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Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis

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Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis molecules Article Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis Aleksei Rusakov * , Maria Kuz’mina and Olga Frank-Kamenetskaya * Crystallography Department, Institute of Earth Sciences, St. Petersburg State University, Universitetskaya nab. 7/9, 199034 St. Petersburg, Russia; [email protected] * Correspondence: [email protected] (A.R.); [email protected] (O.F.-K.) Abstract: The present study is focused on the effect of biofilm medium chemistry on oxalate crys- tallization and contributes to the study of the patterns of microbial biomineralization and the development of nature-like technologies, using the metabolism of microscopic fungi. Calcium ox- alates (weddellite and whewellite in different ratios) were synthesized by chemical precipitation in a weakly acidic environment (pH = 4–6), as is typical for the stationary phase of micromycetes 2+ 2− growth, with a ratio of Ca /C2O4 = 4.0–5.5, at room temperature. Additives, which are common for biofilms on the surface of stone in an urban environment (citric, malic, succinic and fumaric acids; + 2+ 3+ 2+ 2+ 3+ 2+ and K , Mg , Fe , Sr , SO4 , PO4 and CO3 ions), were added to the solutions. The result- ing precipitates were studied via X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS). It was revealed that organic acids, excreted by micromicetes, and some environmental ions, as well as their combinations, significantly affect the weddellite/whewellite ratio and the morphology of their phases (including the appearance of tetragonal prism faces of weddellite). The strongest unique effect leading to intensive crystalliza- tion of weddellite was only caused by the presence of citric acid additive in the medium. Minor changes in the composition of the additive components can lead to significant changes in the weddel- Citation: Rusakov, A.; Kuz’mina, M.; lite/whewellite ratio. The effect of the combination of additives on this ratio does not obey the law of Frank-Kamenetskaya, O. Biofilm additivity. The content of weddellite in the systems containing a representative set of both organic Medium Chemistry and Calcium acids and environmental ions is ~20 wt%, which is in good agreement with natural systems. Oxalate Morphogenesis. Molecules 2021, 26, 5030. https://doi.org/ Keywords: microbe biomineralization; calcium oxalate crystallization; weddellite; whewellite 10.3390/molecules26165030 Academic Editors: Mike H. Whangbo and Jürgen Köhler 1. Introduction In recent years, the scientific community from all over the world has shown a signif- Received: 30 June 2021 icant interest in the mechanisms of biomineralization with the participation of microor- Accepted: 16 August 2021 Published: 19 August 2021 ganisms, which is associated with the study of modern mineral formation at nano- and microlevels, as well as processes and phenomena occurring at the border of living and Publisher’s Note: MDPI stays neutral non-living [1–3]. The study of microbial biomineralization also creates a scientific basis with regard to jurisdictional claims in for the development of modern nature-like biotechnologies (ore enrichment; monuments published maps and institutional affil- conservation, primarily cracks healing; environment bioremediation, etc.) [3–5]. iations. The present study is devoted to oxalate crystallization under the action of microor- ganisms. Oxalic acid salts (oxalates) are usually localized in biofilms with dominance of lichens and microscopic fungi, which are located on the surface of rocks and minerals [6]. Active microbe metabolism products which contain organic acids (including oxalic) dis- solve the underlying substrate and initiate oxalate crystallization. Cations involved in Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. their formation enter the biofilm from the underlying stone substrate, and the environment This article is an open access article (atmospheric air and soil) [7]. Acid rains, dews and fogs containing aerosols of various distributed under the terms and ions (including heavy metals) strongly contribute to oxalate crystallization. conditions of the Creative Commons Calcium oxalates (monohydrous whewellite CaC2O4·H2O and dihydrous weddellite Attribution (CC BY) license (https:// CaC2O4·(2 + x)·H2O) are the most common biofilm minerals [3]. They were found in lichen creativecommons.org/licenses/by/ thalli on the surface of different calcium-containing rocks and minerals [8–12], as well as on 4.0/). artificial items (paintings, writing materials and even mummified human remains) [13,14]. Molecules 2021, 26, 5030. https://doi.org/10.3390/molecules26165030 https://www.mdpi.com/journal/molecules Molecules 2021, 26, 5030 2 of 18 Calcium oxalates under the action of microscopic fungi on the surface of rocks and minerals were also obtained in model experiments [3,15–20]. Whewellite and weddellite stability in temperate environmental conditions have previously been investigated, and it was shown that whewellite is the more stable of the two [18]. It was also discovered that the stability of weddellite depends on the content of water molecules in crystal structure [18,21,22]. The results of works on reasons for the ubiquitous presence of unstable weddellite, as well as the factors controlling its formation, are contradictory [4]. Oxalate patina studies showed that, under 20 ◦C, weddellite precipitates under excess of calcium ions in the medium, while whewellite precipitates under a higher concentration of oxalate ions. Wed- dellite also appears to be favored by low temperatures and a very humid microenvironment with very little exposure to sunlight [12]. Model experiments confirmed that whewellite is stable above room temperature and that weddellite naturally transforms into whewellite via a one-step dehydration process [17]. The stability of whewellite is favored by dry conditions, and the mechanism of dehydrate-to-monohydrate transformation is not the only source of whewellite [18]. In our previous experimental work, it was established that fungal biofilm components may facilitate the formation of metastable calcium oxalate weddellite in crystallization range of whewellite and affect its crystal habit [23]. The decisive role in the formation of weddellite crystals at temperatures near 20 ◦C, according to our data, is played by the ratio between Ca2+ and oxalate ions. The citric acid also released by micromycetes, along with the oxalic acid and Fe3+ ions entrapped by biofilm from the environment, plays a significant role in weddellite precipitation. This work is a continuation of our previous researches. The main goal was to expand the set of biofilm components (organic acids and environmental ions) and establish the influence of medium chemistry on calcium oxalates’ formation and their morphology. 2. Results 2.1. The Precipitate Phase Composition and the Morphology of Calcium Oxalate Crystals 2+ 2− Calcium oxalates were obtained from solutions of various compositions (Ca /C2O4 = 4–5) in all syntheses pHinit = 4–8 (AppendixA Table A1): whewellite (Syntheses 1 and 2; AppendixA Table A2) and weddellite (Syntheses 4–7, 17–19 and 30; AppendixA Table A2). However, most often, a mixture of whewellite and weddellite in various ratios (all other syntheses; AppendixA Table A2; Figures1 and2). Weddellite crystal (and their intergrowth) sizes varied in different syntheses, from 0.6 to 100–200 µm, but were mainly in the range of 4–30 µm. Whewellite crystal sizes varied in the range from 2 to 40 µm. The change in the pH value during the formation of calcium oxalates (pHfin–pHinit up to 1.9; AppendixA Table A1) depends on the composition of the solution. The maximum increase occurred in a solution of a complex composition containing citric acid and the following + 2+ 2− 3− environmental ions: K , Mg , SO4 and PO4 (Synthesis 27). Molecules 2021, 26, x FOR PEER REVIEW 3 of 18 Molecules 2021, 26, 5030 3 of 18 Molecules 2021, 26, x FOR PEER REVIEW 3 of 18 Figure 1. The content of weddellite in precipitate (obtained via XRPD) in the presence of different Figure 1. The content of weddelliteadditives in in precipitate solution: (obtained(a) organic via acids, XRPD) (b in) citric the presence acid and of environmental different additives ions in and solution: (c) organic acids Figure 1. The content of weddellite in precipitate (obtained via XRPD) in the presence of different (a) organic acids, (b) citricand acid environmental and environmental ions. ions Sample and ( cnumbers) organic acidscorrespond and environmental to Appendix ions. A Tables Sample A1 numbers and A2. Pillar thick- additives in solution:ness corresponds (a) organic to acids, the relative(b) citric concentrationacid and environmental of the additive ions and in (c the) organic soluti acidson. The mixture of envi- correspond toand Appendix environmentalA Tables ions. A1 and Sample A2. Pillarnumbers thickness correspond corresponds to Appendix to the A relative Tables concentration A1 and A2. Pillar of the thick- additive in ronmental ions in (c) is grayed for the ease of diagram reading. the solution. Theness mixture corresponds of environmental to the relative ions concentration in (c) is grayed of the for theadditive ease ofin diagramthe soluti reading.on. The mixture of envi- ronmental ions in (c) is grayed for the ease of diagram reading. Figure 2. TypicalFigureFigure XRPD 2. 2. Typical Typicalpatterns XRPD XRPDof the patternsstudied ofsamples:of thethe studiedstudied (a) weddellite samples: samples: in ( a Synthesis)(a weddellite)
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