(III) and Mn(IV) oxyhydroxides while the underlying cells are protected from mineralization (Emerson and Ghiorse 1992, Emerson et al. 2010). However, unlike Calothrix, Leptothrix’s sheath composition suggests that it might behave differently at circumneutral pH (Emerson and Ghiorse 1993). To investigate the surface reactivity of Leptothrix's sheath and cell wall we analyzed isolated sheaths, sheathless cells, and intact filaments of L. cholodnii SP-6. We studied these components using potentiometric titration, zeta-potential, Cd-adsorption, and Fourier transform infrared (FTIR) spectroscopy to elucidate changes in surface charge between the cell wall and sheath. For the isolated sheaths and intact filaments, titration data were fit using a two-site protonation model, resulting in the following pKa values: 6.05 (±0.29) and 9.34 (±0.11); and 7.77 (±0.17) and 10.50 (±0.20), respectively. For the sheathless cells, the best fit was obtained by using a three-site protonation model, resulting in the following pKa values: 5.40 (±0.59), 8.11 (±1.64) and 10.73 (±0.45). Total proton-active site concentrations were lower in isolated sheaths compared to intact filaments. Additionally, at circumneutral pH, net negative charge was lower for sheathless cells compared to intact filaments and isolated sheaths (Fig. 1). This information agrees with the Cd adsorption behaviour found for the three materials (Fig. 2). Thus, our preliminary results suggest that Leptothrix’s sheath is less reactive than the intact filaments at circumneutral pH, leading us to hypothesize that the outermost layer would sequester relatively lower amounts of cations, including Mn2+, from solution and potentially would protect the underlaying cell from deleterious mineralization. In addition to that, the less reactive sheath’s surface would also contribute to cell attachment, which is important for a species commonly found in streams (Phoenix et al. 2002, Emerson et al. 2010).

Nitrate-Reducing Fe(II)-Oxidizing microorganisms: linking Fe, C and N Cycles in subsurface environments

The discovery of the Nitrate-Reducing Fe(II)-Oxidizing (NRFeOx) microbial metabolism, which couples the oxidation of Fe(II) to the reduction of nitrate (NO3-) using organic matter or carbon dioxide (CO2) as carbon source, was a major milestone in microbial ecology (Straub et al. 1996). NRFeOx microorganisms play an essential role on a global scale in three of the most important biogeochemical cycles: iron (Fe), carbon (C) and nitrogen (N) (Kappler et al. 2021, Huang et al. 2021). In addition, these organisms participate in the mobilization or stabilization of organic carbon, as well as in CO2 fixation, thus contributing to the reduction of atmospheric CO2 (Kappler et al. 2021). Finally, the activity of these microorganisms is key to remove the pollutant NO3- from aquifers, which is one of the major worldwide environmental issues since many environments exceed the maximum regulatory concentration (50 mg L-1) (Kazakis et al. 2020 ). A plethora of NRFeOx microorganisms have been described in the last decades. However, most of these microorganisms have been reclassified as chemodenitrifiers. That is to say, Fe(II) is not enzymatically oxidized but indirectly by the reactive nitrogen species produced during denitrification (Fig. 1 ). In fact, only in three cultures so far, named KS, BP and AG, has the presence of true NRFeOx metabolism been unequivocally demonstrated (Straub et al. 1996, Huang et al. 2021b, Jakus et al. 2021b). Cultures KS, BP and AG have been studied thoroughly in the past years, analyzing the rate and mechanism by which these communities carry out autotrophic NRFeOx. Different omics studies have revealed that cultures KS, BP and AG consist of a mixture of bacterial species, which collaborate in order to grow under autotrophic NRFeOx conditions. Each culture is dominated by a novel candidate species of the genus Ferrigenium (Huang et al. 2022) capable of fixing CO2 and oxidizing Fe(II), but which requires flanking species to complete denitrification (Huang et al. 2021b, He et al. 2016, Huang et al. 2021a). Interestingly, these communities not only carry out NRFeOx using dissolved Fe(II) as energy source (Straub et al. 1996, Huang et al. 2021b, Jakus et al. 2021b), but they can also oxidize Fe(II) minerals, the main form in which Fe(II) can be found in the Earth's crust (Huang et al. 2021). In fact, Fe(II)-bearing minerals are thought to be the main drivers of NO3- reduction in subterranean environments (Huang et al. 2021), which has additional ecological consequences. NRFeOx microorganisms can trigger the turnover of the Fe(II)-bearing minerals, resulting in the mobilization of mineral structural elements such as S, P, C or contaminant heavy metals and the precipitation of Fe(III) minerals at circumneutral pH (Weber et al. 2001, Jakus et al. 2021a). Here, we will present a review of the insights learned from the three NRFeOx autotrophic cultures and discuss their ecological role, their importance in biogeochemical cycles, and their potential biotechnological applications.

Microbial pyrite formation: mineral morphology and precipitation kinetics

Pyrite (FeS2) is a mineral of wide interest due to its importance in the biogeochemical cycling of Fe and S, which is tied to those of carbon and other trace metals and nutrients. The mineral itself has potential applications as biosignatures, for environmental remediation and as semiconductors. Despite being a common authigenic mineral in sedimentary environments, most laboratory-based experiments have failed to form pyrite in microbial cultures at ambient temperatures. To fill this knowledge gap, we have employed cultivation-based approaches, using different combinations of microorganisms (Fe(III)- and S0-reducers; S0-disproportionaters) and initial Fe and S sources to identify the conditions that are optimal for pyrite formation. Scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffraction (XRD) demonstrate that pyrite is not formed within ~3 years at circumneutral pH when oxidants (e.g., Fe(III) minerals, elemental sulfur, S0) are exhausted. In contrast, pyrite is formed within months when S0 and Fe(III) minerals are both present. The precipitation timescale is consistent with those expected in sedimentary environments Mansor and Fantle 2019), albeit some natural pyrite framboids are expected to form even faster Rickard 2019). The pyrite crystals formed in our experiments are in the low micrometer range, with either a spherical or euhedral morphology depending on the initial crystallinity of the supplied Fe(III) minerals. Framboids are not formed in our system, perhaps due to the relatively slow precipitation kinetics. Time-based sampling indicates mackinawite (FeS) as the first product, with rare (and minor) detection of greigite (Fe3S4) and vivianite [Fe3(PO4)2.8H2O]. We hypothesize that pyrite formation and growth proceed mainly from transformation of precursor minerals, with potential contributions via dissolution-precipitation and/or particle attachment pathways. Our preliminary study is the first step in optimizing a system for microbial pyrite formation, with the intention of investigating the properties and the reactivity of the mineral with implications for biosignatures, environmental remediation and industrial applications.

Comparative study of the photooxidation of arsenite mediated by dissolved and mineral-associated humic acid under light irradiation

The photochemical processes of dissolved humic acid and its potential contribution to As(III) oxidation in natural water has received considerable attention. However, the role of mineral-humic complexes in As(III) conversion is rarely studied. Herein, two simulated mineral-humic complexes were prepared by coating humic acid on hydrous aluminum oxide, HA@HAO, or montmorillonite, HA@SWy, respectively, and batch experiments at circumneutral pH were performed under light irradiation. Our findings showed that the light-assisted oxidation of As(III) increased with increasing fractions of organic carbon in mineral-humic complexes, and As(III) photooxidation with HA@HAO or HA@SWy was up to 18.2 or 3.5-fold higher compared to that measured in the presence of equivalent amount of free HA, respectively. The reactive triplet state of HA and hydroxyl radicals in HA@HAO and HA@SWy system made a primary contribution to As(III) oxidation under irradiation. The results indicated that mineral-humic complexes have dual roles, an adsorbent and a photosensitizer, to promote As(III) access to reactive intermediates at the particle surfaces. This process was important for As(III) conversion in paddy water as colloidal particles, composed of both minerals and HA, could greatly promote As(III) oxidation and As(V) immobilization. This study provides a previously overlooked, important mechanism of As(III) phototransformation mediated by mineral-associated humic acid in natural environment.

Response of diatom communities to climate and human disturbance: A 4200-year record from Costa Rica

This study integrates diatom analysis with existing records of pollen, charcoal, elemental composition, and stable light isotopes to expand upon the 4200-year history of human activity and climate change from Laguna Los Mangos in southern Pacific Costa Rica. We counted diatoms in peroxide-treated samples and analyzed community composition using cluster analysis, revealing four distinct assemblage zones with diatom variability most closely correlated with phosphorus, titanium, and organic content. The earliest assemblage (Zone D, 4150–3430 cal yr BP) was dominated by Encyonema silesiacum and Nitzschia incognita and aligned with a period of deforestation, erosion, and abundant macrophytes. Gomphonema affine proliferated in Zone C (3430–2450 cal yr BP), reflecting increased pH and productivity likely caused by agriculture-induced nutrient loading. We attributed the preservation gap from 3290 to 2970 cal yr BP in Zone C to silica depletion and erosional deposition that induced decline in diatom abundance by diluting valve concentrations in lake sediments. Nitzschia incognita and G. affine became the dominant taxa in Zone B (2450–1400 cal yr BP), likely reflecting eutrophy, increasing conductivity, and drying climate. Dominance of Diadesmis confervacea indicated reduced lake level in Zone A (1400 cal yr BP–modern) at the onset of the Terminal Classic Drought (TCD). A hiatus in the record indicates lake desiccation from 950 to 450 cal yr BP. During the Little Ice Age (LIA), diatoms reflect conditions similar to Zone B indicating increased lake level, circumneutral pH, and eutrophy. Refilling of the lake indicates increased precipitation during the LIA despite evidence of severe regional drought reported at other sites. Variable precipitation during this period likely resulted from the combined effects of Spanish contact, agricultural collapse, forest recovery, and shifts in Atlantic and Pacific climate forcing mechanisms. Overall, the Los Mangos diatom record reflects shallow, slightly alkaline, eutrophic conditions influenced by nutrient enrichment, erosion, and deforestation associated with maize agriculture.

Cadmium immobilization during nitrate-reducing Fe(II) oxidation by Acidovorax sp. BoFeN1: Contribution of bacterial cells and secondary minerals

Microbially nitrate-reducing Fe(II) oxidation (NRFO) is widespread in anoxic environments at circumneutral pH, in which Fe(II) oxidation is considered to be mainly catalyzed by nitrite via chemodenitrification after microbial nitrate reduction. Cadmium (Cd) is toxic to organisms, and its availability is strongly affected by iron (oxyhydr)oxides and/or bacteria. However, it remains unclear how NRFO affects the fate of Cd with environmentally relevant concentrations, and the relative contributions of microbes and secondary minerals to Cd immobilization during NRFO. Here, Acidovorax sp. BoFeN1, a typical NRFO bacterium, was used to investigate the Cd immobilization during NRFO at pH 7.0 with 0.1, 0.5, and 1.0 mg/L Cd, respectively. Higher initial Cd concentration resulted in a higher amount of Cd immobilized in precipitates, but showed stronger inhibition on nitrate reduction, acetate metabolism, and cell growth. The presence of Cd barely influenced the Fe(II) oxidation during NRFO or chemodenitrification, but retarded the mineral transformation to secondary crystalline minerals, i.e., lepidocrocite and goethite. The extracellular polymeric substances deposited in the bacteria-mineral precipitates were rich in tyrosine-like and tryptophan-like proteins with negatively charged amino and carboxyl groups. The STEM-HAADF images with EDX mapping demonstrated that Cd was strongly co-localized with Fe on the cell surface and in the periplasm. Cadmium immobilization experiments with bacterial cells or during chemodenitrification indicated that the bacterial cells and secondary minerals formed during chemodenitrification are comparably important for Cd immobilization in the Cd0.1 treatment, while the secondary minerals played a predominant role in Cd immobilization in the Cd0.5 and Cd1.0 treatments. These results suggested that Cd was likely associated with the secondary iron minerals, which precipitated with the proteins on the cell surface and in the periplasm. Our findings provide a comprehensive understanding of the roles of Cd, bacterial cells, and secondary minerals formed via chemodenitrification, as well as their interactions during the complicated NRFO process at circumneutral pH.

Efficient and selective electrosynthesis of 4-aminophenol at circumneutral pH from the electrocatalytic reduction of nitrophenol over the nickel-iron phosphide modified electrode

The efficient and sustainable synthesis of 4-aminophenol (4-AP) from the electrocatalytic reduction of 4-nitrophenol (e-NPR) with water as the proton source relies on the development of robust electrocatalysts that readily expedite the kinetics of e-NPR and generate 4-AP with high selectivity at environmentally-benign conditions. In this study, we report on the efficient and sustainable electrosynthesis of 4-AP at circumneutral pH using the micro-structured nickel-iron phosphide modified electrode (CP|microNiFeP). The effects of the iron content of the prepared CP|microNiFeP electrodes as well as electrolysis conditions, including the electrolyte pH, applied potential, and electrolysis duration, on the electrosynthesis of 4-AP were thoroughly examined through a series of controlled-potential electrolyses (CPEs). Under optimal conditions, the CP|microNiFeP electrode exhibited a turnover frequency of 7.25 ± 0.05 h−1 for the generation of 4-AP at 0.0 V vs. RHE and achieved a high 4-NP conversion of 92.29 ± 1.47% with high selectivity for 4-AP generation (SAP:85.77 ± 2.21%) after 8-h CPE at −0.15 V vs. RHE in the H-cell. In addition, the scale-up electrosynthesis of 4-AP with a flow-type electrolyzer was also demonstrated. The 3-h electrolysis using the flow-type electrolyzer resulted in a high 4-NP conversion (93.84 ± 0.84%) with a high SAP (86.32 ± 1.05%). The possible reaction pathways of e-NPR have been proposed, and 4,4′-dihydroxyazobenzene and dimers were identified as the main side products.

Simultaneous degradation of contaminants of emerging concern and disinfection by solar photoelectro-Fenton process at circumneutral pH in a solar electrochemical raceway pond reactor

Simultaneous contaminants of emerging concern (CECs) removal and wild microorganisms’ inactivation was evaluated by applying solar photoelectro-Fenton (SPEF) process in actual secondary effluent collected from a real municipal wastewater treatment plant (MWWTP). 20 L of a mixture of four CECs was used as model pollutants (200 μg/L of acetaminophen, caffeine, sulfamethazine, and sulfamethoxazole each one). The SPEF process was carried out on fully sunny days, at circumneutral pH using the complex Fe3+-EDDS, in a solar electrochemical – raceway pond reactor (SEC-RPR). Initially, the optimal conditions for CECs degradation were determined using a response surface model based on current density, iron complex concentration and Fe3+-EDDS addition time (to allow previous accumulation of H2O2) as model inputs. A current density of 24.6 mA/cm2, a Fe3+-EDDS complex concentration of 0.089 mM and 3.8 min of previous H2O2 accumulation were the resulting optimum conditions that were afterwards applied for the simultaneous degradation of the CECs synthetic mixture and wild microorganisms inactivation in actual secondary effluent. About 85% CECs removal and complete E. coli inactivation were achieved in 30 min, approximately, while E. faecalis and total coliforms could be inactivated under detection limit in 60 min and 75 min, respectively.

Steerable isobutyric and butyric acid production from CO2 and H2 by Clostridium luticellarii.

Clostridium luticellarii is a recently discovered acetogen that is uniquely capable of producing butyric and isobutyric acid from various substrates (e.g. methanol), but it is unclear which factors influence its (iso)butyric acid production from H2 and CO2 . We aimed to investigate the autotrophic metabolism of C. luticellarii by identifying the necessary growth conditions and examining the effects of pH and metabolite levels on product titers and selectivity. Results show that autotrophic growth of C. luticellarii requires the addition of complex nutrient sources and the absence of shaking conditions. Further experiments combined with thermodynamic calculations identified pH as a key parameter governing the direction of metabolic fluxes. At circumneutral pH (~6.5), acetic acid is the sole metabolic end product but C. luticellarii possesses the unique ability to co-oxidize organic acids such as valeric acid under high H2 partial pressures (>1 bar). Conversely, mildly acidic pH (≤5.5) stimulates the production of butyric and isobutyric acid while partly halting the oxidation of organic acids. Additionally, elevated acetic acid concentrations stimulated butyric and isobutyric acid production up to a combined selectivity of 53 ± 3%. Finally, our results suggest that isobutyric acid is produced by a reversible isomerization of butyric acid, but valeric and caproic acid are not isomerized. These combined insights can inform future efforts to optimize and scale-up the production of valuable chemicals from CO2 using C. luticellarii.

Targeting oxidation sites on boreal acid sulfate soil macropore surfaces mitigates acid and metal release to recipient water streams

When reduced sulfidic parent sediments are oxidized, they become acid sulfate soils and discharge metal laden acidic solutions that can damage the environment, infrastructure, and human health. Consequently, methods to mitigate the effect of acid sulfate soils are a priority in affected areas. In this study, acid sulfate soil core samples, consisting of a natural network of preferential-flow soil macropores with defined macropore surfaces and inner cores of denser clay, were characterized and subjected to treatments with calcium carbonate and peat suspensions, or combinations thereof. The effects on the geochemistry and microbial communities were examined on both macropore surfaces and in inner cores. Although transport of treatment substances into the inner cores was demonstrated, no substantial effects were found on the geochemistry and microbial community that consisted of bacterial taxa commonly identified in acid mine drainage. In contrast, positive treatment effects were clearly detected on macropore surfaces and the most promising mitigation effects were detected for treatments combining calcium carbonate and peat suspensions. These treatments increased the pH of the macropore surfaces, added an electron donor in the form of peat, and significantly decreased the relative abundance of acidophilic bacterial populations while shifting the microbial community towards species typically growing at circumneutral pH values. These new environmental conditions were favorable for iron reduction that resulted in a positive effect on permeate quality. The study presents novel data regarding the important differences between acid sulfate soil macropore surfaces and inner cores, as well as their diverse biogeochemical characteristics. It further establishes that the major oxidation-reduction processes occur at the macropore surfaces, and that the combination treatment was the most effective at mitigating the negative environmental effects.

Application of Phanerochaete chrysosporium for enhancing gold recovery via bio-oxidation of refractory sulfidic ores in a circumneutral environment

Regardless of the effectiveness of the industrial process design for gold recovery encompassing acidic bio-oxidation and cyanidation, the substantial neutralization of effluents required after bio-oxidation results in a considerable generation of waste streams. Conducting a bio-oxidation at circumneutral pH with in-situ neutralization is a novel technological opportunity for strengthening environmental protection and safety. For the first time, this research reports the capacity of Phanerochaete chrysosporium to oxidize a low-grade refractory gold ore at circumneutral pH. The fungal treatment was evaluated in five culture media regarding pH variation, enzyme activity, and sulfide oxidation. Thereafter, optimal conditions were investigated and then scaled up in a bioreactor. Results indicated that pH > 5.0 decreased the enzyme concentration released by P. chrysosporium, reducing sulfide oxidation. An initial pH of 5.8 led to a 24.4 ± 2.2% sulfide oxidation after 14 days, comparatively better to reported studies in the same pH range. A higher efficiency was attained by replenishing the fungal culture for three cycles, reaching 47.6 ± 2.3% sulfide oxidation and 49.5 ± 2.4% gold recovery. The results were confirmed by UV–visible, C/S detector, SEM and gold fire assay. Overall, this study opens a possibility to explore a bio-oxidation at higher pH, contributing to the vision of a net-zero target.

Sustainable treatment of municipal secondary effluent from UASB systems by solar photo-Fenton: CECs removal and toxicity control

Upflow Anaerobic Sludge Blanket (UASB) systems are vastly implemented for municipal wastewater treatment in developing tropical countries. Despite that, efforts related to the removal of contaminants of emerging concern (CECs) from municipal secondary effluents (MSE) via post-treatment by solar photo-Fenton are mainly conducted with MSE from Conventional Activated Sludge (CAS). Hence, it is critical to investigate the efficiency of solar photo-Fenton to treat MSE from UASB systems. This is the first study to evaluate the performance of solar photo-Fenton and dark Fenton conducted with intermittent additions of Fe2+ and at circumneutral pH for the removal of CEC from UASB followed by Trickling Filter (UASB+TF) and UASB effluent. Acute and chronic ecotoxicity to Aliivibrio fischeri and Raphidocelis subcapitata, respectively, and phytotoxicity to Lactuca sativa were also evaluated for both matrixes. Solar photo-Fenton removed 83% of ΣCECs from UASB+TF effluent and resulted in non-toxic samples. Solar photo-Fenton performed in MSE from UASB system alone showed 65% ΣCECs removal and reduced chronic effect to R. subcapitata (growth inhibition) from 11% to 26%. In addition, no acute toxicity was verified for A. fischeri nor L. sativa. This work shows the feasibility of applying solar photo-Fenton at circumneutral pH to improve the quality of MSE resulting from UASB systems prior to wastewater discharge or reuse in agriculture.