Calcium isotope fractionation by intracellular amorphous calcium carbonate (ACC) forming cyanobacteria.

The formation of intracellular amorphous calcium carbonate (ACC) by various cyanobacteria is a widespread biomineralization process, yet its mechanism and importance in past and modern environments remain to be fully comprehended. This study explores whether calcium (Ca) isotope fractionation, linked to ACC-forming cyanobacteria, can serve as a reliable tracer for detecting these microorganisms in modern and ancient settings. Accordingly, we measured stable Ca isotope fractionation during Ca uptake by the intracellular ACC-forming cyanobacterium Cyanothece sp. PCC 7425. Our results show that Cyanothece sp. PCC 7425 cells are enriched in lighter Ca isotopes relative to the solution. This finding is consistent with the kinetic isotope effects observed in the Ca isotope fractionation during biogenic carbonate formation by marine calcifying organisms. The Ca isotope composition of Cyanothece sp. PCC 7425 was accurately modeled using a Rayleigh fractionation model, resulting in a Ca isotope fractionation factor (Δ44Ca) equal to -0.72 ± 0.05‰. Numerical modeling suggests that Ca uptake by these cyanobacteria is primarily unidirectional, with minimal back reaction observed over the duration of the experiment. Finally, we compared our Δ44Ca values with those of other biotic and abiotic carbonates, revealing similarities with organisms that form biogenic calcite. These similarities raise questions about the effectiveness of using the Ca isotope fractionation factor as a univocal tracer of ACC-forming cyanobacteria in the environment. We propose that the use of Δ44Ca in combination with other proposed tracers of ACC-forming cyanobacteria such as Ba and Sr isotope fractionation factors and/or elevated Ba/Ca and Sr/Ca ratios may provide a more reliable approach.

Evaluating the multiple sulfur isotope signature of Eoarchean rocks from the Isua Supracrustal Belt (Southwest-Greenland) by MC-ICP-MS: Volcanic nutrient sources for early life.

On the anoxic Archean Earth, prior to the onset of oxidative weathering, electron acceptors were relatively scarce, perhaps limiting microbial productivity. An important metabolite may have been sulfate produced during the photolysis of volcanogenic SO2 gas. Multiple sulfur isotope data can be used to track this sulfur source, and indeed this record indicates SO2 photolysis dating back to at least 3.7 Ga, that is, as far back as proposed evidence of life on Earth. However, measurements of multiple sulfur isotopes in some key strata from that time can be challenging due to low sulfur concentrations. Some studies have overcome this challenge with NanoSIMS or optimized gas-source mass spectrometry techniques, but those instruments are not readily accessible. Here, we applied an aqua regia leaching protocol to extract small amounts of sulfur from whole rocks for analyses of multiple sulfur isotopes by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Measurements of standards and replicates demonstrate good precision and accuracy. We applied this technique to meta-sedimentary rocks with putative biosignatures from the Eoarchean Isua Supracrustal Belt (ISB, >3.7 Ga) and found positive ∆33S (1.40-1.80‰) in four meta-turbidites and negative ∆33S (-0.80‰ and -0.66‰) in two meta-carbonates. Two meta-basalts do not display significant mass-independent fractionation (MIF, -0.01‰ and 0.16‰). In situ Re-Os dating on a molybdenite vein hosted in the meta-turbidites identifies an early ca. 3.7 Ga hydrothermal phase, and in situ Rb-Sr dating of micas in the meta-carbonates suggests metamorphism affected the rocks at ca. 2.2 and 1.7 Ga. We discuss alteration mechanisms and conclude that there is most likely a primary MIF-bearing phase in these meta-sediments. Our new method is therefore a useful addition to the geochemical toolbox, and it confirms that organisms at that time, if present, may indeed have been fed by volcanic nutrients.

A quantitative study on the terrestrial input to the tropical Northeast Atlantic.

Eolian dust and riverine discharge are identified as two key components of terrestrial input to the oceans. They supply micronutrients to the oceans and modify marine carbon biogeochemistry and global climate through dust-land-ocean interactions. However, it is challenging to accurately constrain regional terrestrial inputs in the past, with currently available models and geochemical proxies. The present study utilizes sedimentary wtCaCO3% records to estimate lithogenic fluxes. The depth-dependance of CaCO3 preservation in the Holocene and Last Glacial Maximum (LGM) sediments in two major basins of the tropical Northeast Atlantic Ocean is described using a carbonate dissolution model. Results show that during the LGM, reduced dust deposition and slight drops of fluvial input are found in the Canary Basin and Cape Verde margins, respectively. To supplement, carbonate deposition during the LGM indicates that the deep subtropical Northeast Atlantic is seized by more sluggish deep waters relative to today.

New Oldowan locality Sare-Abururu (ca. 1.7 Ma) provides evidence of diverse hominin behaviors on the Homa Peninsula, Kenya.

The Homa Peninsula, in southwestern Kenya, continues to yield insights into Oldowan hominin landscape behaviors. The Late Pliocene locality of Nyayanga (∼3-2.6 Ma) preserves some of the oldest Oldowan tools. At the Early Pleistocene locality of Kanjera South (∼2 Ma) toolmakers procured a diversity of raw materials from over 10 km away and strategically reduced them in a grassland-dominated ecosystem. Here, we report findings from Sare-Abururu, a younger (∼1.7 Ma) Oldowan locality approximately 12 km southeast of Kanjera South and 18 km east of Nyayanga. Sare-Abururu has yielded 1754 artifacts in relatively undisturbed low-energy silts and sands. Stable isotopic analysis of pedogenic carbonates suggests that hominin activities were carried out in a grassland-dominated setting with similar vegetation structure as documented at Kanjera South. The composition of a nearby paleo-conglomerate indicates that high-quality stone raw materials were locally abundant. Toolmakers at Sare-Abururu produced angular fragments from quartz pebbles, representing a considerable contrast to the strategies used to reduce high quality raw materials at Kanjera South. Although lithic reduction at Sare-Abururu was technologically simple, toolmakers proficiently produced cutting edges, made few mistakes and exhibited a mastery of platform management, demonstrating that expedient technical strategies do not necessarily indicate a lack of skill or suitable raw materials. Lithic procurement and reduction patterns on the Homa Peninsula appear to reflect variation in local resource contexts rather than large-scale evolutionary changes in mobility, energy budget, or toolmaker cognition.

Bipolar membrane electrodialysis integrated with in-situ CO2 absorption for simulated seawater concentrate utilization, carbon storage and production of sodium carbonate.

In the context of carbon capture, utilization, and storage, the high-value utilization of carbon storage presents a significant challenge. To address this challenge, this study employed the bipolar membrane electrodialysis integrated with carbon utilization technology to prepare Na2CO3 products using simulated seawater concentrate, achieving simultaneous saline wastewater utilization, carbon storage and high-value production of Na2CO3. The effects of various factors, including concentration of simulated seawater concentrate, current density, CO2 aeration rate, and circulating flow rate of alkali chamber, on the quality of Na2CO3 product, carbon sequestration rate, and energy consumption were investigated. Under the optimal condition, the CO32- concentration in the alkaline chamber reached a maximum of 0.817 mol/L with 98 mol% purity. The resulting carbon fixation rate was 70.50%, with energy consumption for carbon sequestration and product production of 5.7 kWhr/m3 CO2 and 1237.8 kWhr/ton Na2CO3, respectively. This coupling design provides a triple-win outcome promoting waste reduction and efficient utilization of resources.

Nubecularia-coralline algal-serpulid-microbial bioherms of the Paratethys Sea-Distribution and paleoecological significance (upper Serravallian, upper Sarmatian, Middle Miocene).

Nubecularia bioherms represent unique bioconstructions that are restricted to the upper Serravallian of the Paratethys and have been reported since the 19th century. They occur in the Central Paratethys in the late Sarmatian and the Eastern Paratethys in the Bessarabian both regional stages of the respective Paratethyan areas. In this study, several locations in the Vienna and Styrian basins of the Central Paratethys were studied out of which four localities were documented in detail (Wolfsthal, Maustrenk, St. Margarethen-Zollhaus, Vienna-Ruzickagasse) to reconstruct their sedimentary setting, their internal composition, and their indications of environmental parameters. The detailed studies included logging of outcrop sections, petrographic, facies and biotic analyses of polished slabs and thin sections and also cathodoluminescence analyses. These concluded that these bioconstructions are not only composed of the foraminifer Nubecularia but represent a complex mixture and interrelationships of Nubecularia, serpulids and microbial carbonate. Four boundstone types can be differentiated: Nubecularia boundstone, Nubecularia-coralline algal boundstone, stromatolitic/thrombolitic boundstone and serpulid-nubeculariid-microbial boundstone. The first 3 types are characteristic of specific localities; the fourth type occurs in all studied locations and represents the terminal association on top of the three other types. The three basal boundstones are predominantly of columnar growth form irrespective of dominance of Nubecularia, coralline algae or microbial carbonate, and the terminal boundstone is widely irregularly organized. The general depositional environment is characterized by cross-bedded oolitic grainstones with abundant quartz grains, miliolid foraminifers and mollusks. Intercalated are microbial carbonates mostly stromatolites but also thrombolites. This indicates a general high water energy environment interrupted by more calm periods when the microbial carbonate was built. The 3 basal types of bioconstructions are interpreted to reflect decreasing food supply and/or oxygenation from Nubecularia over Nubecularia-coralline algal to stromatolitic/thrombolitic boundstone. The serpulid-nubeculariid-microbial boundstone reflects an internal succession with a decrease of the same parameters. Water depth is considered very shallow ranging from 0 to a few meters, and salinity was normal marine to hypersaline. The reconstructed paleoenvironment with dominating oolite shoals and seagrass meadows was not restricted to the Central Paratethys but extended over the entire Paratethys and represented the largest oolite facies area of the entire Cenozoic!

CO2 sequestration in microbial electrolytic cell-anaerobic digestion system combined with mineral carbonation for sludge hydrolysate treatment.

The combination of microbial electrolytic cells and anaerobic digestion (MEC-AD) became an efficient method to improve CO2 capture for waste sludge treatment. By adding CaCl2 and wollastonite, the CO2 sequestration effect with mineral carbonation under 0 V and 0.8 V was studied. The results showed that applied voltage could increase dissolved chemical oxygen demand (SCOD) degradation efficiency and biogas yield effectively. In addition, wollastonite and CaCl2 exhibited different CO2 sequestration performances due to different Ca2+ release characteristics. Wollastonite appeared to have a better CO2 sequestration effect and provided a wide margin of pH change, but CaCl2 released Ca2+ directly and decreased the pH of the MEC-AD system. The results showed methane yield reached 137.31 and 163.50 mL/g SCOD degraded and CO2 content of biogas is only 12.40 % and 2.22 % under 0.8 V with CaCl2 and wollastonite addition, respectively. Finally, the contribution of chemical CO2 sequestration by mineral carbonation and biological CO2 sequestration by hydrogenotrophic methanogenesis was clarified with CaCl2 addition. The chemical and biological CO2 sequestration percentages were 46.79 % and 53.21 % under 0.8 V, respectively. With the increased applied voltage, the contribution of chemical CO2 sequestration rose accordingly. The findings in this study are of great significance for further comprehending the mechanism of calcium addition on CO2 sequestration in the MEC-AD system and providing guidance for the later engineering application.

Study on the Mechanism of Lipid Peroxidation Induced by Carbonate Radicals.

Based on the reported research, hydroxyl radicals can be rapidly transformed into carbonate radicals in the carbonate-bicarbonate buffering system in vivo. Many of the processes considered to be initiated by hydroxyl radicals may be caused by carbonate radicals, which indicates that lipid peroxidation initiated by hydroxyl radicals can also be caused by carbonate radicals. To date, theoretical research on reactions of hydrogen abstraction from and radical addition to polyunsaturated fatty acids (PUFAs) of carbonate radicals has not been carried out systematically. This paper employs (3Z,6Z)-nona-3,6-diene (NDE) as a model for polyunsaturated fatty acids (PUFAs). Density functional theory (DFT) with the CAM-B3LYP method at the 6-311+g(d,p) level was used to calculate the differences in reactivity of carbonate radicals abstracting hydrogen from different positions of NDE and their addition to the double bonds of NDE under lipid solvent conditions with a dielectric constant of 4.0 (CPCM model). Grimme's empirical dispersion correction was taken into account through the D3 scheme. The energy barrier, reaction rate constants, internal energy, enthalpy and Gibbs free energy changes in these reactions were calculated With zero-point vibrational energy (ZPVE) corrections. The results indicated that carbonate radicals initiate lipid peroxidation primarily through hydrogen abstraction from diallyl carbon atoms. The reaction of hydrogen abstraction from diallyl carbon atoms exhibits the highest reaction rate, with a reaction rate constant approximately 43-fold greater than the second-ranked hydrogen abstraction from allyl carbon atoms. This process has the lowest energy barrier, internal energy, enthalpy, and Gibbs free energy changes, indicating that it is also the most spontaneous process.

Hydrothermal Treatment of Wheat Bran under Mild Acidic or Alkaline Conditions for Enhanced Polyphenol Recovery and Antioxidant Activity.

This study was undertaken to investigate the effects of hydrothermal treatments under mild acid and alkaline conditions on polyphenol release and recovery from wheat bran (WB). After an initial screening of various food-grade substances, strong evidence was raised regarding the potency of citric acid and sodium carbonate to provide WB extracts exceptionally enriched in polyphenols. Thus, these two catalysts were tested under various time and temperature combinations, and the processes were described by linear models based on severity factor. The most effective treatments were those performed with 10% of either citric acid or sodium carbonate, at a constant temperature of 90 °C for 24 h, providing yields in total polyphenols of 23.76 and 23.60 mg g-1 dry mass of ferulic acid equivalents, respectively. Liquid chromatography-mass spectrometry analyses revealed that, while the sodium carbonate treatment afforded extracts enriched in ferulic acid, treatments with citric acid gave extracts enriched in a ferulate pentose ester. The extracts produced from those treatments also exhibited diversified antioxidant characteristics, a fact ascribed to the different polyphenolic composition. To the best of the authors' knowledge, this is the first report demonstrating the effective release of ferulic acid and a ferulate pentose ester from WB, using benign acid and alkali catalysts, such as citric acid and sodium carbonate.

Calcareous termite mounds in South Africa are ancient carbon reservoirs.

Ecosystems that offer carbon sequestration by leaching bicarbonate to groundwater are valuable natural capital. One region that may offer this service is the west coast of South Africa. Over 20 % is covered by soil mounds ("heuweltjies") up to 40 m diameter, 2 m high, inhabited by the southern harvester termite Microhodotermes viator and enriched in soil organic and inorganic carbon and soluble minerals. We aimed to generate radiogenic and stable isotope data for soils and groundwater in a region where these data are absent, to 1) verify the atmosphere-soil-groundwater link, and 2) resolve the timing and pattern of calcite dissolution and water infiltration in the landscape. Results show that soil and groundwater sulfate have the same marine aerosol source. Episodic calcite dissolution in mound centers, which increased during periods of global cooling, has been set against background input of marine aerosols since before the Last Glacial according to radiocarbon (14C) ages. Our data push back soil organic carbon 14C ages of inhabited termite mounds to 13-19 ka (kiloannum, thousand years before present), nest carbonate 14C ages to 33 ka, and mound soil carbonate 14C ages to 34 ka, making these the oldest active termite features ever dated. These ages are consistent with soil organic carbon and carbonate 14C ages of regional, non-mound, coastal petrocalcic horizons formed by accumulation of carbonate leached from their overlying aeolian dune fields. Harvesting activities of termites inject younger organic material around nests >1 m deep, leading to continuous renewal of important soil carbon reservoirs at depth. Termite bioturbation increases the system's ability to dissolve carbonate. The central, bioturbated part of the mounds have greater infiltration depths and greater calcite dissolution, whereas surrounding soils experienced more surface runoff. Calcareous termite mounds offer a mechanism to sequester CO2 through dissolution and leaching of soil carbonate-bicarbonate to groundwater.

Analysis of the chemical characteristics and causes of high total hardness of groundwater in Jianghan Plain, China.

Familiarity with the chemical characteristics of regional groundwater can provide important guidance and reference for the development of regional groundwater exploitation. Jianghan Plain has been reported to have high groundwater total hardness (TH), resulting in the inability of local groundwater to be directly used as drinking water. In order to explore the causes of high TH, the paper analyzed the hydrochemical characteristics of shallow groundwater in Jianghan Plain combined with software of SPSS, JMP, and PHEEQC. The results showed that the cations in the groundwater in the area were mainly Ca2+, while the anions were mainly HCO3-. 20% of groundwater exceed the China national guideline for TH (i.e., 450 mg/L). The groundwater chemistry in the study area was controlled by three main factors of dissolution of carbonate rocks, human activities, and redox conditions, among which the interaction between water and rock had the greatest impact. The water carbonate rock interaction within Jianghan Plain was affected by various factors such as water flow and aquifers and showed a gradually weakening trend from west to east. This work not only strengthened the understanding of the causes of the high TH of groundwater in the region, but also provided reference value for regional groundwater environmental management.

Buffer-Dependent Photophysics of 2-Aminopurine: Insights into Fluorescence Quenching and Excited-State Interactions.

2-Aminopurine (2AP) is the most widely used fluorescent nucleobase analogue in DNA and RNA research. Its unique photophysical properties and sensitivity to environmental changes make it a useful tool for understanding nucleic acid dynamics and DNA-protein interactions. We studied the effect of ions present in commonly used buffer solutions on the excited-state photophysical properties of 2AP. Fluorescence quenching was negligible for tris(hydroxymethyl)aminomethane (TRIS), but significant for phosphate, carbonate, 3-(N-morpholino) propanesulfonic acid (MOPS), and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffers. Results indicate that the two tautomers of 2AP (7H, 9H) are quenched by phosphate ions to different extents. Quenching by the H2PO4- ion is more pronounced for the 7H tautomer, while the opposite is true for the HPO42- ion. For phosphate ions, the results of the time-resolved fluorescence study cannot be explained using a simple collisional quenching mechanism. Instead, results are consistent with transient interactions between 2AP and the phosphate ions. We postulate that excited-state interactions between the 2AP tautomers and an H-bond acceptor (phosphate and carbonate) result in significant quenching of the singlet-excited state of 2AP. Such interactions manifest in biexponential fluorescence intensity decays with pre-exponential factors that vary with quencher concentration, and downward curvatures of the Stern-Volmer plots.

Synthesis of an Immunologically Active Heptamannoside of Mycobacterium tuberculosis by the [Au]/[Ag]-Catalyzed Activation of Ethynylcyclohexyl Glycosyl Carbonate Donor.

Tuberculosis (TB) is one of the most dreadful diseases, killing more than 3 million humans annually. M. tuberculosis (MTb) is the causative agent for TB and has a thick and waxy cell wall, making it an attractive target for immunological studies. In this study, a heptamannopyranoside containing 1 → 2 and 1 → 6 α-mannopyranosidic linkages has been explored for the immunological evaluations. The conjugation-ready heptamannopyranoside was synthesized by exploiting the salient features of recently discovered [Au]/[Ag]-glycosidation of ethynylcyclohexyl glycosyl carbonate donors. The glycan was conjugated to the ESAT6, an early secreted protein of MTb for further characterization as a potential subunit vaccine candidate.

Coral restoration can drive rapid reef carbonate budget recovery.

Restoration is increasingly seen as a necessary tool to reverse ecological decline across terrestrial and marine ecosystems.1,2 Considering the unprecedented loss of coral cover and associated reef ecosystem services, active coral restoration is gaining traction in local management strategies and has recently seen major increases in scale. However, the extent to which coral restoration may restore key reef functions is poorly understood.3,4 Carbonate budgets, defined as the balance between calcium carbonate production and erosion, influence a reef's ability to provide important geo-ecological functions including structural complexity, reef framework production, and vertical accretion.5 Here we present the first assessment of reef carbonate budget trajectories at restoration sites. The study was conducted at one of the world's largest coral restoration programs, which transplants healthy coral fragments onto hexagonal metal frames to consolidate degraded rubble fields.6 Within 4 years, fast coral growth supports a rapid recovery of coral cover (from 17% ± 2% to 56% ± 4%), substrate rugosity (from 1.3 ± 0.1 to 1.7 ± 0.1) and carbonate production (from 7.2 ± 1.6 to 20.7 ± 2.2 kg m-2 yr-1). Four years after coral transplantation, net carbonate budgets have tripled and are indistinguishable from healthy control sites (19.1 ± 3.1 and 18.7 ± 2.2 kg m-2 yr-1, respectively). However, taxa-level contributions to carbonate production differ between restored and healthy reefs due to the preferential use of branching corals for transplantation. While longer observation times are necessary to observe any self-organization ability of restored reefs (natural recruitment, resilience to thermal stress), we demonstrate the potential of large-scale, well-managed coral restoration projects to recover important ecosystem functions within only 4 years.

Immature porcine cortical bone mechanical properties and composition change with maturation and displacement rate.

Computational models of mature bone have been used to predict fracture; however, analogous study of immature diaphyseal fracture has not been conducted due to sparse experimental mechanical data. A model of immature bone fracture may be used to aid in the differentiation of accidental and non-accidental trauma fractures in young, newly ambulatory children (0-3 years). The objective of this study was to characterize the evolution of tissue-level mechanical behavior, composition, and microstructure of maturing cortical porcine bone with uniaxial tension, Raman spectroscopy, and light microscopy as a function of maturation. We asked: 1) How do the monotonic uniaxial tensile properties change with maturation and displacement rate; 2) How does the composition and microstructure change with maturation; and 3) Is there a correlation between composition and tensile properties with maturation? Elastic modulus (p < 0.001), fracture stress (p < 0.001), and energy absorption (p < 0.014) increased as a function of maturation at the quasistatic rate by 110%, 86%, and 96%, respectively. Fracture stress also increased by 90% with maturation at the faster rate (p = 0.001). Fracture stress increased as a function of increasing displacement rate by 28% (newborn p = 0.048; 1-month p = 0.004; 3-month p= < 0.001), and fracture strain decreased by 68% with increasing displacement rate (newborn p = 0.002; 1-month p = 0.036; 3-month p < 0.001). Carbonate-to-phosphate ratio was positively linearly related to elastic modulus, and fracture stress was positively related to carbonate-to-phosphate ratio and matrix maturation ratio. The results of this study support that immature bone is strain-rate dependent and becomes more brittle at faster rates, contributing to the foundation upon which a computational model can be built to evaluate immature bone fracture.

Effect of Ba(II), Eu(III), and U(VI) on rat NRK-52E and human HEK-293 kidney cells in vitro.

Heavy metals pose a potential health risk to humans when they enter the organism. Renal excretion is one of the elimination pathways and, therefore, investigations with kidney cells are of particular interest. In the present study, the effects of Ba(II), Eu(III), and U(VI) on rat and human renal cells were investigated in vitro. A combination of microscopic, biochemical, analytical, and spectroscopic methods was used to assess cell viability, cell death mechanisms, and intracellular metal uptake of exposed cells as well as metal speciation in cell culture medium and inside cells. For Eu(III) and U(VI), cytotoxicity and intracellular uptake are positively correlated and depend on concentration and exposure time. An enhanced apoptosis occurs upon Eu(III) exposure whereas U(VI) exposure leads to enhanced apoptosis and (secondary) necrosis. In contrast to that, Ba(II) exhibits no cytotoxic effect at all and its intracellular uptake is time-independently very low. In general, both cell lines give similar results with rat cells being more sensitive than human cells. The dominant binding motifs of Eu(III) in cell culture medium as well as cell suspensions are (organo-) phosphate groups. Additionally, a protein complex is formed in medium at low Eu(III) concentration. In contrast, U(VI) forms a carbonate complex in cell culture medium as well as each one phosphate and carbonate complex in cell suspensions. Using chemical microscopy, Eu(III) was localized in granular, vesicular compartments near the nucleus and the intracellular Eu(III) species equals the one in cell suspensions. Overall, this study contributes to a better understanding of the interactions of Ba(II), Eu(III), and U(VI) on a cellular and molecular level. Since Ba(II) and Eu(III) serve as inactive analogs of the radioactive Ra(II) and Am(III)/Cm(III), the results of this study are also of importance for the health risk assessment of these radionuclides.

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.

Sizeable net export of base cations from a Carpathian flysch catchment indicates their geogenic origin while the 26Mg/24Mg, 44Ca/40Ca and 87Sr/86Sr isotope ratios in runoff are indistinguishable from atmospheric input.

Nutrient imbalances may negatively affect the health status of forests exposed to multiple stress factors, including drought and bark beetle calamities. We studied the origin of base cations in runoff from a small Carpathian catchment underlain by base-poor flysch turbidites using magnesium (Mg), calcium (Ca) and strontium (Sr) isotope composition of 10 ecosystem compartments. Our objective was to constrain conclusions drawn from long-term hydrochemical monitoring of inputs and outputs. Annual export of Mg, Ca and Sr exceeds 5-to-15 times their atmospheric input. Mass budgets per se thus indicate sizeable net leaching of Mg, Ca and Sr from bedrock sandstones and claystones. Surprisingly, δ26Mg, δ44Ca and 87Sr/86Sr isotope ratios of runoff were practically identical to those of atmospheric deposition and soil water but significantly different from bedrock isotope ratios. We did not find any carbonates in the studied area as a hypothetical, easily dissolvable source of base cations whose isotope composition might corroborate the predominance of geogenic base cations in the runoff. Marine carbonates typically have lower δ26 Mg and 87Sr/86Sr ratios, and silicate sediments often have higher δ26Mg and 87Sr/86Sr ratios than runoff at the study site. Mixing of these two sources, if confirmed, could reconcile the flux and isotope data.

A conserved asparagine residue stabilizes iron binding in Manduca sexta transferrin-1.

Transferrin 1 (Tsf1) is an insect-specific iron-binding protein that is abundant in hemolymph and other extracellular fluids. It binds iron tightly at neutral pH and releases iron under acidic conditions. Tsf1 influences the distribution of iron in the body and protects against infection. Elucidating the mechanisms by which Tsf1 achieves these functions will require an understanding of how Tsf1 binds and releases iron. Previously, crystallized Tsf1 from Manduca sexta was shown to have a novel type of iron coordination that involves four iron-binding ligands: two tyrosine residues (Tyr90 and Tyr204), a buried carbonate anion, and a solvent-exposed carbonate anion. The solvent-exposed carbonate anion was bound by a single amino acid residue, a highly conserved asparagine at position 121 (Asn121); thus, we predicted that Asn121 would be essential for high-affinity iron binding. To test this hypothesis, we analyzed the iron-binding and -release properties of five forms of recombinant Tsf1: wild-type, a Y90F/Y204F double mutant (negative control), and three Asn121 mutants (N121A, N121D and N121S). Each of the Asn121 mutants exhibited altered spectral properties, confirming that Asn121 contributes to iron coordination. The N121D and N121S mutations resulted in slightly lower affinity for iron, especially at acidic pH, while iron binding and release by the N121A mutant was indistinguishable from that of the wild-type protein. The surprisingly minor consequences of mutating Asn121, despite its high degree of conservation in diverse insect species, suggest that Asn121 may play a role that is essential in vivo but non-essential for high affinity iron binding in vitro.

Refinement of kinetic model and understanding the role of dichloride radical (Cl2•-) in radical transformation in the UV/NH2Cl process.

The ultraviolet/monochloramine (UV/NH2Cl) process is an emerging advanced oxidation process with promising prospects in water treatment. Previous studies developed kinetic models of UV/NH2Cl for simulating radical concentrations and pollutant degradation. However, the reaction rate constants of Cl2•- with bicarbonate and carbonate (kCl2•-, HCO3- and kCl2•-, CO32-) were overestimated in literature. Consequently, when dosing 1 mM chloride and 1 mM bicarbonate, the current models of UV/NH2Cl severely under-predicted the experimental concentrations of three important radicals (i.e., hydroxyl radical (HO•), chlorine radical (Cl•), and dichloride radical (Cl2•-)) with great deviations (> 90 %). To investigate this issue, the transformation reactions among these three radicals in UV/NH2Cl were systematically studied. For the first time, it was found that in addition to Cl•, Cl2•- was also an important parent radical of HO• in the presence of chloride, and chloride could effectively compensate the inhibitory effect of bicarbonate on HO• generation in the system. Moreover, reactions and rate constants in current models were scrutinized from corresponding literature, and the reaction rate constants of Cl2•- with bicarbonate and carbonate (kCl2•-, HCO3- and kCl2•-, CO32-) were reevaluated to be 1.47 × 105 and 3.78 × 106 M-1s-1, respectively, by laser flash photolysis. With the newly obtained rate constants, the refined model could accurately simulate concentrations of all three radicals under different chloride and bicarbonate dosages with satisfactory deviations (< 30 %). Meanwhile, the refined model performed much better in predicting pollutant degradation and radical contribution compared with the unrefined model (with the previously estimated kCl2•-, HCO3- and kCl2•-, CO32-). The results of this study enhanced the accuracy and applicability of the kinetic model of UV/NH2Cl, and deepened the understanding of radical transformation in the process.