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Bio-Mineralisation, Characterization, and Stability of Calcium Carbonate Containing Organic Matter

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Bio-Mineralisation, Characterization, and Stability of Calcium Carbonate Containing Organic Matter RSC Advances View Article Online PAPER View Journal | View Issue Bio-mineralisation, characterization, and stability of calcium carbonate containing organic matter† Cite this: RSC Adv.,2021,11, 14415 Renlu Liu,ab Shanshan Huang,b Xiaowen Zhang,b Yongsheng Song,a Genhe He,*a Zaifeng Wangb and Bin Lian *b The composition of organic matter in biogenic calcium carbonate has long been a mystery, and its role has not received sufficient attention. This study is aimed at elucidating the bio-mineralisation and stability of amorphous calcium carbonate (ACC) and vaterite containing organic matter, as induced by Bacillus subtilis. The results showed that the bacteria could induce various structural forms of CaCO3, such as biogenic ACC (BACC) or biogenic vaterite (BV), using the bacterial cells as their template, and the carbonic anhydrase secreted by the bacteria plays an important role in the mineralisation of CaCO3. The 2+ effects of Ca concentration on the crystal structure of CaCO3 were ascertained; when the amount of CaCl2 increased from 0.1% (m/v) to 0.8% (m/v), the ACC was transformed to polycrystalline vaterite. The XRD results demonstrated that the ACC and vaterite have good stability in air or deionised water for one Creative Commons Attribution-NonCommercial 3.0 Unported Licence. year, or even when heated to 200 C or 300 C for 2 h. Moreover, the FTIR results indicated that the BACC or BV is rich in organic matter, and the contents of organic matter in biogenic ACC and vaterite Received 23rd January 2021 are 39.67 wt% and 28.47 wt%, respectively. The results of bio-mimetic mineralisation experiments Accepted 7th April 2021 suggest that the protein secreted by bacterial metabolism may be inclined to inhibit the formation of DOI: 10.1039/d1ra00615k calcite, while polysaccharide may be inclined to promote the formation of vaterite. Our findings advance rsc.li/rsc-advances our knowledge of the CaCO3 family and are valuable for future research into organic-CaCO3 complexes. Carbonic anhydrase (CA) was rst found in human erythro- This article is licensed under a 1 Introduction cytes and is widely present in plants, animals, and microbes. CA CaCO3 comes from a variety of sources, and the mineralisation is capable of catalyzing the reversible hydration reaction, CO2 + ! + À 13 of CaCO3 induced by microbes is an important source that H2O H + HCO3 , of atmospheric and self-generated CO2. Open Access Article. Published on 19 April 2021. Downloaded 9/27/2021 9:56:04 PM. cannot be ignored. These biogenic CaCO3 crystals are normally CA is currently recognised as being involved in carbonate 13–15 nanometric, of diverse crystal types, wrapped in rich organic synthesis. Although bio-induce mineralisation of CaCO3 is matter, and complex elemental compositions, differing from related to urease secreted by bacteria, but it requires the addi- – non-biogenic carbonates.1–6 Calcium carbonate deposition is tion of urea as its substrate.16 19 A variety of microbes, such as a common phenomenon in seawater, fresh water, soil, and eukaryotic algae,20,21 fungi,22,23 and bacteria3,12,24 can induce other environments. Calcium carbonate generates seven struc- CaCO3 mineralisation, however, the morphology and crystal ff tural forms: calcite, monohydrocalcite, ikaite, aragonite, vater- structure of CaCO3 induced by di erent microbes are quite ff ite, hemihydrate calcium carbonate, and amorphous calcium di erent. Even the morphology and crystal structure of CaCO3 carbonate (ACC), among which calcite is the most stable induced by the same microbe are also quite different under structural form at normal temperature and pressure.7–12 The different culturing conditions. ACC is normally a precursor of process and mechanism of calcite biomineralisation have been crystalline calcium carbonates that plays a key role in bio- researched deeply, but the research on the process and mech- mineralisation and polymorph evolution.25 Where, the regula- ff anisms of ACC and vaterite biomineralisation continues to be tory mechanism a ecting the speci c type of CaCO3 (especially lacking. metastable ACC and vaterite) is far from clear in the case of microbial participation and further research into the direc- tional induction mechanism of biogenic CaCO3 is needed. Recent research has established that CaCO precipitation a 3 School of Life Sciences, Key Laboratory of Agricultural Environmental Pollution 26,27 Prevention and Control in Red Soil Hilly Region of Jiangxi Province, Jinggangshan induced by microbe contains organic components, while the University, Ji'an 343009, China. E-mail: [email protected] role of organic matter in the formation and structural stability bSchool of Life Sciences, School of Marine Science and Engineering, Nanjing Normal (especially thermal stability) of biogenic mineral is rarely re- University, Nanjing 210023, China. E-mail: [email protected] ported. Biogenic CaCO3 has broad application prospects in † Electronic supplementary information (ESI) available. See DOI: biotechnology, civil engineering, and palaeontology.10 Because 10.1039/d1ra00615k © 2021 The Author(s). Published by the Royal Society of Chemistry RSC Adv.,2021,11,14415–14425 | 14415 View Article Online RSC Advances Paper the formation and precipitation of CaCO3 lead to the deposition temperature oscillation incubator at 30 C and 180 rpm for 0–14 of atmospheric CO2, or reduces CO2 emissions in water or soil, days. The OD600nm value of the culture solution was measured daily, it plays a positive role in reducing atmospheric CO2 concen- then centrifuged at 8000 rpm for 15 min at 4 C. The supernatant ff 28–30 À 34 2+ trations and retarding the greenhouse e ect. In addition, was used for the determination of HCO3 concentration, Ca biogenic CaCO3 has good adsorption properties for heavy concentration (atomic absorption spectrophotometer, AAS, AA- metals,5 and compared with abiotic calcium carbonate, it shows 6300C, Shimadzu), pH (pH meter, SevenEasy S20), and CA greater potential.31 Our purpose is to elucidate the nucleation activity.34,35 We weighed the dry mass of precipitate from groups E1 patterns and crystallisation processes involved and determine and E2 aer shaking-culturing for 7 days. the composition and structure of biogenic CaCO3. In addition, we hope to identify factors controlling biogenic CaCO 3 2.3 The role of CA in biogenic CaCO3 mineralisation morphology, and discover how crystallisation parameters Acetazolamide (AZ) is widely used as a CA inhibitor.36,37 To inuence particle morphology in bacterial systems containing 2+ clarify the role of CA in CaCO3 mineralisation, different different concentrations of Ca ions. The research is believed to À concentrations (0, 1.0, and 1.5 mg mL 1) of AZ experimental be benecial to the comprehensive exploitation and utilisation groups were established and cultured at 30 C and 180 rpm for 7 of the different types of biogenic CaCO . 3 days. The centrifugal supernatant Ca2+ concentration was Bacillus subtilis, as a popular strain used in microbial fertil- measured by AAS. Ignoring the Ca2+ utilised by the strain, most isers, has been developed rapidly and widely in agricultural of the Ca2+ would be converted to CaCO , and then the Ca2+ production across China.5,32,33 During the process of bacterial 3 biomineralisation efficiency was calculated by use of eqn (1):38 culture, a large amount of ACC and vaterite precipitation was ff C1 À C2 observed, which showed obvious biological e ects. Although Biomineralisation efficiency of Ca2þ ð%Þ¼  100 there are already some research reports on bacteria-induced C1 carbonate, further study is still needed outlining the ACC and (1) Creative Commons Attribution-NonCommercial 3.0 Unported Licence. vaterite mineralisation micro-process induced by agricultural where C1 and C2 are the initial, and end (a er shaking-culturing fertiliser strain. Here, the bacterial induction of ACC and À for 7 days) concentrations of Ca2+ (mg L 1), respectively. vaterite mineralisation and its structural characteristics were researched, which will increase the understanding of biogenic ff 2+ calcium carbonate polymorphisms. 2.4 The e ect of Ca concentrations on biogenic CaCO3 mineralisation and its stability analysis ff 2+ To explore the e ect of Ca concentration on biogenic CaCO3 2 Materials and methods ff mineralisation, we added di erent amounts of CaCl2 (0, 0.1, 0.2, 2.1 Strain 0.4, and 0.8 g) to 100 mL LB liquid culture medium, each group This article is licensed under a was dosed with 2 mL bacterial seed liquid, each group was Experimental strain: B. subtilis (GenBank accession number: KT343639) is China's official certied microbial fertiliser cultured at 180 rpm for 7 days at 30 C. The culture medium was strain.5,32 The strain is adapted to growth in neutral and weakly centrifuged at 8000 rpm for 15 min a er measuring the OD600nm 2+ Open Access Article. Published on 19 April 2021. Downloaded 9/27/2021 9:56:04 PM. alkaline conditions. The bacterial colony is opaque, milk-white values and the number of bacterial cells. The supernatant Ca 2+ and yellowish, with a rough, folded surface and irregular edges; concentration was determined by AAS, and the Ca bio- ffi the bacteria are seen in short rod form, measuring about (0.6 to mineralisation e ciency was calculated by use of eqn (1). We 0.8) mm  (1.2 to 1.6) mm. collected the precipitate, then added 5% HCl to observe whether there were any bubbles visible, preliminarily to determine whether there was any CaCO3 present, or not. The sample was 2.2 The bacterial culture and related indicators for CaCO3 dropped on a clean cover glass and then observed by eld bio-mineralisation emission scanning electron microscopy and energy dispersive The B. subtilis was inoculated with two loops into 200 mL LB liquid spectrometry (FESEM-EDS, Zeiss Supra55) to analyse its medium (tryptone 1% (m/v), yeast extract 0.5% (m/v), NaCl 1% (m/ morphology and elemental composition.
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