A mineral-based origin of Earth's initial hydrogen peroxide and molecular oxygen.

Terrestrial reactive oxygen species (ROS) may have played a central role in the formation of oxic environments and evolution of early life. The abiotic origin of ROS on the Archean Earth has been heavily studied, and ROS are conventionally thought to have originated from H2O/CO2 dissociation. Here, we report experiments that lead to a mineral-based source of oxygen, rather than water alone. The mechanism involves ROS generation at abraded mineral-water interfaces in various geodynamic processes (e.g., water currents and earthquakes) which are active where free electrons are created via open-shell electrons and point defects, high pressure, water/ice interactions, and combinations of these processes. The experiments reported here show that quartz or silicate minerals may produce reactive oxygen-containing sites (≡SiO•, ≡SiOO•) that initially emerge in cleaving Si-O bonds in silicates and generate ROS during contact with water. Experimental isotope-labeling experiments show that the hydroxylation of the peroxy radical (≡SiOO•) is the predominant pathway for H2O2 generation. This heterogeneous ROS production chemistry allows the transfer of oxygen atoms between water and rocks and alters their isotopic compositions. This process may be pervasive in the natural environment, and mineral-based production of H2O2 and accompanying O2 could occur on Earth and potentially on other terrestrial planets, providing initial oxidants and free oxygen, and be a component in the evolution of life and planetary habitability.

Multi-imaging platform for rhizosphere studies: Phosphorus and oxygen fluxes.

Rhizosphere is a soil volume of high spatio-temporal heterogeneity and intensive plant-soil-microbial interactions, for which visualization and process quantification is of highest scientific and applied relevance, but still very challenging. A novel methodology for quick assessment of two-dimensional distribution of available phosphorus (P) in rhizosphere was suggested, tested, and development up to the application platform. Available P was firstly trapped by an in-situ diffusive gradients in thin-films (DGT) sampler with precipitated zirconia as the binding gel, and subsequently, the loaded gel was analyzed with an optimized colorimetric imaging densitometry (CID). The imaging platform was established linking: i) DGT, ii) planar optode, and iii) soil zymography techniques to simultaneously determine available P, oxygen, and acid phosphatase in rhizosphere at sub-millimeter spatial scales. The DGT identified available P level in rice rhizosphere were spatially overlapping to the localized redox hotspots and phosphatase activity. The spatial relationship between available P and acid phosphatase activity was dependent on root development. The root radial oxygen loss (ROL) remained active during the experimental observations (2-3 days), while a flux of available P of 10 pg cm-2 s-1 was visualized within 2-3 mm of roots, confirming the correlative response of rice roots to oxygen secretion and P uptake. Summarizing, the established imaging platform is suitable to capture spatial heterogeneity and temporal dynamics of root activities, nutrient bioavailability, ROL and enzyme activities in rhizosphere.

Arabidopsis seedlings respond differentially to nutrient efficacy of three rock meals by regulating root architecture and endogenous auxin homeostasis.

BACKGROUND: Plants show developmental plasticity with variations in environmental nutrients. Considering low-cost rock dust has been identified as a potential alternative to artificial fertilizers for more sustainable agriculture, the growth responses of Arabidopsis seedlings on three rock meals (basalt, granite, and marlstone) were examined for the different foraging behavior, biomass accumulation, and root architecture. RESULTS: Compared to ½ MS medium, basalt and granite meal increased primary root length by 13% and 38%, respectively, but marlstone caused a 66% decrease, and they all drastically reduced initiation and elongation of lateral roots but lengthened root hairs. Simultaneous supply of organic nutrients and trace elements increased fresh weight due to the increased length of primary roots and root hairs. When nitrogen (N), phosphorus (P), and potassium (K) were supplied individually, N proved most effective in improving fresh weight of seedlings growing on basalt and granite, whereas K, followed by P, was most effective for those growing on marlstone. Unexpectedly, the addition of N to marlstone negatively affected seedling growth, which was associated with repressed auxin biosynthesis in roots. CONCLUSIONS: Our data indicate that plants can recognize and adapt to complex mineral deficiency by adjusting hormonal homeostasis to achieve environmental sensitivity and developmental plasticity, which provide a basis for ecologically sound and sustainable strategies to maximize the use of natural resources and reduce the production of artificial fertilizers.

Unraveling the complexities of Cd-aniline composite pollution: Insights from standalone and joint toxicity assessments in a bacterial community.

Cadmium (Cd) and aniline frequently co-occur in industrial settings but have rarely been addressed as composite toxicants in terms of the overall toxicity despite extensive knowledge of the environmental impact of each individual pollutant. In this study, we attempt to assess the relation of individual and combined toxic effects of Cd and aniline using a bacterial consortium cultured from soils as a model system. Results showed that the consortial bacteria exhibited drastically stronger tolerance to stand-alone Cd and aniline in comparison to literature data acquired from single species studies. When occurring simultaneously, the joint toxicity displayed a concentration-dependent behavior that wasn't anticipated based on individual chemical tests. Specifically, additive effects manifested with Cd and aniline at their IC10s, but changed to synergistic when the concentrations increased to IC20, and finally transitioned into antagonistic at IC30s and beyond. In addition, co-occurring aniline appeared to have retarded the cellular accumulation of Cd while increasing the enzymatic activities of superoxide dismutase and catalase relative to that in Cd-alone treatments. Finally, the bacterial community experienced distinct compositional changes under solo and combined toxicities with several genera exhibiting inconsistent behavior between treatments of single and composite toxicants. Findings from this study highlight the complexity of bacterial response to composite pollutions and point to the need for more comprehensive references in risk and toxicology assessment at multi-chemical contamination sites.

Molecular Trade-Offs between Lattice Oxygen and Oxygen Vacancy Drive Organic Pollutant Degradation in Fungal Biomineralized Exoskeletons.

Fungal-mineral interactions can effectively alleviate cellular stress from organic pollutants, the production of which are expected to rapidly increase owing to the Earth moving into an unprecedented geological epoch, the Anthropocene. The underlying mechanisms that may enable fungi to combat organic pollution during fungal-mineral interactions remain unclear. Inspired by the natural fungal sporulation process, we demonstrate for the first time that fungal biomineralization triggers the formation of an ultrathin (hundreds of nanometers thick) exoskeleton, enriched in nanosized iron (oxyhydr)oxides and biomolecules, on the hyphae. Mapped biochemical composition of this coating at a subcellular scale via high spatial resolution (down to 50 nm) synchrotron radiation-based techniques confirmed aromatic C, C-N bonds, amide carbonyl, and iron (oxyhydr)oxides as the major components of the coatings. This nanobiohybrid system appeared to impart a strong (×2) biofunctionality for fungal degradation of bisphenol A through altering molecular-level trade-offs between lattice oxygen and oxygen vacancy. Together, fungal coatings could act as "artificial spores", which enable fungi to combat physical and chemical stresses in natural environments, providing crucial insights into fungal biomineralization and coevolution of the Earth's lithosphere and biosphere.

Testing the cation-hydration effect on the crystallization of Ca-Mg-CO3 systems.

Dolomite and magnesite are simple anhydrous calcium and/or magnesium carbonate minerals occurring mostly at Earth surfaces. However, laboratory synthesis of neither species at ambient temperature and pressure conditions has been proven practically possible, and the lack of success was assumed to be related to the strong solvation shells of magnesium ions in aqueous media. Here, we report the synthesis of MgCO3 and MgxCa(1-x)CO3 (0 < x < 1) solid phases at ambient conditions in the absence of water. Experiments were carried out in dry organic solvent, and the results showed that, although anhydrous phases were readily precipitated in the water-free environment, the precipitates' crystallinity was highly dependent on the Mg molar percentage content in the solution. In specific, magnesian calcite dominated in low [Mg(2+)]/[Ca(2+)] solutions but gave way to exclusive formation of amorphous MgxCa(1-x)CO3 and MgCO3 in high-[Mg(2+)]/[Ca(2+)] and pure-Mg solutions. At conditions of [Mg(2+)]/[Ca(2+)] = 1, both nanocrystals of Ca-rich protodolomite and amorphous phase of Mg-rich MgxCa(1-x)CO3 were formed. These findings exposed a previously unrecognized intrinsic barrier for Mg(2+) and CO3(2-) to develop long-range orders at ambient conditions and suggested that the long-held belief of cation-hydration inhibition on dolomite and magnesite mineralization needed to be reevaluated. Our study provides significant insight into the long-standing "dolomite problem" in geochemistry and mineralogy and may promote a better understanding of the fundamental chemistry in biomineralization and mineral-carbonation processes.

Mechanisms of Arbuscular Mycorrhizal Fungi Increasing Silicon Uptake by Rice.

Arbuscular mycorrhizal fungi (AMF) influence silicon (Si) uptake by plants, but the mechanisms remain unclear. This study investigated the mechanisms of AMF-mediated Si uptake by rice, a model Si-accumulating plant, and explored the tripartite interactions among AMF, Si, and phosphorus (P). AMF inoculation increased shoot Si content by 97% when supplied with silicic acid and by 29% with calcium silicate and upregulated expression of Si transporters Lsi1 and Lsi2 in roots. Supplying Si only to AMF hyphae increased the root Si content by 113%, indicating direct Si uptake by hyphae. Mechanisms of AMF-induced Si uptake were elucidated: 1) direct Si uptake by hyphae, 2) increased silicate dissolution, and 3) upregulation of Si transporters. Silicon application also increased AMF colonization by 28%, and the absence of interactions was observed on P uptake. Altogether, AMF support Si acquisition and Si fosters AMF colonization in rice, whereas the P uptake depends more on AMF than on Si.

A combined strategy to mitigate the accumulation of arsenic and cadmium in rice (Oryza sativa L.).

Arsenic and cadmium in rice grain are of growing concern in the global food supply chain. Paradoxically, the two elements have contrasting behaviors in soils, making it difficult to develop a strategy that can concurrently reduce their uptake and accumulation by rice plant. This study examined the combined impacts of watering (irrigation) schemes, different fertilizers and microbial populations on the bioaccumulation of arsenic and cadmium by rice as well as on rice grain yield. Compared to drain-flood and flood-drain treatments, continuously flooded condition significantly reduced the accumulation of cadmium in rice plant but the level of arsenic in rice grain remained above 0.2 mg/kg, which exceeded the China national food safety standard. Application of different fertilizers under continuously flooded condition showed that compared to inorganic fertilizer and biochar, manure addition effectively reduced the accumulation of arsenic over three to four times in rice grain and both elements were below the food safety standard (0.2 mg/kg) while significantly increasing the rice yield. Soil Eh was the critical factor in the bioavailability of cadmium, while the behavior of arsenic in rhizosphere was associated with the iron cycle. The results of the multi-parametric experiments can be used as a roadmap for low-cost and in-situ approach for producing safe rice without compromising the yield.

Isolation of dissolved organic matter from aqueous solution by precipitation with FeCl3: mechanisms and significance in environmental perspectives.

Ferric ions can bind strongly with dissolved organic matter (DOM), including humic acids (HA), fulvic acids (FA), and protein-like substances, whereas isolation of Fe-DOM precipitates (Fe-DOMP) and their biochemical characteristics remain unclear. In this work FeCl3 was used to isolate DOM components from various sources, including river, lake, soil, cow dung, and standard tryptophan and tyrosine, through precipitation at pH 7.5-8.5. The Fe-DOMP contribute to total DOM by approximately 38.6-93.8% of FA, 76.2% of HA and 25.0-30.4% of tryptophan and tyrosine, whilst fluorescence spectra allowed to monitor/discriminate the various DOM fractions in the samples. The relative intensity of the main infrared peaks such as 3406‒3383 cm-1 (aromatic OH), 1689‒1635 cm-1 (‒COOH), 1523-1504 cm-1 (amide) and 1176-1033 cm-1 (‒S=O) show either to decline or disappear in Fe‒DOMP. These results suggest the occurrence of Fe bonds with various functional groups of DOM, indicating the formation of π-d electron bonding systems of different strengths in Fe‒DOMP. The novel method used for isolation of Fe-DOMP shows promising in opening a new frontier both at laboratory and industrial purposes. Furthermore, results obtained may provide a better understanding of metal-organic complexes involved in the regulation of the long-term stabilization/sequestration of DOM in soils and waters.

Nickel bioaccessibility in soils with high geochemical background and anthropogenic contamination.

Abnormally high concentrations of metals including nickel (Ni) in soils result from high geochemical background (HB) or anthropogenic contamination (AC). Metal bioaccessibility in AC-soils has been extensively explored, but studies in HB-soils are limited. This study examined the Ni bioaccessibility in basalt and black shale derived HB-soils, with AC-soils and soils without contamination (CT) being used for comparison. Although HB- and AC-soils had similar Ni levels (123 ± 43.0 vs 155 ± 84.7 mg kg-1), their Ni bioaccessibility based on the gastric phase of the Solubility Bioaccessibility Research Consortium (SBRC) in vitro assay was different. Nickel bioaccessibility in HB-soils was 6.42 ± 3.78%, 2-times lower than the CT-soils (12.0 ± 9.71%) and 6-times lower than that in AC-soils (42.6 ± 16.3%). Based on the sequential extraction, a much higher residual Ni fractionation in HB-soils than that in CT- and AC-soils was observed (81.9 ± 9.52% vs 68.6 ± 9.46% and 38.7 ± 16.0%). Further, correlation analysis indicate that the available Ni (exchangeable + carbonate-bound + Fe/Mn hydroxide-bound) was highly correlated with Ni bioaccessibility, which was also related to the organic carbon content in soils. The difference in co-localization between Ni and other elements (Fe, Mn and Ca) from high-resolution NanoSIMS analysis provided additional explanation for Ni bioaccessibility. In short, based on the large difference in Ni bioaccessibility in geochemical background and anthropogenic contaminated soils, it is important to base contamination sources for proper risk assessment of Ni-contaminated soils.

Transformation of tetracycline antibiotics with goethite: Mechanism, kinetic modeling and toxicity evaluation.

Tetracycline antibiotics (TCs) are a group of the top selling and widely used antibiotics that have been frequently detected in various environments. The interaction between TCs and goethite (α-FeOOH), one of the most common crystalline oxide minerals in aqueous environment and soil, is unclear. Apart from adsorption, this study firstly demonstrated that transformation of tetracycline (TTC) occurred in the presence of goethite. The transformation kinetics and mechanism of TTC with goethite were investigated to gain a better understanding of the fate of TCs in the natural environment. The results showed that the transformation of TCs by goethite explicitly exhibited two-stage kinetics, wherein an initial period of fast transformation was followed by a continuous slow transformation. Hydroxyl groups on goethite were identified as major reactive sites, among which singly coordinated hydroxyls (FeOH) were more reactive than doubly coordinated hydroxyls (Fe2OH) towards the transformation of TTC. On the basis of transformation rates, speciation of TTC and functional groups on goethite surface, a kinetic model was established successfully describing the transformation of TTC by goethite under conditions of varying reactant concentration and pH. The transformation of TTC by goethite mainly resulted in a N,N-dedimethylation product that did not show antimicrobial properties towards Escherichia coli. This study indicates that Fe(III)-(hydro)oxides in soils and sediments may play an important role in the natural attenuation of tetracycline antibiotics and their bioactivity.

Comparing CaCl2, EDTA and DGT methods to predict Cd and Ni accumulation in rice grains from contaminated soils.

Urbanization and industrialization have elevated metal concentrations in soils. However, systematic investigation on their availability in regional soils under industrial impacts is lacking. In this study, 230 paired soil-rice samples were collected from two areas in Southeast China, with low and high industrial impacts. Classic equilibrium-based CaCl2 and EDTA extraction methods, and dynamic-based diffusive gradients in thin-films (DGT) technique were used to study metal availability in soils, with the results being compared with metal concentrations in soils and rice grains. Generally, Cd, Ni, Cu, Zn, Cr and Pb concentrations in soils exceeded the Chinese Soil Quality Standard (GB15618-2018), whereas only Cd and Ni in some rice grains exceeded the Chinese Safety Guidelines. CaCl2 and EDTA extractions, DGT method and soil total metal concentrations provided good predication of grain Cd (R = 0.51-0.66, p < 0.01), whereas only CaCl2 and DGT tests provided good predication of grain Ni (R = 0.36-0.47, p < 0.01). Overall, CaCl2 extraction best predicted Cd and Ni accumulation in rice grains, explaining 66% of grain Cd and 47% of grain Ni. The extraction rate of available Cd was higher than that of Ni, indicating higher Cd availability than Ni, consistent with the parameters (response time, Tc, and desorption rate, k-1) from DIFS (DGT-induced flux in soils) model and bioconcentration factor values. This study showed that, at regional scale, CaCl2 extraction method is efficient in predicting Cd and Ni accumulation in rice grains from contaminated soils.

Microbial flocculation by Bacillus mucilaginosus: Applications and mechanisms.

Microbiological flocculation in wastewater by a strain of Bacillus mucilaginosus was examined and the flocculation mechanism was investigated using Coomassie brilliant blue reaction, Anthrone reaction, thin-layer chromatography (TLC), scanning electronic microscope, and infrared spectroscopy. The GY03 strain, isolated from farmland soil, was identified as B. mucilaginosus by its morphology and 16S rDNA sequence. Cultivated in a nitrogen-free medium, the flocculation material (bacterium-mineral complex) was used to treat domestic, brewage, and pharmaceutical wastewater. On the basis of one-way experimental results, orthogonal experiments were carried out and the optimum processing conditions of the microbial flocculants were obtained. In the optimal conditions, the maximal removal ratio of COD in domestic, brewage, and pharmaceutical wastewater reached 74.6%, 70.5%, and 66.2%, respectively; the maximal removal ratio of BOD was 42.3%, 77.4%, and 41.7%, respectively; and the maximal removal of SS amounted 93.3%, 93.6%, and 88.4%, respectively. The treatment to kaolin suspended liquid by the GY03 strain may act as a model of studying microbial flocculation mechanisms in which bridging and charge neutralization hypothesis were proposed as the critical reasons based upon the experimental observations.

A composite reactor with wetted-wall column for mineral carbonation study in three-phase systems.

Despite the availability of various reactors designed to study gas-liquid reactions, no appropriate devices are available to accurately investigate triple-phased mineral carbonation reactions involving CO2 gas, aqueous solutions (containing divalent cations), and carbonate minerals. This report presents a composite reactor that combines a modified conventional wetted-wall column, a pH control module, and an attachment to monitor precipitation reactions. Our test and calibration experiments show that the absorption column behaved largely in agreement with theoretical predictions and previous observations. Experimental confirmation of CO2 absorption in NaOH and ethanolamine supported the effectiveness of the column for gas-liquid interaction. A test run in the CO2-NH3-MgCl2 system carried out for real time investigation of the relevant carbonation reactions shows that the reactor's performance closely followed the expected reaction path reflected in pH change, the occurrence of precipitation, and the rate of NH3 addition, indicating the appropriateness of the composite device in studying triple-phase carbonation process.

Nanoparticle delivery by controlled bacteria.

We present a new approach for nano-object directional delivery by bacteria based upon a taxis-controlled mechanism. In this method, a stimulus is used to direct the bacteria's motion. When carrying nano-objects, the bacteria demonstrated the ability to deliver the "loads" to targets where the stimulus is positioned. The scheme of using taxis for targeted delivery may hold a promising future for a new route to bridge nanotechnology and biotechnology.

Aqueous carbonation of natural brucite: relevance to CO2 sequestration.

Carbonation of natural brucite in H2O and diluted HCl is investigated at room temperature and moderate pCO2 to explore the products' mineralogy and reaction kinetics. Results show nesquehonite is by far the dominant carbonate species formed, despite its poorer thermodynamic stability relative to magnesite and possibly hydromagnesite. Time-dependent measurements reveal carbonate formation within 30 min, regardless of the original acidity of the slurry. However, while the fraction of reacted brucite in H2O increases gradually over time and approaches unity ( approximately 98%) at 2.5 h, it rises rapidly in HCl within the first hour and levels off thereafter, leaving a significant amount of brucite unreacted. Such behavior suggests that the initial quantity of Mg2+ affects the reaction kinetics. Fitting a pseudo first-order rate law to the data yields a higher rate constant for the HCl experiments. These observations may imply that the carbonation does not proceed through heterogeneous reaction between gaseous CO2 and solid brucite. Solution chemistry analysis indicates that most CO2 stays in aqueous phase in both media; however, the concentration of HCO3(-) becomes high in H2O after about 2 h, agreeing with the observed inferior carbonation extent in HCl.

Design and application of the method for isolating magnetotactic bacteria.

A simple apparatus was designed to effectively isolate magnetotactic bacteria from soils or sediments based on their magnetotaxis. Through a series of processes including sample incubation, MTB harvesting, isolation, purification and identification, several strains of bacteria were isolated from the samples successfully. By Transmission Electron Microscopy (TEM) and Energy-Dispersive X-ray Analysis (EDXA), these bacteria were certificated to be magnetotactic bacteria. The phylogenetic relationship between the isolated magnetic strains and some known magnetotactic bacteria was inferred by the construction of phylogenetic tree based on 16SrDNA sequences. This apparatus has been proven to have the advantages of being inexpensive, simple to assemble, easy to perform and highly efficient to isolate novel magnetotactic bacteria. The research indicated that the combined approach of harvesting MTB by home-made apparatus and the method of plate colony isolation could purify and isolate magnetotactic bacteria effectively.

Direction specific interactions of 1,4-dicarboxylic acid with calcite surfaces.

Interactions of succinic acid (SUC) with the {104} cleavage faces of calcite show a strong preference in crystallographic directions. In situ atomic force microscopy revealed that the morphology of etch pits on the crystal surfaces experienced a transition from the common rhombus to a hexagon upon the introduction of SUC. The pit shape further evolved from 6-sided to 7-sided and eventually to 5-sided with increasing concentrations of SUC. Analysis indicates that the morphology changes may result from SUC preferentially binding to the [42] and [010] edges of the (104) plane to selectively slow down their step speed.