Porous Nano-Fiber Structure of Modified Electrospun Chitosan GBR Membranes Improve Osteoblast Calcium Phosphate Deposition in Osteoblast-Fibroblast Co-Cultures.

Desirable characteristics of electrospun chitosan membranes (ESCM) for guided bone regeneration are their nanofiber structure that mimics the extracellular fiber matrix and porosity for the exchange of signals between bone and soft tissue compartments. However, ESCM are susceptible to swelling and loss of nanofiber and porous structure in physiological environments. A novel post-electrospinning method using di-tert-butyl dicarbonate (tBOC) prevents swelling and loss of nanofibrous structure better than sodium carbonate treatments. This study aimed to evaluate the hypothesis that retention of nanofiber morphology and high porosity of tBOC-modified ESCM (tBOC-ESCM) would support more bone mineralization in osteoblast-fibroblast co-cultures compared to Na2CO3 treated membranes (Na2CO3-ESCM) and solution-cast chitosan solid films (CM-film). The results showed that only the tBOC-ESCM retained the nanofibrous structure and had approximately 14 times more pore volume than Na2CO3-ESCM and thousands of times more pore volume than CM-films, respectively. In co-cultures, the tBOC-ESCM resulted in a significantly greater calcium-phosphate deposition by osteoblasts than either the Na2CO3-ESCM or CM-film (p < 0.05). This work supports the study hypothesis that tBOC-ESCM with nanofiber structure and high porosity promotes the exchange of signals between osteoblasts and fibroblasts, leading to improved mineralization in vitro and thus potentially improved bone healing and regeneration in guided bone regeneration applications.

Effects of different oxidants on the behaviour of microplastic hetero-aggregates.

Microplastic hetero-aggregates are stable forms of microplastics in the aqueous environment. However, when disinfecting water containing microplastic hetero-aggregates, the response of them in water to different oxidizing agents and the effect on water quality have not been reported. Our results showed that Ca(ClO)2, K2S2O8, and sodium percarbonate (SPC) treatment could lead to the disaggregation of microplastic hetero-aggregates as well as a rise in cell membrane permeability, which caused a large amount of organic matter to be released. When the amount of oxidant dosing is insufficient, the oxidant cannot completely degrade the released organic matter, resulting in DOC, DTN, DTP and other indicators being higher than before oxidation, thus causing secondary pollution of the water body. In comparison, K2FeO4 can purify the water body stably without destroying the microplastic hetero-aggregates, but it only weakly inhibits the toxic cyanobacteria Microcystis and Pseudanabaena, which may cause cyanobacterial bloom as well as algal toxin and odorant contamination in practical application. Compared with the other oxidizers, K2S2O8 provides better inhibition of toxic cyanobacteria and has better ecological safety. Therefore, when treating microplastic-containing water bodies, we should consider both water purification and ecological safety, and select appropriate oxidant types and dosages to optimize the water treatment.

Deterioration phenomenon of Pb-contaminated aqueous solution remediation and enhancement mechanism of nano-hydroxyapatite-assisted biomineralization.

Modern metallurgical and smelting activities discharge the lead-containing wastewater, causing serious threats to human health. Bacteria and urease applied to microbial-induced carbonate precipitation (MICP) and enzyme-induced carbonate precipitation (EICP) are denatured under high Pb2+ concentration. The nano-hydroxyapatite (nHAP)-assisted biomineralization technology was applied in this study for Pb immobilization. Results showed that the extracellular polymers and cell membranes failed to secure the urease activity when subjected to 60 mM Pb2+. The immobilization efficiency dropped to below 50% under MICP, whereas it due to a lack of extracellular polymers and cell membranes dropped to below 30% under EICP. nHAP prevented the attachment of Pb2+ either through competing with bacteria and urease or promoting Ca2+/Pb2+ ion exchange. Furthermore, CO32- from ureolysis replaced the hydroxyl (-OH) in hydroxylpyromorphite to encourage the formation of carbonate-bearing hydroxylpyromorphite of higher stability (Pb10(PO4)6CO3). Moreover, nHAP application overcame an inability to provide nucleation sites by urease. As a result, the immobilization efficiency, when subjected to 60 mM Pb2+, elevated to above 80% under MICP-nHAP and to some 70% under EICP-nHAP. The findings highlight the potential of applying the nHAP-assisted biomineralization technology to Pb-containing water bodies remediation.

Statistical modelling, optimization, and mechanistic exploration of novel ureolytic Enterobacter hormaechei IITISM-SA3 in cadmium immobilization under microbial inclusive and cell-free conditions through microbially induced calcite precipitation.

The study aimed to evaluate the potential of a novel isolated ureolytic Enterobacter hormaechei IITISM-SA3 in cadmium bioremoval through MICP. The optimization and modelling of the biotic and abiotic factors affecting the process of mineralization were also performed. In addition, the underlying mechanism of MICP-driven Cd mineralization under microbial-inclusive and cell-free conditions was revealed and supported through the characterization of the bio-precipitates obtained using various characterization techniques. The results indicated that the isolate could remove 97.18% Cd2+ of 11.4 ppm under optimized conditions of 36.86 h, pH 7.63, and biomass dose of 1.75 ml. Besides, the presence and absence of bacterial cells were found to influence both the morphologies and crystalline structures of precipitates. The precipitates obtained under microbial-inclusive conditions showed typical rhombohedral crystalline structures of the composition comprising CaCO3, CdCO3, and 0.67Ca0.33CdCO3. However, the crystalline nature of the precipitate reduced to a nano-sized granular structure in cell-free media. Unlike the cadmium mineralization process under microbial-inclusive media, where bacterial cells serve as nucleation sites for crystallization, the carbonate precipitation effectively captures Cd2+ through co-precipitation, chemisorption, or alternative mechanisms involving interactions between metal ions and CaCO3 under cell-free conditions. The findings presented suggest that using cell-free culture supernatant enriched with carbonate ions provides an avenue that could be harnessed for sustainable metal remediation.

Interaction of microorganisms with carbonates from the micro to the macro scales during sedimentation: Insights into the early stage of biodegradation.

The assembly process of Organic Matter (OM) from single molecules to polymers and the formation process of Ca-CO3 ion-pairs are explored at the micro-scale, and then the relationship between OM and carbonate based on the results of microbially-induced carbonate precipitation (MICP) laboratory experiments is established at the macro-scale. Molecular dynamics (MD) is used to model the assembly of OM (a) in an aqueous solution, (b) on surfaces of calcite (10 1‾ 4) crystals and (c) on defective calcite (101‾ 4) crystal surfaces. From the MICP experiments, carbonate minerals containing abundant OM were precipitated and were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffractometry (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The results of the MD show that OM is assembled into polymers in all three simulation systems. Although the Ca-CO3 ion-pairs and OM were briefly combined, the aggregation assembly of OM molecules and the precipitation of carbonate calcium are not related in the long run. The highly specific surface area of the defective calcite shows an increase in the adsorption of OM. The van der Waals forces, which are primarily responsible for controlling the assembly of OM molecules, increase with the degree of aggregation. According to the MICP experiments, OM is enriched on the mineral surfaces, and more OM is found at the steps of defective crystals with their larger surface areas. Through MD and MICP laboratory experiments, this work systematically describes the interaction of OM and carbonate minerals from the micro to the macro scales, and this provides insight into the interaction between OM and carbonates and biogeochemical processes related to the accumulation of OM in sediments.

High CO2 permeation using a new Ce0.85Gd0.15O2-δ-LaNiO3 composite ceramic-carbonate dual-phase membrane.

This work shows the synthesis, characterization and evaluation of dense-ceramic membranes made of Ce0.85Gd0.15O2-δ-LaNiO3 (CG-LN) composites, where the fluorite-perovskite ratio (CG:LN) was varied as follows: 75:25, 80:20 and 85:15 wt.%. Supports were initially characterized by XRD, SEM and electrical conductivity (using vacuum and oxygen atmospheres), to determine the composition, microstructural and ionic-electronic conductivity properties. Later, supports were infiltrated with an eutectic carbonates mixture, producing the corresponding dense dual-phase membranes, in which CO2 permeation tests were conducted. Here, CO2 permeation experiments were performed from 900 to 700°C, in the presence and absence of oxygen (flowed in the sweep membrane side). Results showed that these composites possess high CO2 permeation properties, where the O2 addition significantly improves the ionic conduction on the sweep membrane side. Specifically, the GC80-LN20 composition presented the best results due to the following physicochemical characteristics: high electronic and ionic conductivity, appropriate porosity, interconnected porous channels, as well as thermal and chemical stabilities between the composite support and carbonate phases.

Implications of dietary carbon incorporation in fish carbonates for the global carbon cycle.

Marine bony fish are important participants in Earth's carbon cycle through their contributions to the biological pump and the marine inorganic carbon cycle. However, uncertainties in the composition and magnitude of fish contributions preclude their integration into fully coupled carbon-climate models. Here, we consider recent upwards revisions to global fish biomass estimates (2.7-9.5×) and provide new stable carbon isotope measurements that show marine fish are prodigious producers of carbonate with unique composition. Assuming the median increase (4.17×) in fish biomass estimates is linearly reflected in fish carbonate (ichthyocarbonate) production rate, marine fish are estimated to produce between 1.43 and 3.99 Pg CaCO3 yr-1, but potentially as much as 9.03 Pg CaCO3 yr-1. Thus, marine fish carbonate production is equivalent to or potentially higher than contributions by coccolithophores or pelagic foraminifera. New stable carbon isotope analyses indicate that a significant proportion of ichthyocarbonate is derived from dietary carbon, rather than seawater dissolved inorganic carbon. Using a statistical mixing model to derive source contributions, we estimate ichthyocarbonate contains up to 81 % dietary carbon, with average compositions of 28-56 %, standing in contrast to contents <10 % in other biogenic carbonate minerals. Results also indicate ichthyocarbonate contains 5.5-40.4 % total organic carbon. When scaled to the median revised global production of ichthyocarbonate, an additional 0.08 to 1.61 Pg C yr-1 can potentially be added to estimates of fish contributions to the biological pump, significantly increasing marine fish contributions to total surface carbon export. Our integration of geochemical and physiological analyses identifies an overlooked link between carbonate production and the biological pump. Since ichthyocarbonate production is anticipated to increase with climate change scenarios, due to ocean warming and acidification, these results emphasize the importance of quantitative understanding of the multifaceted role of marine fish in the global carbon cycle.

Green and effective remediation of heavy metals contaminated water using CaCO3 vaterite synthesized through biomineralization.

Heavy metal pollution has attracted significant attention due to its persistent presence in aquatic environments. A novel vaterite-based calcium carbonate adsorbent, named biogenic CaCO3, was synthesized utilizing a microbially induced carbonate precipitation (MICP) method to remediate heavy metal-contaminated water. The maximum Cd2+ removal capacity of biogenic CaCO3 was 1074.04 mg Cd2+/g CaCO3 with a high Cd2+ removal efficiency greater than 90% (initial Cd2+ concentration 400 mg/L). Furthermore, the biogenic CaCO3 vaterite, induced by microbial-induced calcium carbonate precipitation (MICP) process, demonstrated a prolonged phase transformation to calcite and enhanced stability. This resulted in a sustained high effectiveness (greater than 96%) following six consecutive recycling tests. Additionally, X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses revealed that the semi-stable vaterite type of biogenic CaCO3 spontaneously underwent dissolution and recrystallization to form thermodynamic stable calcite in aquatic environments. However, the presence of Cd2+ leads to the transformation of vaterite into CdCO3 rather than undergoing direct converting to calcite. This transformation is attributed to the relatively low solubility of CdCO3 compared to calcite. Meanwhile, the biogenic CaCO3 proved to be an efficient and viable method for the removal of Pb2+, Cu2+, Zn2+, Co2+, Ni2+ and Mn2+ from water samples, surpassing the performance of previously reported adsorbents. Overall, the efficient and promising adsorbent demonstrates potential for practical in situ remediation of heavy metals-contaminated water.

Mobility, speciation of cadmium, and bacterial community composition along soil depths during microbial carbonate precipitation under simulated acid rain.

An overexploitation of earth resources results in acid deposition in soil, which adversely impacts soil ecosystems and biodiversity and affects conventional heavy metal remediation using immobilization. A series of column experiments was conducted in this study to compare the cadmium (Cd) retention stability through biotic and abiotic carbonate precipitation impacted by simulated acid rain (SAR), to build a comprehensive understanding of cadmium speciation and distribution along soil depth and to elucidate the biogeochemical bacteria-soil-heavy metal interfaces. The strain of Sporosarcina pasteurii DSM 33 was used to trigger the biotic carbonate precipitation and cultivated throughout the 60-day column incubation. Results of soil pH, electrical conductivity (EC), and quantitative CdCO3/CaCO3 analysis concluded that the combination of biotic and abiotic soil treatment could reinforce soil buffering capacity as a strong defense mechanism against acid rain disturbance. Up to 1.8 ± 0.04 U/mg urease enzyme activity was observed in combination soil from day 10, confirming the sustained effect of urease-mediated microbial carbonate precipitation. Cadmium speciation and distribution analyses provided new insights into the dual stimulation of carbonate-bound and Fe/Mn-bound phases of cadmium immobilization under microbially induced carbonate precipitation (MICP). As confirmed by the microbial community analysis, outsourcing urea triggered diverse microbial metabolic responses, notably carbonate precipitation and dissimilatory iron metabolism, in both oxygen-rich topsoil and oxygen-depleted subsurface layers. The overall investigation suggests the feasibility of applying MICP for soil Cd remediation under harsh environments and stratagem by selecting microbial functionality to overcome environmental challenges.

Properties and mechanisms of steel slag strengthening microbial cementation of cyanide tailings.

The advantages of microbial induced carbonate precipitation (MICP) as bio-cementation technology for tailings-solidification are under extensive investigation. In order to improve performance of bio-cementation, many strengthening materials were applied to the bio-cementation of tailings. Steel slag (SS) is a kind of industrial solid waste, its chemical composition and mineral composition are similar to cement, and it has a certain application prospect as an auxiliary cementing material. In this study, the properties and mechanism of SS strengthening MICP cementation of cyanide tailings (CT) were investigated. The results showed that Sporosarcina pasteurii growth is not inhibited by SS, and Sporosarcina pasteurii can promote the hydration reaction of SS, providing a suitable alkaline environment and Ca2+, promoting the production of more CaCO3 in the MICP process. When 200 mL of CT leachate was added 1.4 g SS (200-400 mesh), the adsorption of Cu, Pb, Zn, Cd, total cyanide (T-CN), and free cyanide (F-CN) reached 48.05%, 44.28%, 36.25%, 16.67%, 79.05%, and 67.20%, respectively. The maximum unconfined compressive strength（UCS） of the cemented body (with 5%, 150 mesh SS) was 1.97 MPa, which was 3.396 times as high as that without SS. The cemented body with the addition of SS (5%, 150 mesh) contained more carbonate bound Cu (2.75%), Pb (4.89%), Zn (5.37%), and Cd (5.75%), and less exchangeable Cu (3.65%), Pb (6.85%), Zn (2.27%), and Cd (4.42%) than that without SS. In summary, the addition of SS improved the UCS of cemented bodies and the stability of heavy metals and cyanide, reduced the environmental risks existing in the process of CT storage. Meanwhile, it also provides new ideas for resource utilization of industrial solid waste SS and improvement of mine filling materials.

Potential use of two Serratia strains for cadmium remediation based on microbiologically induced carbonate precipitation and their cadmium resistance.

Cadmium (Cd) presence and bioavailability in soils is a serious concern for cocoa producers. Cocoa plants can bioaccumulate Cd that can reach humans through the food chain, thus posing a threat to human health, as Cd is a highly toxic metal. Currently, microbiologically induced carbonate precipitation (MICP) by the ureolytic path has been proposed as an effective technique for Cd remediation. In this work, the Cd remediation potential and Cd resistance of two ureolytic bacteria, Serratia sp. strains 4.1a and 5b, were evaluated. The growth of both Serratia strains was inhibited at 4 mM Cd(II) in the culture medium, which is far higher than the Cd content that can be found in the soils targeted for remediation. Regarding removal efficiency, for an initial concentration of 0.15 mM Cd(II) in liquid medium, the maximum removal percentages for Serratia sp. 4.1.a and 5b were 99.3% and 99.57%, respectively. Their precipitates produced during Cd removal were identified as calcite by X-ray diffraction. Energy dispersive X-ray spectroscopy analysis showed that a portion of Cd was immobilized in this matrix. Finally, the presence of a partial gene from the czc operon, involved in Cd resistance, was observed in Serratia sp. 5b. The expression of this gene was found to be unaffected by the presence of Cd(II), and upregulated in the presence of urea. This work is one of the few to report the use of bacterial strains of the Serratia genus for Cd remediation by MICP, and apparently the first one to report differential expression of a Cd resistance gene due to the presence of urea.

A Novel Spectrophotometric Method for Determination of Percarbonate by Using N, N-Diethyl-P-Phenylenediamine as an Indicator and Its Application in Activated Percarbonate Degradation of Ibuprofen.

Sodium percarbonate (SPC) concentration can be determined spectrophotometrically by using N, N-diethyl-p-phenylenediamine (DPD) as an indicator for the first time. The ultraviolet-visible spectrophotometry absorbance of DPD•+ measured at 551 nm was used to indicate SPC concentration. The method had good linearity (R2 = 0.9995) under the optimized experimental conditions (pH value = 3.50, DPD = 4 mM, Fe2+ = 0.5 mM, and t = 4 min) when the concentration of SPC was in the range of 0-50 µM. The blank spiked recovery of SPC was 95-105%. The detection limit and quantitative limit were 0.7-1.0 µM and 2.5-3.3 µM, respectively. The absorbance values of DPD•+ remained stable within 4-20 min. The method was tolerant to natural water matrix and low concentration of hydroxylamine (<0.8 mM). The reaction stoichiometric efficiency of SPC-based advanced oxidation processes in the degradation of ibuprofen was assessed by the utilization rate of SPC. The DPD and the wastewater from the reaction were non-toxic to Escherichia coli. Therefore, the novel Fe2+/SPC-DPD spectrophotometry proposed in this work can be used for accurate and safe measurement of SPC in water.

Biopolymer-assisted enzyme-induced carbonate precipitation for immobilizing Cu ions in aqueous solution and loess.

Wastewater, discharged in copper (Cu) mining and smelting, usually contains a large amount of Cu2+. Immobilizing Cu2+ in aqueous solution and soils is deemed crucial in preventing its migration into surrounding environments. In recent years, the enzyme-induced carbonate precipitation (EICP) has been widely applied to Cu immobilization. However, the effect of Cu2+ toxicity denatures and even inactivates the urease. In the present work, the biopolymer-assisted EICP technology was proposed. The inherent mechanism affecting Cu immobilization was explored through a series of test tube experiments and soil column tests. Results indicated that 4 g/L chitosan may not correspond to a higher immobilization efficiency because it depends as well on surrounding pH conditions. The use of Ca2+ not only played a role in further protecting urease and regulating the environmental pH but also reduced the potential for Cu2+ to migrate into nearby environments when malachite and azurite minerals are wrapped by calcite minerals. The species of carbonate precipitation that are recognized in the numerical simulation and microscopic analysis supported the above claim. On the other hand, UC1 (urease and chitosan colloid) and UC2 (urea and calcium source) grouting reduced the effect of Cu2+ toxicity by transforming the exchangeable state-Cu into the carbonate combination state-Cu. The side effect, induced by 4 g/L chitosan, promoted the copper-ammonia complex formation in the shallow ground, while the acidic environments in the deep ground prevented Cu2+ from coordinating with soil minerals. These badly degraded the immobilization efficiency. The Raman spectroscopy and XRD test results tallied with the above results. The findings shed light on the potential of applying the biopolymer-assisted EICP technology to immobilizing Cu ions in water bodies and sites.

Resilience of Emiliania huxleyi to future changes in subantarctic waters.

Lower pH and elevated temperature alter phytoplankton growth and biomass in short-term incubations, but longer-term responses and adaptation potential are less well-studied. To determine the future of the coccolithophore Emiliania huxleyi, a mixed genotype culture from subantarctic water was incubated for 720 days under present-day temperature and pH, and also projected future conditions by the year 2100. The future population exhibited a higher growth rate relative to present-day cells transferred to future conditions after 309 days, indicating adaptation or genotype selection; this was reflected by an increase in optimum growth temperature of ~2.5°C by the end of the experiment. Following transfer to opposing conditions in short-term cross-over incubations, cell volume responded rapidly, within eight generations, confirming trait plasticity. The changes in growth rate and cell volume were larger than reported in previous single stressor relationships and incubations, suggesting synergistic or additive effects of combined elevated temperature and lower pH and highlighting the importance of long-term multiple stressor experiments. At the end of the incubation there were no significant differences in cellular composition (particulate organic content and chlorophyll a), or primary production between present-day and future populations. Conversely, two independent methods showed a 50% decrease in both particulate inorganic carbon and calcification rate, consistent with the decrease in cell volume, in the future population. The observed plasticity and adaptive capacity of E. huxleyi indicate resilience to future conditions in subantarctic waters, although changes in cell volume and carbonate may alter grazing loss and cell ballast, so influencing carbon export to the deep ocean.

Anion elements incorporation into corals skeletons: Experimental approach for biomineralization and paleo-proxies.

The elemental composition of coral skeletons provides important information for palaeoceanographic reconstructions and coral biomineralization. Partition of anions and their stable isotopes in coral skeleton enables the reconstruction of past seawater carbonate chemistry, paleo-CO2, and past climates. Here, we investigated the partition of B, S, As, Br, I, and Mo into the skeletons of two corals, Acropora cervicornis and Pocillopora damicornis, as a function of calcium and carbonate concentrations.* Anion-to-calcium ratio in the corals (An/CaCoral) were correlated with the equivalent ratios in the culturing seawater (An/CO32-SW). Negative intercepts of these relationships suggest a higher CO32- concentration in the coral extracellular calcifying fluid (ECF) relative to seawater, from which the skeleton precipitates. The enrichment factor of CO32- at the ECF was 2.5 for A. cervicornis and 1.9 for P. damicornis, consistent with their relative calcification rates. The CO32-ECF concentrations thus calculated are similar to those proposed by previous studies based on B/Ca coupled with δ11B, as well as by direct measurements using microsensors and fluorescent dyes. Rayleigh fractionation modeling demonstrates a uniform Ca utilization at various CaSW concentrations, providing further evidence that coral calcification occurs directly from a semiclosed seawater reservoir as reported previously. The partition coefficients reported in this study for B, S, As, Br, I, and Mo open up wide possibilities for past ocean chemistry reconstructions based on Br having long residence time (~160 Ma) in the ocean. Other elements like S, Mo, B, as well as pCO2 may also be calculated based on these elements in fossil coral.

Oyster reefs' control of carbonate chemistry-Implications for oyster reef restoration in estuaries subject to coastal ocean acidification.

Globally, oyster reef restoration is one of the most widely applied coastal restoration interventions. While reefs are focal points of processes tightly linked to the carbonate system such as shell formation and respiration, how these processes alter reef carbonate chemistry relative to the surrounding seawater is unclear. Moreover, coastal systems are increasingly impacted by coastal acidification, which may affect reef carbonate chemistry. Here, we characterized the growth of multiple constructed reefs as well as summer variations in pH and carbonate chemistry of reef-influenced seawater (in the middle of reefs) and ambient seawater (at locations ~50 m outside of reefs) to determine how reef chemistry was altered by the reef community and, in turn, impacts resident oysters. High frequency monitoring across three subtidal constructed reefs revealed reductions of daily mean and minimum pH (by 0.05-0.07 and 0.07-0.12 units, respectively) in seawater overlying reefs relative to ambient seawater (p < .0001). The proportion of pH measurements below 7.5, a threshold shown to negatively impact post-larval oysters, were 1.8×-5.2× higher in reef seawater relative to ambient seawater. Most reef seawater samples (83%) were reduced in total alkalinity relative to ambient seawater samples, suggesting community calcification was a key driver of modified carbonate chemistry. The net metabolic influence of the reef community resulted in reductions of CaCO3 saturation state in 78% of discrete samples, and juvenile oysters placed on reefs exhibited slower shell growth (p < .05) compared to oysters placed outside of reefs. While differences in survival were not detected, reef oysters may benefit from enhanced survival or recruitment at the cost of slowed growth rates. Nevertheless, subtidal restored reef communities modified seawater carbonate chemistry in ways that likely increased oyster vulnerability to acidification, suggesting that carbonate chemistry dynamics warrant consideration when determining site suitability for oyster restoration, particularly under continued climate change.

Armoring of MgO by a Passivation Layer Impedes Direct Air Capture of CO2.

It has been proposed to use magnesium oxide (MgO) to separate carbon dioxide directly from the atmosphere at the gigaton level. We show experimental results on MgO single crystals reacting with the atmosphere for longer (decades) and shorter (days to months) periods with the goal of gauging reaction rates. Here, we find a substantial slowdown of an initially fast reaction as a result of mineral armoring by reaction products (surface passivation). In short-term experiments, we observe fast hydroxylation, carbonation, and formation of amorphous hydrated magnesium carbonate at early stages, leading to the formation of crystalline hydrated Mg carbonates. The preferential location of Mg carbonates along the atomic steps on the crystal surface of MgO indicates the importance of the reactive site density for carbonation kinetics. The analysis of 27-year-old single-crystal MgO samples demonstrates that the thickness of the reacted layer is limited to ∼1.5 µm on average, which is thinner than expected and indicates surface passivation. Thus, if MgO is to be employed for direct air capture of CO2, surface passivation must be circumvented.

Stromatolite-like Structures Within Microbially Laminated Sandstones of the Paleoarchean Moodies Group, Barberton Greenstone Belt, South Africa.

We report abundant small calcareous mounds associated with fossilized kerogenous microbial mats in tidal-facies sandstones of the predominantly siliciclastic Moodies Group (ca. 3.22 Ga) of the Barberton Greenstone Belt (BGB), South Africa and Eswatini. Most of the bulbous, internally microlaminated mounds are several centimeters in diameter and formed at the sediment-water interface contemporaneously with sedimentation. They originally consisted of Fe-Mg-Mn carbonate, which is now largely silicified; subtle internal compositional laminations are composed of organic matter and sericite. Their presence for >6 km along strike, their restriction to the inferred photic zone, and the internal structure suggest that mineral precipitation was induced by photosynthetic microorganisms. Similar calcareous mounds in this unit also occur within and on top of fluid-escape conduits, suggesting that carbonate precipitation may either have occurred abiogenically or involved chemotrophic metabolism(s) utilizing the oxidation of organic matter, methane, or hydrogen, the latter possibly generated by serpentinization of underlying ultramafic rocks. Alternatively or additionally, carbonate may have precipitated abiotically where heated subsurface fluids, sourced by the intrusion of a major Moodies-age sill, reached the tidal flats. In summary, precipitation mechanisms may have been variable; the calcareous mounds may represent "hybrid carbonates" that may have originated from the small-scale overlap of bioinduced and abiotic processes in space and time. Significantly, the widespread occurrence of these stromatolite-like structures in a fully siliciclastic, high-energy tidal setting broadens search criteria in the search for life on Mars while their possible hybrid origin challenges our ability to unambiguously identify a biogenic component.

Synthesis and Characterization of Nano-Hydroxyapatite Obtained from Eggshell via the Hydrothermal Process and the Precipitation Method.

Hydroxyapatite (HA) is a major component of the inorganic minerals in the hard tissues of humans and has been widely used as a biomedical ceramic material in orthopedic and dentistry applications. Because human bone contains several impurities, including carbonates, chlorides, fluorides, magnesium, and strontium, human bone minerals differ from stoichiometric HA. Additionally, natural bone is composed of nano-sized HA, and the nanoscale particles exhibit a high level of biological activity. In this paper, HA is prepared via the hydrothermal process because its reaction conditions are easy to control and it has been shown to be quite feasible for large-scale production. Therefore, the hydrothermal process is an effective and convenient method for the preparation of HA. Furthermore, eggshell is adopted as a source of calcium, and mulberry leaf extract is selectively added to synthesize HA. The eggshell accounts for 11% of the total weight of a whole egg, and it consists of calcium carbonate, calcium phosphate, magnesium carbonate, and organic matter. Eggshell contains a variety of trace elements, such as magnesium and strontium, making the composition of the synthesized HA similar to that of the human skeleton. These trace elements exert considerable benefits for bone growth. Moreover, the use of eggshell as a raw material can permit the recycling of biowaste and a reduction in process costs. The purpose of this study is to prepare HA powder via the hydrothermal method and to explore the effects of hydrothermal conditions on the structure and properties of the synthesized HA. The room-temperature precipitation method is used for the control group. Furthermore, the results of an immersion test in simulated body fluid confirm that the as-prepared HA exhibits good apatite-forming bioactivity, which is an essential requirement for artificial materials to bond to living bones in the living body and promote bone regeneration. In particular, it is confirmed that the HA synthesized with the addition of the mulberry leaf extract exhibits good in vitro biocompatibility. The morphology, crystallite size, and composition of the carbonated nano-HA obtained herein are similar to those of natural bones. The carbonated nano-HA appears to be an excellent material for bioresorbable bone substitutes or drug delivery. Therefore, the nano-HA powder prepared in this study has great potential in biomedical applications.

Fungal biorecovery of cerium as oxalate and carbonate biominerals.

Cerium is the most sought-after rare earth element (REE) for application in high-tech electronic devices and versatile nanomaterials. In this research, biomass-free spent culture media of Aspergillus niger and Neurospora crassa containing precipitant ligands (oxalate, carbonate) were investigated for their potential application in biorecovery of Ce from solution. Precipitation occurred after Ce3+ was mixed with biomass-free spent culture media and >99% Ce was recovered from media of both organisms. SEM showed that biogenic crystals with distinctive morphologies were formed in the biomass-free spent medium of A. niger. Irregularly-shaped nanoparticles with varying sizes ranging from 0.5 to 2 µm and amorphous biominerals were formed after mixing the carbonate-laden N. crassa supernatant, resulting from ureolysis of supplied urea, with Ce3+. Both biominerals contained Ce as the sole metal, and X-ray diffraction (XRD) and thermogravimetric analyses identified the biominerals resulting from the biomass-free A. niger and N. crassa spent media as cerium oxalate decahydrate [Ce2(C2O4)3·10H2O] and cerium carbonate [Ce2(CO3)3·8H2O], respectively. Thermal decomposition experiments showed that the biogenic Ce oxalates and carbonates could be subsequently transformed into ceria (CeO2). FTIR confirmed that both amorphous and nanoscale Ce carbonates contained carbonate (CO32-) groups. FTIR-multivariate analysis could classify the biominerals into three groups according to different Ce concentrations and showed that Ce carbonate biominerals of higher purity were produced when precipitated at higher Ce3+ concentrations. This work provides new understanding of fungal biotransformations of soluble REE species and their biorecovery using biomass-free fungal culture systems and indicates the potential of using recovered REE as precursors for the biosynthesis of novel nanomaterials.