Predicting Biogeochemical Calcium Precipitation in Landfill Leachate Collection Systems

Clogging of leachate collection systems within municipal solid waste landfills can result in greater potential for contaminants to breach the landfill barrier system. The primary cause of clogging is calcium carbonate (CaCO_3(s)) precipitation from leachate and its accumulation within the pore space of the drainage medium. CaCO_3(s) precipitation is caused by the anaerobic fermentation of volatile fatty acids (VFAs), which adds carbonate to and raises the pH of the leachate. An important relationship in modeling clogging in leachate collections systems is a yield coefficient that relates microbial fermentation of VFAs to precipitation of calcium carbonate. This paper develops a new, mechanistically based yield coefficient, called the carbonic acid yield coefficient (Y_H), which relates the carbonic acid (H₂CO₃) produced from microbial fermentation of acetate, propionate, and butyrate to calcium precipitation. The empirical values of Y_H were computed from the changes in acetate, propionate, butyrate, and calcium concentrations in leachate as it permeated through gravel-size material. The theoretical and empirical results show that the primary driver of CaCO_3(s) precipitation is acetate fermentation. Additionally, other non-calcium cations (e.g., iron and magnesium) precipitated with carbonate (CO_2-) when present in the leachate. A common yield between total cations bound to CO₃ ^2- and H₂CO₃ produced, called the calcium carbonate yield coefficient (Y_c), can reconcile the empirical yield coefficient for synthetic and actual leachates.     

Calcification by juvenile corals under heterotrophy and elevated CO2

Ocean acidification (OA) threatens the existence of coral reefs by slowing the rate of calcium carbonate (CaCO₃) production of framework-building corals thus reducing the amount of CaCO₃ the reef can produce to counteract natural dissolution. Some evidence exists to suggest that elevated levels of dissolved inorganic nutrients can reduce the impact of OA on coral calcification. Here, we investigated the potential for enhanced energetic status of juvenile corals, achieved via heterotrophic feeding, to modulate the negative impact of OA on calcification. Larvae of the common Atlantic golf ball coral, Favia fragum, were collected and reared for 3 weeks under ambient (421 μatm) or significantly elevated (1,311 μatm) CO₂ conditions. The metamorphosed, zooxanthellate spat were either fed brine shrimp (i.e., received nutrition from photosynthesis plus heterotrophy) or not fed (i.e., primarily autotrophic). Regardless of CO₂ condition, the skeletons of fed corals exhibited accelerated development of septal cycles and were larger than those of unfed corals. At each CO₂ level, fed corals accreted more CaCO₃ than unfed corals, and fed corals reared under 1,311 μatm CO₂ accreted as much CaCO₃ as unfed corals reared under ambient CO₂. However, feeding did not alter the sensitivity of calcification to increased CO₂; ? calcification/?Ω was comparable for fed and unfed corals. Our results suggest that calcification rates of nutritionally replete juvenile corals will decline as OA intensifies over the course of this century. Critically, however, such corals could maintain higher rates of skeletal growth and CaCO₃ production under OA than those in nutritionally limited environments.     

Biogenic Polyamines Capture CO2 and Accelerate Extracellular Bacterial CaCO3 Formation

Bacteria, including cyanobacteria, as well as some fungi, are known to deposit calcium carbonate (CaCO₃) extracellularly in calcium-containing artificial medium. Despite extensive investigation, the mechanisms involved in extracellular formation of CaCO₃ by bacteria have remained unclear. The ability of synthetic amines to remove carbon dioxide (CO₂) from natural gas led us to examine the role of biogenic polyamines in CaCO₃ deposition by bacteria. Here, we demonstrated that biogenic polyamines such as putrescine, spermidine, and spermine were able to react with atmospheric CO₂ and the resultant carbamate anion was characterized by using nuclear magnetic resonance (NMR) analysis. Biogenic polyamines accelerated the formation of CaCO₃, and we artificially synthesized the dumbbell-shaped calcites, which had the same form as observed with bacterial CaCO₃ precipitates, under nonbacterial conditions by using polyamines. The reaction rate of calcification increased with temperature with an optimum of around 40 °C. Our observation suggests a novel scheme for CO₂ dissipation that could be a potential tool in reducing atmospheric CO₂ levels and, therefore, global warming.     

Engineered Escherichia coli with Periplasmic Carbonic Anhydrase as a Biocatalyst for CO2 Sequestration

Carbonic anhydrase is an enzyme that reversibly catalyzes the hydration of carbon dioxide (CO₂). It has been suggested recently that this remarkably fast enzyme can be used for sequestration of CO₂, a major greenhouse gas, making this a promising alternative for chemical CO₂ mitigation. To promote the economical use of enzymes, we engineered the carbonic anhydrase from Neisseria gonorrhoeae (ngCA) in the periplasm of Escherichia coli, thereby creating a bacterial whole-cell catalyst. We then investigated the application of this system to CO₂ sequestration by mineral carbonation, a process with the potential to store large quantities of CO₂. ngCA was highly expressed in the periplasm of E. coli in a soluble form, and the recombinant bacterial cell displayed the distinct ability to hydrate CO₂ compared with its cytoplasmic ngCA counterpart and previously reported whole-cell CA systems. The expression of ngCA in the periplasm of E. coli greatly accelerated the rate of calcium carbonate (CaCO₃) formation and exerted a striking impact on the maximal amount of CaCO₃ produced under conditions of relatively low pH. It was also shown that the thermal stability of the periplasmic enzyme was significantly improved. These results demonstrate that the engineered bacterial cell with periplasmic ngCA can successfully serve as an efficient biocatalyst for CO₂ sequestration.     

Induction of Calcium Carbonate by Bacillus cereus

The purpose of this research was to study how the bacteria Bacillus cereus (DCB1) utilizes calcium ions in a culture medium with carbon dioxide (CO₂) to yield calcium carbonate (CaCO₃). The bacteria strain DCB1 was a dominant strain isolated from dolomitic surfaces in areas of Karst topographies. The experimental method was as follows: a modified beef extract-peptone medium (beef extract 3.0 g, peptone 10 g, NaCl 5.0 g, CaCl₂ 2.0 g, glass powder 2.0 g, distilled water 1 L, and a pH between 6.5 and 7.5) was inoculated with B. cereus to attempt to induce the synthesis of CaCO₃. The sample was then processed by centrifugation every 24 h during the 7-day cultivation period. The pH, carbonic anhydrase (CA) activity, and the concentrations of both HCO^- ₃ and Ca²⁺ in the supernatant fluid were measured. Subsequently, precipitation in the culture medium was analyzed to confirm, or otherwise, the presence and if present, the formation, of CaCO₃. Methods used included X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Energy Dispersive Spectroscopy (EDS). Meanwhile, the carbon source in the carbonate was classified by its isotope composition. Results showed that B. cereus can improve its pH value in this culture medium; concentrations of HCO^- ₃ and Ca²⁺ showed a significant decline over the duration of the cultivation period. CA activity reached its maximum during the second day; XRD, SEM, TEM, and isotope analysis all revealed the presence of CaCO₃ as a precipitate. Additionally, these results did not occur in an aseptic control group: no detectable level of CaCO₃ was produced therein. In conclusion: B. cereus can metabolize active materials, such as secretase, by its own growth and metabolism, and can either utilize atmospheric CO₂, or respire, to induce CaCO₃ production. Experimental evidence is offered for a concomitant CO₂ reduction and CaCO₃ induction by microorganisms.     

Characterization of crystalline structures in Opuntia ficus-indica

This research studies the crystalline compounds present in nopal (Opuntia ficus-indica) cladodes. The identification of the crystalline structures was performed using X-ray diffraction, scanning electron microscopy, mass spectrometry, and Fourier transform infrared spectroscopy. The crystalline structures identified were calcium carbonate (calcite) [CaCO₃], calcium-magnesium bicarbonate [CaMg(CO₃)₂], magnesium oxide [MgO], calcium oxalate monohydrate [Ca(C₂O₄)•(H₂O)], potassium peroxydiphosphate [K₄P₂O₈] and potassium chloride [KCl]. The SEM images indicate that calcite crystals grow to dipyramidal, octahedral-like, prismatic, and flower-like structures; meanwhile, calcium-magnesium bicarbonate structures show rhombohedral exfoliation and calcium oxalate monohydrate is present in a drusenoid morphology. These calcium carbonate compounds have a great importance for humans because their bioavailability. This is the first report about the identification and structural analysis of calcium carbonate and calcium-magnesium bicarbonate in nopal cladodes, as well as the presence of magnesium oxide, potassium peroxydiphosphate and potassium chloride in these plants. The significance of the study of the inorganic components of these cactus plants is related with the increasing interest in the potential use of Opuntia as a raw material of products for the food, pharmaceutical, and cosmetic industries.     

Calcium carbonate-methylene blue nanohybrids for photodynamic therapy and ultrasound imaging

Photodynamic therapy plays an important role in cancer treatment. In this work, methylene blue (MB)-embedded calcium carbonate nanorods (CaCO₃-MB NRs) have been synthesized for pH-responsive photodynamic therapy and ultrasound imaging. The morphology of CaCO₃-MB NRs can be controlled by modulating the concentration of Na₂CO₃ aqueous solution. The generation of effective reactive oxygen species (ROS) were confirmed by 1,3-diphenylisobenzofuran (DPBF) probe. Both photodynamic therapy performance and echogenic performance of CaCO₃-MB NRs were investigated to confirm the feasibility of CaCO₃-MB nanohybrids for ultrasound image-guided photodynamic therapy.     

Calcium content of liming material and its effect on sulphur release in a coniferous forest soil

Soil columns with O + A (Experiment I) or Ohorizons (Experiment II) from a Haplic Podsol wereincubated at 15 °C for 368 and 29 + 106 days,respectively. Three types of liming material differingin Ca²⁺ content, i.e. calcium carbonate(CaCO₃), dolomite (CaMg(CO₃)₂) andmagnesium carbonate (MgCO₃), were mixed into theO horizons in equimolar amounts corresponding to 6000kg of CaCO₃ per ha. In the limed treatments ofExperiment I, the leaching of dissolved organic carbon(DOC) and the net sulphur mineralization (estimated asaccumulated SO ₄ ^2– leaching corrected forchanges in the soil pools of adsorbed and waterextractable SO ₄ ^2– ) increased with decreasingCa²⁺ content of the lime and increasing degree oflime dissolution. In relation to the controltreatment, only the MgCO₃ treatment resulted ina significantly higher net sulphur mineralization. InExperiment I the net sulphur mineralization was 4.06,1.68, 0.57, and 2.14 mg S in the MgCO₃,CaMg(CO₃)₂, CaCO₃ and control treatment,respectively. The accumulated SO ₄ ^2– leachingin Experiment II during the first 29 days was 1.70,0.74 and 0.48 mg S in the MgCO₃,CaMg(CO₃)₂ and control treatment,respectively. In the two experiments there wereconsistently significant positive correlations betweenleached amounts of SO ₄ ^2– and DOC. It wasconcluded that net sulphur mineralization was stronglyconnected to the solubilization of the organic matter(DOC formation) and that pH and/or Ca²⁺ ionsaffected the net sulphur mineralization through theireffects on organic matter solubility.     

CO2 bioconversion using carbonic anhydrase (CA): Effects of PEG rigidity on the structure of bio-mineralized crystal composites

The combined effect of both carbonic anhydrase (CA) and the rigidity of polyethylene glycol (PEG) were found to assist the bio-mineralized crystallization behavior of CO₂ differentially. In this study, different forms of magnetically responsive calcium carbonate (CaCO₃) crystal composites were successfully formed from gaseous CO₂ by using the different forms of polyethylene glycols (PEGs) in a constant CO₂ pressure controlled chamber. Polygonal particles were produced with more rigid polymer chains (branched PEG), whereas less rigid polymer chains (PEG) induced the formation of ellipsoidal particles. However, no morphological changes occurred without the presence of CA.     

The relative contributions of biological and abiotic processes to carbon dynamics in subarctic sea ice

Knowledge on the relative effects of biological activity and precipitation/dissolution of calcium carbonate (CaCO₃) in influencing the air-ice CO₂ exchange in sea-ice-covered season is currently lacking. Furthermore, the spatial and temporal occurrence of CaCO₃ and other biogeochemical parameters in sea ice are still not well described. Here we investigated autotrophic and heterotrophic activity as well as the precipitation/dissolution of CaCO₃ in subarctic sea ice in South West Greenland. Integrated over the entire ice season (71 days), the sea ice was net autotrophic with a net carbon fixation of 56 mg C m^?2, derived from a sea-ice-related gross primary production of 153 mg C m^?2 and a bacterial carbon demand of 97 mg C m^?2. Primary production contributed only marginally to the TCO₂ depletion of the sea ice (7–25 %), which was mainly controlled by physical export by brine drainage and CaCO₃ precipitation. The net biological production could only explain 4 % of this sea-ice-driven CO₂ uptake. Abiotic processes contributed to an air-sea CO₂ uptake of 1.5 mmol m^?2 sea ice day^?1, and dissolution of CaCO₃ increased the air-sea CO₂ uptake by 36 % compared to a theoretical estimate of melting CaCO₃-free sea ice. There was a considerable spatial and temporal variability of CaCO₃ and the other biogeochemical parameters measured (dissolved organic and inorganic nutrients).     

Methanogenesis in Eocene Arctic soils inferred from δC of tree fossil carbonates

We report on the carbon and oxygen stable isotope composition of fossil tree material collected at the White Mountain locality of the Buchanan Lake Formation on Axel Heiberg Island in the High Arctic of Canada. The fossils are Middle Eocene in age and have been permineralized with carbonate. Microscopic examination of fossils revealed them to be the remains of Metasequoia stems, composed of secondary carbonate (calcite) and original wood intermingled at the cellular level. Because the specimens show little compression, crushing, or tissue degradation, we believe that carbonate permineralization occurred soon after burial, and therefore provides insight into Eocene carbon cycling at the locality. The carbon isotope signature of the carbonate suggests that methanogenesis resulted in a ¹³C-enriched CO₂ pool that equilibrated with soil water and gave rise to unusually ¹³C-enriched CaCO₃. Tree fossil carbonate exhibited strikingly high δ¹³C values (+4.0 to +7.4‰) compared to published Phanerozoic pedogenic carbonate δ¹³C values. These δ¹³C values, in conjunction with fractionation factors (α) previously determined for carbonate precipitation and methanogenic pathways, indicate an Eocene soil CO₂ pool containing 80-95% CO₂ produced as a by-product of acetate-fermentation methanogenesis. Because methane in the atmosphere is a powerful greenhouse gas, we suggest that methane emissions from Axel Heiberg soils contributed to the relatively warm Arctic climate during the Middle Eocene.     

Is Coal Fly Ash a Suitable Alkaline Resource for Manufacturing New Calcium Carbonate–based Cements? A Systems Analytical Evaluation

At present, the production of cement contributes approximately 8% to global carbon dioxide (CO₂) emissions, whereas a further increase in the future is expected. To reduce these emissions, a prominent measure of the cement industry is to use materials such as coal fly ash (CFA) as a cement substitute, but the availability of qualified ash is limited. The development of “green cements” with lower CO₂ emissions attracts attention within the cement industry and politics. Recently, a new invention for a calcium carbonate (CaCO₃)‐based cement intends to use CFA as an alkaline resource during a manufacturing process based on CO₂ mineralization converting anthropogenic CO₂ into stable calcareous materials by using calcium‐bearing brines. In our systems analysis, we demonstrate that the alkalinity of CFA usable for mass production of cements is poor. The alkalinity of CFA primarily depends on the dissolution of free lime. For CO₂ mineralization, the resulting alkalinity is just sufficient to precipitate the calcium supplied by the CFA itself, and the capacity of CO₂ mineralization is low. Thus, CFA could only be used as a supplementary resource. Even at locations where exceptional calcium‐rich ash is available, very large amounts of ash must be processed. Globally, only a few million tonnes of calcium could be extracted in this way. Because qualified CFA is already used in the construction industry, the extraction of calcium from nonqualified, more polluted CFA is associated with a risk of unwanted environmental effects and implies an elaborated pollutant control.     

Maltobionic acid enhances intestinal absorption of calcium and magnesium in rats

ABSTRACT

In Experiment 1, the effects of calcium maltobionate (MBCa) on calcium and magnesium absorption were examined using male rats. Four diets were designed in which 25%, 50%, and 100% of calcium carbonate (CaCO₃, Control) were substituted with MBCa and were designated as MBCa-25, MBCa-50, and MBCa-100, respectively. The cecal concentration of short-chain fatty acids was significantly higher in groups MBCa-50 and MBCa-100; however, pH of cecal contents did not significantly differ among the groups. Retention rates of calcium and magnesium were significantly higher in all MBCa groups as compared to the Control. In Experiment 2, the efficiency of calcium absorption was compared using everted sacs of jejunum and ileum with CaCO₃ and MBCa as calcium sources. More calcium from MBCa was absorbed as the concentration of calcium increased in comparison to CaCO₃. It was concluded that MBCa is a better calcium source than CaCO₃ in terms of both calcium retention and absorption.

Abbreviations: ANOVA: analysis of variance; Ca: Calcium; CaCO_3: calcium carbonate; ICP-OES: Inductivity coupled plasma optical emission spectrometer; Mg: magnesium; MBCa: calcium maltobionate; OCPC: o-cresolphthalein complexone; SCFAs: short-chain fatty acids; SE: standard error; TRPM6: transient receptor potential melastatin 6.     

Mechanism of calcium accumulation in acetate-fed aerobic granule

High calcium content has been widely reported in acetate-fed aerobic granules, but the reason behind this is unclear yet. By SEM–energy dispersive X-ray mapping analysis, this study showed that the majority of calcium was presented in the central part of the acetate-fed aerobic granule, and the granule shell part was nearly calcium-free. The elemental analysis of calcium ions coupled with the chemical titration of carbonate further revealed that the calcium ions that accumulated in the acetate-fed aerobic granule mainly existed in the form of calcium carbonate (CaCO₃). The formation of the CaCO₃ appeared to be highly dependent on the size of the aerobic granule, i.e., the CaCO₃ precipitation was found only in aerobic granules with radiuses larger than 0.5 mm. These experimental observations with regard to the formation of CaCO₃ in the acetate-fed aerobic granule were further confirmed by the model simulation, which was based on the principles of mass diffusion and carbonate dissociation in liquid phase. This study for the first time showed that the size of the acetate-fed aerobic granule would indeed play an essential role in the CaCO₃ formation, and provided experimental evidence that a crystal CaCO₃ core was not necessarily required for granulation.     

Mineral Deposition in Bacteria-Filled and Bacteria-Free Calcium Bodies in the Crustacean Hyloniscus riparius (Isopoda: Oniscidea)

Crustacean calcium bodies are epithelial sacs which contain a mineralized matrix. The objectives of this study were to describe the microscopic anatomy of calcium bodies in the terrestrial isopod Hyloniscus riparius and to establish whether they undergo molt-related structural changes. We performed 3D reconstruction of the calcium bodies from paraffin sections and analyzed their structure with light and electron microscopy. In addition, we analyzed the chemical composition of their mineralized matrices with micro-Raman spectroscopy. Two pairs of these organs are present in H. riparius. One pair is filled with bacteria while the other pair is not. In non-molting animals, the bacteria-filled calcium bodies contain apatite crystals and the bacteria-free calcium bodies enclose CaCO₃-containing concretions with little organic matrix. During preparation for molt, an additional matrix layer is deposited in both pairs of calcium bodies. In the bacteria-filled calcium bodies it contains a mixture of calcium carbonate and calcium phosphate, whereas only calcium carbonate is present in bacteria-free calcium bodies. After ecdysis, all mineral components in bacteria-free calcium bodies and the additional matrix layer in bacteria-filled calcium bodies are completely resorbed. During calcium resorption, the apical surface of the calcium body epithelium is deeply folded and electron dense granules are present in spaces between epithelial cells. Our results indicate that the presence of bacteria might be linked to calcium phosphate mineralization. Calcium bodies likely provide a source of calcium and potentially phosphate for the mineralization of the new cuticle after molt. Unlike other terrestrial isopods, H. riparius does not form sternal CaCO₃ deposits and the bacteria-free calcium bodies might functionally replace them in this species.     

Effects of neutralizing agents on lactic acid production by Rhizopus oryzae using sweet potato starch

A neutralizing agent is usually employed to counteract the pH reduction during lactic acid fermentation by Rhizopus oryzae. Calcium carbonate (CaCO₃) is used as such a pH controlling agent. The low solubility of CaCO₃ in the fermentation broth could however lead to low efficiency in pH control and cause problems in the subsequent purification process. Therefore, an alternative agent in place of CaCO₃ was examined in this study. The effect of four different neutralizing agents, including CaCO₃, sodium hydroxide (NaOH), ammoniacal solution and sodium bicarbonate (NaHCO₃) on lactic acid production and the morphology of the pellets were investigated. Results indicated that CaCO₃ was still the preferred choice, because of the pellet morphology and the highest lactic acid concentration (43.3 g/L) obtained in the batch using 60 g/L of sweet potato starch as feedstock. It is noteworthy that the lactic acid purification is relatively easier when using NaHCO₃ instead of CaCO₃, due to the higher solubility of sodium lactate than calcium lactate. Therefore, even the batch with CaCO₃ had a slightly higher productivity (1.23 g/L/h) than the batch with NaHCO₃ (1.14 g/L/h), NaHCO₃ might be the first choice for process designers whenever recovery is vital.     

An Unaccounted Fraction of Marine Biogenic CaCO3 Particles

Biogenic production and sedimentation of calcium carbonate in the ocean, referred to as the carbonate pump, has profound implications for the ocean carbon cycle, and relate both to global climate, ocean acidification and the geological past. In marine pelagic environments coccolithophores, foraminifera and pteropods have been considered the main calcifying organisms. Here, we document the presence of an abundant, previously unaccounted fraction of marine calcium carbonate particles in seawater, presumably formed by bacteria or in relation to extracellular polymeric substances. The particles occur in a variety of different morphologies, in a size range from <1 to >100 µm, and in a typical concentration of 10⁴–10⁵ particles L⁻¹ (size range counted 1–100 µm). Quantitative estimates of annual averages suggests that the pure calcium particles we counted in the 1–100 µm size range account for 2–4 times more CaCO₃ than the dominating coccolithophoride Emiliania huxleyi and for 21% of the total concentration of particulate calcium. Due to their high density, we hypothesize that the particles sediment rapidly, and therefore contribute significantly to the export of carbon and alkalinity from surface waters. The biological and environmental factors affecting the formation of these particles and possible impact of this process on global atmospheric CO₂ remains to be investigated.     

Litho‐diagenetic implications of the calcium oxalate‐carbonate biogeochemical cycle in semiarid Calcretes,Nazareth, Israel

Microscopic observations of calcrete soil samples in semiarid environments from Israel reveal a particular vesicular microfabric. The calcrete horizon is indurated but highly porous and all the pores are coated with a gray layer (quasi‐coating) of secondary calcium carbonate. Two kinds of needles are found inside the pores: thin and regular needles (calcite), and filaments with very sharp spikes that are of fungal origin. Analysis of the proportions of C, O, and Ca were made with an E.D.S. microprobe connected with a scanning electron microscope to distinguish calcite (CaCO₃) from calcium oxalate (CaC₂O₄) and to differentiate inorganic from organic influences. Under biological control, calcium oxalate coexists with calcium carbonate; both contribute to rock diagenesis. In the pores, biological activity promotes a complex cycling of calcium leading to recementation of the matrix and further lithification. Thus, this kind of calcrete is due to geological evolution as much as to biochemical control.     

Cyanobacterial calcification, carbon dioxide concentrating mechanisms, and Proterozoic–Cambrian changes in atmospheric composition

Photosynthetic uptake of inorganic carbon can raise the pH adjacent to cyanobacterial cells, promoting CaCO₃ precipitation. This effect is enhanced by CO₂ concentrating mechanisms that actively transport into cells for carbon fixation. CO₂ concentrating mechanisms presumably developed in response to atmospheric decrease in CO₂ and increase in O₂ over geological timescales. In present‐day cyanobacteria, CO₂ concentrating mechanisms are induced when the atmospheric partial pressure of CO₂ (p_CO2) falls below ～0.4%. Reduction in p_CO2 during the Proterozoic may have had two successive effects on cyanobacterial calcification. First, fall in p_CO2 below ～1% (33 times present atmospheric level, PAL) resulted in lower dissolved inorganic carbon (DIC) concentrations that reduced pH buffering sufficiently for isolated CaCO₃ crystals to begin to nucleate adjacent to cyanobacterial cells. As a result, blooms of planktic cyanobacteria induced precipitated ‘whitings’ of carbonate mud in the water column whose sedimentary accumulation began to dominate carbonate platforms ～1400–1300 Ma. Second, fall in p_CO2 below ～0.4% (10 PAL) induced CO₂‐concentrating mechanisms that further increased pH rise adjacent to cells and promoted in vivo cyanobacterial sheath calcification. Crossing of this second threshold is indicated in the fossil record by the appearance of Girvanella 750–700 Ma. Coeval acquisition of CO₂ concentrating mechanisms by planktic cyanobacteria further stimulated whiting production. These inferences, that p_CO2 fell below ～1%～1400–1300 Ma and below ～0.4% 750–700 Ma, are consistent with empirical and modelled palaeo‐atmosphere estimates. Development of CO₂ concentrating mechanisms was probably temporarily slowed by global cooling ～700–570 Ma that favoured diffusive entry of CO₂ into cells. Lower levels of temperature and DIC at this time would have reduced seawater carbonate saturation state, also hindering cyanobacterial calcification. It is suggested that as Earth emerged from ‘Snowball’ glaciations in the late Neoproterozoic, global warming and O₂ rise reactivated the development of CO₂ concentrating mechanisms. At the same time, rising levels of temperature, calcium ions and DIC increased seawater carbonate saturation state, stimulating widespread cyanobacterial in vivo sheath calcification in the Early Cambrian. This biocalcification event promoted rapid widespread development of calcified cyanobacterial reefs and transformed benthic microbial carbonate fabrics.     

Nitrogen fertilization raises CO2 efflux from inorganic carbon: A global assessment

Nitrogen (N) fertilization is an indispensable agricultural practice worldwide, serving the survival of half of the global population. Nitrogen transformation (e.g., nitrification) in soil as well as plant N uptake releases protons and increases soil acidification. Neutralizing this acidity in carbonate‐containing soils (7.49 × 10⁹ ha; ca. 54% of the global land surface area) leads to a CO₂ release corresponding to 0.21 kg C per kg of applied N. We here for the first time raise this problem of acidification of carbonate‐containing soils and assess the global CO₂ release from pedogenic and geogenic carbonates in the upper 1 m soil depth. Based on a global N‐fertilization map and the distribution of soils containing CaCO₃, we calculated the CO₂ amount released annually from the acidification of such soils to be 7.48 × 10¹² g C/year. This level of continuous CO₂ release will remain constant at least until soils are fertilized by N. Moreover, we estimated that about 273 × 10¹² g CO₂‐C are released annually in the same process of CaCO₃ neutralization but involving liming of acid soils. These two CO₂ sources correspond to 3% of global CO₂ emissions by fossil fuel combustion or 30% of CO₂ by land‐use changes. Importantly, the duration of CO₂ release after land‐use changes usually lasts only 1–3 decades before a new C equilibrium is reached in soil. In contrast, the CO₂ released by CaCO₃ acidification cannot reach equilibrium, as long as N fertilizer is applied until it becomes completely neutralized. As the CaCO₃ amounts in soils, if present, are nearly unlimited, their complete dissolution and CO₂ release will take centuries or even millennia. This emphasizes the necessity of preventing soil acidification in N‐fertilized soils as an effective strategy to inhibit millennia of CO₂ efflux to the atmosphere. Hence, N fertilization should be strictly calculated based on plant‐demand, and overfertilization should be avoided not only because N is a source of local and regional eutrophication, but also because of the continuous CO₂ release by global acidification.