Biogenic Minerals Research Articles

Multimodal analysis of renal stones to explore new biomarkers of urolithiasis

Despite advances in minimally invasive surgery, urolithiasis still recurs within the first five years after the first episode in more than 50% of patients. Researchers continue to search for new crystallisation inhibitors, metaphylaxis strategies and laser sources for stone destruction. Therefore, to achieve these goals, it is necessary to study kidney stones not only as the result of an isolated process of pathological biomineralisation in the human body, but also as a biogenic mineral or rock that obeys universal patterns and has certain properties. Consequently, kidney stones need to be studied using methods that are widely used in the geological sciences for the study of minerals, such as computed microtomography and petrological analysis. In this review, the properties of kidney stones studied using various research methods used in geosciences are discussed. These properties are also considered as new biomarkers of urolithiasis. This review discusses how new data from multimodal stone analysis can be used to develop personalised metaphylaxis and treatment strategies for all types of urolithiasis, including the most common idiopathic calcium-oxalate urolithiasis.

Analysis of Ca1-xSrxCO3 phases generated by competitive Sr2+ replacement in pre-formed aragonite

The ratio of Sr/Ca ions in marine biogenic minerals is considered advantageous for tracking geochemical and biomineralization processes that occur in the oceans. It is debatable, though, whether the ratio in biominerals such as coral skeleton is simply related to values in the seawater environment or controlled by the organism. Recent data show that coral larvae produce partially disordered immature aragonite in Mg-containing Sr-poor calcifying fluids, which transforms into well-ordered aragonite in Mg-depleted Sr-enriched environments, upon animal metamorphosis into the sessile polyp state.Inspired by the process in young coral, we explored in vitro substitution of Ca by Sr in aragonite by exposing aragonite crystals precipitated a priori to Sr solutions with variable concentrations. The resulting biphasic material, comprised of Sr-doped aragonite and Ca-doped strontianite, was carefully analyzed for foreign cation substitution in each polymorph. This allowed to establish a linear correlation between Sr levels in mineralizing solutions and Sr in aragonite as well as Ca in strontianite. It indicated that ca. 5-fold higher Sr solution concentration is needed for substitution in the crystal to reach the level found in corals. It also provided with Sr levels required for a putative strontianite phase to form.

Physicochemical Mechanics Approach for Geological Soft Mater (Including Inorganic Polymer and Liquid Crystal Structures) in Analysis of Weathering and Formations of Chemogenic, Mechanogenic and Biogenic Mineral Sediments

Physicochemical Mechanics Approach for Geological Soft Mater (Including Inorganic Polymer and Liquid Crystal Structures) in Analysis of Weathering and Formations of Chemogenic, Mechanogenic and Biogenic Mineral Sediments

Origin and modern microbial ecology of secondary mineral deposits in Lehman Caves, Great Basin National Park, NV, USA.

Lehman Caves is an extensively decorated high desert cave that represents one of the main tourist attractions in Great Basin National Park, Nevada. Although traditionally considered a water table cave, recent studies identified abundant speleogenetic features consistent with a hypogenic and, potentially, sulfuric acid origin. Here, we characterized white mineral deposits in the Gypsum Annex (GA) passage to determine whether these secondary deposits represent biogenic minerals formed during sulfuric acid corrosion and explored microbial communities associated with these and other mineral deposits throughout the cave. Powder X-ray diffraction (pXRD), scanning electron microscopy with electron dispersive spectroscopy (SEM-EDS), and electron microprobe analyses (EPMA) showed that, while most white mineral deposits from the GA contain gypsum, they also contain abundant calcite, silica, and other phases. Gypsum and carbonate-associated sulfate isotopic values of these deposits are variable, with δ34SV-CDT between +9.7‰ and +26.1‰, and do not reflect depleted values typically associated with replacement gypsum formed during sulfuric acid speleogenesis. Petrographic observations show that the sulfates likely co-precipitated with carbonate and SiO2 phases. Taken together, these data suggest that the deposits resulted from later-stage meteoric events and not during an initial episode of sulfuric acid speleogenesis. Most sedimentary and mineral deposits in Lehman Caves have very low microbial biomass, with the exception of select areas along the main tour route that have been impacted by tourist traffic. High-throughput 16S rRNA gene amplicon sequencing showed that microbial communities in GA sediments are distinct from those in other parts of the cave. The microbial communities that inhabit these oligotrophic secondary mineral deposits include OTUs related to known ammonia-oxidizing Nitrosococcales and Thaumarchaeota, as well as common soil taxa such as Acidobacteriota and Proteobacteria. This study reveals microbial and mineralogical diversity in a previously understudied cave and expands our understanding of the geomicrobiology of desert hypogene cave systems.

Influence of the fruit parts on bioactive compounds, antioxidant capacity, polyphenols, fatty acid and mineral contents of the pumpkin (Cucurbita maxima L.) fruits

SummaryIn the current work, the effect of pumpkin parts on the oil content, total phenol, flavonoid, carotenoid quantities, antioxidant capacity, phenolic components, fatty acid profiles and mineral profiles of pumpkin parts was investigated. Total carotenoid and phenolic amounts of pumpkin parts were recorded to be from 36.84 (seed) and 29.92 μg g−1 (pulp) to 28.75 (pulp) and 67.68 mgGAE/100 g (peel) respectively. Also, total flavonoid quantities of the parts of pumpkin were assigned between 21.07 mg/100 g (pulp) and 220.36 mg/100 g (seed), while antioxidant activities of pumpkin samples range from 0.04 mmol kg−1 (pulp) to 0.82 mmol kg−1 (seed). Catechin and caffeic acid amounts of pumpkin parts varied from 13.25 (seed) and 77.31 mg/100 g (peel) to 4.70 (seed) and 7.60 mg/100 g (peel) respectively. The amount of catechin detected in the pumpkin peel was approximately two and five times higher than the pulp part. Resveratrol content was lowest in the pulp part of the pumpkin. Oleic and linoleic acid values of the oils ranged from 19.23% (peel) to 29.16% (seed) and from 18.15% (peel) to 51.06% (seed) respectively. Stearic, oleic and linoleic acids of pumpkin pulp oil were higher than pumpkin peel oil. Pumpkin seed oils are rich in oleic and linoleic acids. P, K, Mg, S and Fe were the dominant biogenic minerals of pumpkin parts. The most of total carotenoids and total phenols were accumulated in the peel part of the pumpkin fruit. The total flavonoid quantity of pumpkin seeds was approximately three times higher than the pumpkin peel part and ten times higher than the pulp part.

Bio-protection of cementitious materials below ground: The significance of natural soil environments

This study explores the potential impact of natural soil on concrete crack self-healing in sub-surface structures. Three types of pre-cracked cement mortar samples were prepared for laboratory experiments, with some samples inoculated with bacterial healing agents, others supplemented with nutrients to attract indigenous soil bacteria, and plain mortar served as controls. The samples were placed within saturated soil under two conditions: slightly organic natural soil and sterilised soil. After 100 days, crack closure was evaluated through microscopic inspection, water absorption tests, and SEM-EDX scanning. The results indicated calcite precipitation on crack surfaces across all samples, but with varying ratios of crack closure (16%–81%). Notably, most samples incubated in natural soil exhibited an overall increase (up to 59.4%) in healing ratio compared to those in sterilised soil, highlighting the potential of indigenous soil microorganisms and their microbial activity in enhancing the biogenic mineral precipitation and thus protecting sub-surface concrete structures.

Formation and properties of spindle-shaped aragonite mesocrystals from Mg-bearing solutions.

The formation of aragonite under ambient conditions is typically linked to Mg-rich aqueous environments. The grains that form in such environments show peculiar properties such as aggregate-like appearance and mesocrystalline character. We tested the effect of dissolved Mg2+ ions on the formation of aragonite mesocrystals by synthesizing aragonite with an automatic titrator at constant pH and at different dissolved Mg : Ca ratios, and by studying the properties of the precipitated material with various scanning transmission electron microscopy (STEM) techniques. At all studied Mg : Ca ratios the firstly condensed carbonate phase was Mg-bearing amorphous calcium carbonate (Mg-ACC) that transformed into aragonite during the synthesis experiments. The aragonite grains had typically aggregate-like appearance and spindle shapes, with the external morphologies of the spindles unaffected by variation in solution chemistry. The alignment of the nanocrystals within the aggregates was crystallographically highly coherent, the [001] directions of nanocrystals showing only a small misorientation with respect to one another; however, both parallel and twin assembly of neighbouring crystals occurred. An increase in the dissolved Mg concentration decreased the crystallographic coherence between the aragonite nanocrystals, suggesting an important role of Mg2+ ions in the assembly of aragonite spindles. Whereas the mesoscale-ordered arrangement of nanocrystals implies a particle-mediated assembly, the observed differences in particle size and composition between the amorphous precursor and the crystalline end-product suggest that the crystallization includes at least partial dissolution and re-precipitation. These findings provide insight into the formation of aragonite and could contribute to the understanding of important aspects of the formation of mesocrystals and hierarchically structured biogenic minerals.

Attenuated Total Reflection Infrared and Far-Infrared, and Raman Spectroscopy Studies of Minerals, Rocks, and Biogenic Minerals.

Attenuated total reflection infrared (ATR-IR, 4000-400 cm-1), ATR-far-IR (ATR-FIR, 400-50 cm-1), and Raman spectra (4000-10 cm-1) were measured for calcium carbonate, three kinds of minerals (calcite, aragonite, and quartz), two kinds of rocks (obsidian and pumice), and four kinds of biogenic minerals, i.e., coral (aragonite), Ruditapes philippinarum (aragonite), Meretrix lusoria (aragonite), and Corbicula japonica (aragonite), to investigate the polymorphism of minerals and biogenic minerals, differences in the crystal structure among aragonite and aragonite biogenic minerals, water in the minerals and biogenic minerals, Boson peaks of obsidian and pumice, very small amounts of carotenoids in the three kinds of shells, and so on. In this study, we put some emphasis on the low-frequency region of IR (FIR) and Raman spectra. ATR-FIR spectra were measured down to 50 cm-1 and Raman spectra were obtained down to 10 cm-1. Second derivative spectra were calculated for the FIR spectra. It has been found from the present study that the FIR spectra are the most powerful for exploring polymorphism and differences in the crystal structure among aragonite and aragonite biogenic minerals. A Boson peak, which is a characteristic low-frequency Raman band for amorphous materials, was observed at around 40 cm-1 in the Raman spectra of obsidian and pumice. The Boson peak of pumice is located at a lower frequency by 12 cm-1 than that of obsidian, indicating that the mean atomic volume of pumice is larger than that of obsidian. The present study has revealed that IR spectra are useful to investigate the amounts and structure of fluid and bound water. Moreover, it has also been found that Raman spectra can detect a very tiny amount of carotenoids in the shells due to the resonance Raman effect.

Unlocking the mysterious polytypic features within vaterite CaCO3

Calcium carbonate (CaCO3), the most abundant biogenic mineral on earth, plays a crucial role in various fields such as hydrosphere, biosphere, and climate regulation. Of the four polymorphs, calcite, aragonite, vaterite, and amorphous CaCO3, vaterite is the most enigmatic one due to an ongoing debate regarding its structure that has persisted for nearly a century. In this work, based on systematic transmission electron microscopy characterizations, crystallographic analysis and machine learning aided molecular dynamics simulations with ab initio accuracy, we reveal that vaterite can be regarded as a polytypic structure. The basic phase has a monoclinic lattice possessing pseudohexagonal symmetry. Direct imaging and atomic-scale simulations provide evidence that a single grain of vaterite can contain three orientation variants. Additionally, we find that vaterite undergoes a second-order phase transition with a critical point of ~190 K. These atomic scale insights provide a comprehensive understanding of the structure of vaterite and offer advanced perspectives on the biomineralization process of calcium carbonate.

Anthropogenic disturbances influence mineral and elemental constituents of freshwater lake sediments.

Lake sediments can provide valuable insights into anthropogenic disturbances such as intensive aquaculture and land use changes. These disturbances often manifest as elevated levels of nutrients and elements within the sediments. This paper uses several analytical techniques, i.e., FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction), EDS (energy-dispersive X-ray spectroscopy), and SEM (scanning electron microscopy), to examine the elemental constituents of lake sediments, along with their relative mineral abundances and surface morphology. The selected freshwater lakes are from the Central Gangetic Plain. The analysis provides a "fingerprint" of geogenic and biogenic mineral constituents of the sediments. Physicochemical, mineralogical, and elemental analysis shows that intensive aquaculture activities in lake alter the sediment chemistry as evidenced by the increase in pH, organic carbon, organic matter, and total phosphorus which is not observed in the lake where aquaculture is prohibited. Freshwater lake sediment is characterized by a high content of biogenic silica and carbonate minerals. The variations in sediment nutrients and mineral fluxes of the selected lakes are mainly attributed to diverse anthropogenic pressures, differences in lake productivity, and the overall ecological condition of the lakes. In the selected three lakes, major variation was reported in the autochthonous sediments in comparison to the allochthonous sediments. The study concludes that catchment and biotic deposit variations in the lakes cannot be evened out by in-lake mixing mechanisms due to variations in the terrigenous and pelagic deposits of the lake. The results highlight the importance of studying annual fluctuations and spatial variations in geogenic and biogenic mineral particle fluxes in lakes. Such investigations provide valuable insights into the annual dynamics of minerals within lakes, contributing to a more comprehensive understanding of their behavior and distribution.

Microbial communities and mineral assemblages in sediments from various habitats at the Haima Cold Seep, South China Sea

Cold seeps create diverse habitats in the deep sea and play an important role in the global carbon cycling. Anaerobic oxidation of methane (AOM) and biogenic mineralization are essential carbon pathways of methane and carbon transformation in cold seeps, however, the effects of habitat heterogeneity on the processes are still poorly understood. In this study, we investigated the microbial communities and mineral assemblages at distinct habitats in the Haima cold seep and their relationships with environmental factors. These habitats were classified as methane seep site (MS), seep-free faunal habitat (FH), and control site (CS). Bacterial communities were significantly different among the three habitats. ANME-3 archaea, Sulfurovum bacteria, and mineralization-associated microbes (e.g., Campylobacterales) were detected in high relative abundances at ROV2. Mineralogical analysis revealed abundant calcite minerals at the seep site, indicating that authigenic carbonate minerals were formed at highly active seep. Multivariate statistical analysis demonstrated that the concentrations of SO42–, Ca2+, and Mg2+ were significantly correlated with the presence of calcite minerals and bacterial communities. These results suggested that AOM-accompanied authigenic carbonate formation is an important factor influencing the mineral assemblages in seep habitats. This finding improves our understanding of marine microbial carbon cycling.

Fe(III) (oxyhydr)oxide reduction by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens.

Some thermophilic bacteria from deep-sea hydrothermal vents grow by dissimilatory iron reduction, but our understanding of their biogenic mineral transformations is nascent. Mineral transformations catalyzed by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens during growth at 55°C were examined using synthetic nanophase ferrihydrite, akaganeite, and lepidocrocite separately as terminal electron acceptors. Spectral analyses using visible-near infrared (VNIR), Fourier-transform infrared attenuated total reflectance (FTIR-ATR), and Mössbauer spectroscopies were complemented with x-ray diffraction (XRD) and transmission electron microscopy (TEM) using selected area electron diffraction (SAED) and energy dispersive X-ray (EDX) analyses. The most extensive biogenic mineral transformation occurred with ferrihydrite, which produced a magnetic, visibly dark mineral with spectral features matching cation-deficient magnetite. Desulfovulcanus ferrireducens also grew on akaganeite and lepidocrocite and produced non-magnetic, visibly dark minerals that were poorly soluble in the oxalate solution. Bioreduced mineral products from akaganeite and lepidocrocite reduction were almost entirely absorbed in the VNIR spectroscopy in contrast to both parent minerals and the abiotic controls. However, FTIR-ATR and Mössbauer spectra and XRD analyses of both biogenic minerals were almost identical to the parent and control minerals. The TEM of these biogenic minerals showed the presence of poorly crystalline iron nanospheres (50-200 nm in diameter) of unknown mineralogy that were likely coating the larger parent minerals and were absent from the controls. The study demonstrated that thermophilic bacteria transform different types of Fe(III) (oxyhydr)oxide minerals for growth with varying mineral products. These mineral products are likely formed through dissolution-reprecipitation reactions but are not easily predictable through chemical equilibrium reactions alone.

Microbial reduction of synthetic Biogenic Iron Oxides containing various amounts of Organic Carbon and Silica

Iron oxides formed in close association with bacteria are referred to as biogenic minerals (BIOS). Both the organic part of BIOS and the iron oxide particles affect the net surface charge of those iron-organic carbon aggregates and offer reactive sites that can immobilize many soluble contaminants (Warren and Haack 2001) making BIOS a contender in bioremediation technologies. However, before using BIOS in bioremediation, it is essential to understand the interactions of impurities such as organic matter and other minor components (including silica) (Dyer et al. 2010). This project involves the synthesis of Biogenic Iron Oxides (BIOS) using various silica contents and different soluble alginate concentrations (as an analogue for bacterial exopolysaccharides) close to natural environmental conditions. The mineralogical, chemical and physical composition of the synthesized samples was determined by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Field Emission Scanning Electron Microscopy (FESEM), Fourier-transform Infrared Spectroscopy (FTIR), and with a Malvern Zetasizer Nano instrument. The various samples (mainly ferrihydrite) were then reduced in the presence of Shewanella putrefaciens CN32, a well-known iron reducing bacterium. All microbial reduction experiments (see Table 1) with different types of BIOS were performed under anoxic conditions. Results indicate that the ratio of organic matter and silica to Fe (III) in BIOS affects the reduction rate. It is proposed that alginate binds to iron oxide particles and protects them from reduction. However, samples in presence of high concentration of silica (i.e.,> 0.05) showed structural disorder which likely prevented nucleation of well ordered ferrihydrite, which in return increased their rate of reduction. In addition, higher reduction rates of ferrihydrite were reported at higher concentrations of silica in BIOS, even in the presence of alginate.

In situ mapping of biomineral skeletal proteins by molecular recognition imaging with antibody-functionalized AFM tips.

Spatial localizing of skeletal proteins in biogenic minerals remains a challenge in biomineralization research. To address this goal, we developed a novel in situ mapping technique based on molecular recognition measurements via atomic force microscopy (AFM), which requires three steps: (1) the development and purification of a polyclonal antibody elicited against the target protein, (2) its covalent coupling to a silicon nitride AFM tip ('functionalization'), and (3) scanning of an appropriately prepared biomineral surface. We applied this approach to a soluble shell protein - accripin11 - recently identified as a major component of the calcitic prisms of the fan mussel Pinna nobilis [1]. Multiple tests reveal that accripin11 is evenly distributed at the surface of the prisms and also present in the organic sheaths surrounding the calcitic prisms, indicating that this protein is both intra- and inter-crystalline. We observed that the adhesion force in transverse sections is about twice higher than in longitudinal sections, suggesting that accripin11 may exhibit preferred orientation in the biomineral. To our knowledge, this is the first time that a protein is localized by molecular recognition atomic force microscopy with antibody-functionalized tips in a biogenic mineral. The 'pros' and 'cons' of this methodology are discussed in comparison with more 'classical' approaches like immunogold. This technique, which leaves the surface to analyze clean, might prove useful for clinical tests on non-pathological (bone, teeth) or pathological (kidney stone) biomineralizations. Studies using implants with protein-doped calcium phosphate coating can also benefit from this technology. STATEMENT OF SIGNIFICANCE: Our paper deals with an unconventional technical approach for localizing proteins that are occluded in biominerals. This technique relies on the use of molecular recognition atomic force microscopy with antibody-functionalized tips. Although such approach has been employed in other system, this is the very first time that it is developed for biominerals. In comparison to more classical approaches (such as immunogold), AFM microscopy with antibody-functionalized tips allows higher magnification and keeps the scanned surface clean for other biophysical characterizations. Our method has a general scope as it can be applied in human health, for non-pathological (bone, teeth) and pathological (kidney stone) biomineralizations as well as for bone implants coated with protein-doped calcium phosphate.

Mineral transformation of poorly crystalline ferrihydrite to hematite and goethite facilitated by an acclimated microbial consortium in electrodes of soil microbial fuel cells

In this study, we investigated the biogenic mineral transformation of poorly crystalline ferrihydrite in the presence of an acclimated microbial consortium after confirming successful soil microbial fuel cell optimization. The acclimated microbial consortia in the electrodes distinctly transformed amorphous ferrihydrite into crystallized hematite (cathode) and goethite (anode) under ambient culture conditions (30 °C). Serial analysis, including transmission/scanning electron microscopy and X-ray/selected area electron diffraction, confirmed that the biogenically synthesized nanostructures were iron nanospheres (~100 nm) for hematite and nanostars (~300 nm) for goethite. Fe(II) ion production with acetate oxidation via anaerobic respiration was much higher in the anode electrode sample (3.2- to 17.8-fold) than for the cathode electrode or soil samples. Regarding the culturable bacteria from the acclimated microbial consortium, the microbial isolates were more abundant and diverse at the anode. These results provide new insights into the biogeochemistry of iron minerals and microbial fuel cells in a soil environment, along with physiological characters of microbes (i.e., iron-reducing bacteria), for in situ applications in sustainable energy research.

Involvement of Bacterial and Fungal Extracellular Products in Transformation of Manganese-Bearing Minerals and Its Environmental Impact.

Manganese oxides are considered an essential component of natural geochemical barriers due to their redox and sorptive reactivity towards essential and potentially toxic trace elements. Despite the perception that they are in a relatively stable phase, microorganisms can actively alter the prevailing conditions in their microenvironment and initiate the dissolution of minerals, a process that is governed by various direct (enzymatic) or indirect mechanisms. Microorganisms are also capable of precipitating the bioavailable manganese ions via redox transformations into biogenic minerals, including manganese oxides (e.g., low-crystalline birnessite) or oxalates. Microbially mediated transformation influences the (bio)geochemistry of manganese and also the environmental chemistry of elements intimately associated with its oxides. Therefore, the biodeterioration of manganese-bearing phases and the subsequent biologically induced precipitation of new biogenic minerals may inevitably and severely impact the environment. This review highlights and discusses the role of microbially induced or catalyzed processes that affect the transformation of manganese oxides in the environment as relevant to the function of geochemical barriers.

Earthworm granules: A model of non-classical biogenic calcium carbonate phase transformations.

Different non-classical crystallization mechanisms have been invoked to explain structural and compositional properties of biocrystals. The identification of precursor amorphous nanoparticle aggregation as an onset process in the formation of numerous biominerals (crystallization via particle attachment) constituted a most important breakthrough for understanding biologically mediated mineralization. A comprehensive understanding about how the attached amorphous particles transform into more stable, crystalline grains has yet to be elucidated. Here, we document structural, biogeochemical, and crystallographic aspects of the formation as well as the further phase transformations of the amorphous calcium carbonate particles formed by cultured specimens of earthworm Lumbricus terrestris. In-situ observations evidence the formation of proto-vaterite after dehydration of earthworm-produced ACC, which is subsequently followed by proto-vaterite transformation into calcite through nanoparticle attachment within the organic framework. In culture medium spiked with trace amounts of Mn2+, the cauliflower-like proto-vaterite structures become longer-lived than in the absence of Mn2+. We propose that the formation of calcite crystals takes place through a non-classical recrystallization path that involves migration of proto-vaterite nanoparticles to the crystallization site, and then, their transformation into calcite via a dissolution-recrystallization reaction. The latter is complemented by ion-by-ion crystal growth and associated with impurity release. These observations are integrated into a new model of the biocrystallization of earthworm-produced carbonate granules which highlights the sensibility of this process to environmental chemical changes, its potential impact on the bioavailability of contaminants as well as the threat that chemical pollution poses to the normal development of its early stages. STATEMENT OF SIGNIFICANCE: Understanding the mechanisms of nucleation, stabilization and aggregation of amorphous calcium carbonate (ACC) and factors controlling its further transformation into crystalline phases is fundamental for elucidation of biogenic mineralization. Some species of earthworms are natural workbench to understand the biogenic ACC, stabilization and the transformation mechanisms, because they create millimeter-sized calcareous granules from amorphous calcium carbonate, which crystallize to a more stable mineral phase (mostly calcite). This study undergoes into the mechanisms of ACC stabilization by the incorporation of trace elements, as manganese, and the ulterior precipitation of calcareous granules by a coupled process of amorphous particle attachment and ion-by-ion growth. The study points to sensibility of this process to environmental chemical changes.

Limits of calcium isotopes diagenesis in fossil bone and enamel

Diagenesis has been recognized for decades to significantly alter the trace elements biogenic signatures in fossil tooth enamel and bone that are routinely used for paleobiological and paleoenvironmental reconstructions. This signature is modified during diagenesis according to a complex continuum between two main processes, addition and substitution. For an additive-like, or early diagenesis, the trace elements biogenic profiles can be restored by leaching secondary minerals, but this technique is inefficient for a substitutive-like, or extensive diagenesis for which secondary trace elements are incorporated into the biogenic mineral. This scheme is however unclear for Ca, the major cation in tooth enamel and bone hydroxylapatite, whose stable isotope composition (δ44/42Ca) also conveys biological and environmental information. We present a suite of leaching experiments for monitoring δ44/42Ca values in artificial and natural fossil enamel and bone from different settings. The results show that enamel δ44/42Ca values are insensitive to an additive-like diagenesis that involves the formation of secondary Ca-carbonate mineral phases, while bone shows a consistent offset toward 44Ca-enriched values, that can be restored to the biogenic baseline by a leaching procedure. In the context of a substitutive-like diagenesis, bone exhibits constant δ44/42Ca values, insensitive to leaching, and shows a REE pattern symptomatic of extensive diagenesis. Such a REE pattern can be observed in fossil enamel for which δ44/42Ca values are still fluctuating and follow a trophic pattern. We conclude that Ca isotopes in fossil enamel are probably not prone to extensive diagenesis and argue that this immunity is due to the very low porosity of enamel that cannot accommodate enough secondary minerals to significantly modify the isotopic composition of the enamel Ca pool.

Determination of Concentration of Free Carbon Dioxide in Artificial Seawater by Difference Balance System/Henry’s Law

The concentration of dissolved carbon dioxide in seawater affects the formation of seabed biogenic minerals, and controls the development and evolution of marine organisms, which is one of the most important indices in the marine environment and geology survey. The concentration of free carbon dioxide in bottom seawater has important academic value for the exploration of seabed minerals, marine environment monitoring, the study of the carbon cycle in seabed sediments and even the global carbon cycle. Titration is used to determine the index, whose range is between 4 mg/L and 400 mg/L. However, the concentration of free carbon dioxide in bottom seawater in some sea areas is lower than this range, thus titration may not be suitable. A method for the determination of free carbon dioxide in artificial seawater, whose name is D.B.S/Henry’s Law, is described in this paper. D.B.S/Henry’s Law indirectly determines the content of free carbon dioxide in seawater instead of directly titrating with reagents. It is simple, fast and accurate, and it is based on the law of conservation of mass/Henry’s law and CO2 dissolution mechanisms. This discovery mainly provides a new scientific perspective for the determination of trace free carbon dioxide concentration in seawater. In addition, Henry’s law constants of carbon dioxide in artificial seawater at 3–20 degrees Celsius are determined with D.B.S/Henry’s Law. These data will be used as an important reference for the determination of free carbon dioxide in seawater in the future. D.B.S/Henry’s Law may be used as a supplement of the methods specified in national and industrial standards, which are applied to the detection of carbon dioxide Henry’s constant and free carbon dioxide content in various temperature and salinity seawater. D.B.S/Henry’s Law provides a new perspective for CO2 determination and has extensive practical application value.

Global Trends in the Distribution of Biogenic Minerals in the Ocean

AbstractThe cycling of marine particulate matter is critical for sequestering carbon in the deep ocean and in marine sediments. Biogenic minerals such as calcium carbonate (CaCO3) and opal add density to more buoyant organic material, facilitating particle sinking and export. Here, we compile and analyze a global data set of particulate organic carbon (POC), particulate inorganic carbon (PIC, or CaCO3), and biogenic silica (bSi, or opal) concentrations collected using large volume pumps (LVPs). We analyze the distribution of all three biogenic phases in the small (1–53 μm) and large (>53 μm) size classes. Over the entire water column 76% of POC exists in the small size fraction. Similarly, the small size class contains 82% of PIC, indicating the importance of small‐sized coccolithophores to the PIC budget of the ocean. In contrast, 50% of bSi exists in the large size fraction, reflecting the larger size of diatoms and radiolarians compared with coccolithophores. We use PIC:POC and bSi:POC ratios in the upper ocean to document a consistent signal of shallow mineral dissolution, likely linked to biologically mediated processes. Sediment trap PIC:POC and bSi:POC are elevated with respect to LVP samples and increase strongly with depth, indicating the concentration of mineral phases and/or a deficit of POC in large sinking particles. We suggest that future sampling campaigns pair LVPs with sediment traps to capture the full particulate field, especially the large aggregates that contribute to mineral‐rich deep ocean fluxes, and may be missed by LVPs.