Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

Ruíz-Agudo, Encarnación; Putnis, Christine V.; Wang, Lijun; Putnis, Andrew

doi:10.1016/j.gca.2011.04.012

Cited by 64 publications

(81 citation statements)

References 32 publications

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“…The larger (micrometer-sized), scattered growth structures display features that could correspond to growth hillocks associated with emerging dislocations (72). However, despite the fact that in many cases these precipitates are well aligned with the Ͻ4 41Ͼ directions, in a few cases they are not.…”

Section: Discussionmentioning

confidence: 99%

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

Rodríguez-Navarro

Jroundi

Schiro

et al. 2012

Appl Environ Microbiol

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191

101

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ABSTRACTThe influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus,Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

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Section: Discussionmentioning

confidence: 99%

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

Rodríguez-Navarro

Jroundi

Schiro

et al. 2012

Appl Environ Microbiol

Self Cite

191

101

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“…This faster calcite dissolution along acute (a) steps contradicts the usual trend reported for calcite dissolution 26,56 , but similar observations have been reported 23 in the presence of Mg 2+ , even at very low concentrations. 32 Other ions present in the brine can affect the surface restructuring dynamics with K + increasing the spreading rate of both acute and obtuse steps 28 and SO 4 2-inducing an elongation of the etch pits 57 , but Mg 2+ ions dominate the evolution of the crystal morphology with the usual rounding of the (o)/(o) etch pits corner 23,32 (blue box in Figure 5B), and determine the 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 14 preferred direction of dissolution. The pinning effect of the adsorbed organic patches further complicates the dissolution process: when a step edge reaches an SA patch, it needs to dissolve laterally in order to avoid the organic layer protecting the edge (blue arrows in Figure 5).…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Growth and Dissolution of Calcite in the Presence of Adsorbed Stearic Acid

Ricci¹,

Segura²,

Erickson³

et al. 2015

Langmuir

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The interaction of organic molecules with the surface of calcite plays a central role in many geochemical, petrochemical and industrial processes and in biomineralization. Adsorbed organics, typically fatty acids, can interfere with the evolution of calcite when immersed in aqueous solutions. Here we use atomic force microscopy in liquid to explore in real-time the evolution of the (101 ത 4) surface of calcite covered with various densities of stearic acid and exposed to different saline solutions. Our results show that the stearic acid molecules tend to act as 'pinning points' on the calcite's surface and slow down the crystal's restructuring kinetics. Depending on the amount of material adsorbed, the organic molecules can form monolayers or bilayer islands that become embedded into the growing crystal. The growth process can also displaces the organic molecules and actively concentrate them into stacked multilayers. Our results provide molecular-level insights into the interplay between the adsorbed fatty acid molecules and the evolving calcite crystal, highlighting mechanisms that could have important implications for several biochemical and geochemical processes and for the oil industry.

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“…Background electrolytes can affect nucleation kinetics, crystal growth, dissolution, crystal size distribution, and the purity of precipitates by inducing changes in the aqueous solvation environment [21][22][23][24][25]. Ions in solution are able to modify water structure dynamics in their local environment as a result of effects associated with their hydration shells [26], which immobilize and electrostrict water [27].…”

Section: Introductionmentioning

confidence: 99%

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

et al. 2017

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Recent experimental evidence and computer modeling have shown that the crystallization of a range of minerals does not necessarily follow classical models and theories. In several systems, liquid precursors, stable pre-nucleation clusters and amorphous phases precede the nucleation and growth of stable mineral phases. However, little is known on the effect of background ionic species on the formation and stability of pre-nucleation species formed in aqueous solutions. Here, we present a systematic study on the effect of a range of background ions on the crystallization of solid phases in the CaCO 3 -H 2 O system, which has been thoroughly studied due to its technical and mineralogical importance, and is known to undergo non-classical crystallization pathways. The induction time for the onset of calcium carbonate nucleation and effective critical supersaturation are systematically higher in the presence of background ions with decreasing ionic radii. We propose that the stabilization of water molecules in the pre-nucleation clusters by background ions can explain these results. The stabilization of solvation water hinders cluster dehydration, which is an essential step for precipitation. This hypothesis is corroborated by the observed correlation between parameters such as the macroscopic equilibrium constant for the formation of calcium/carbonate ion associates, the induction time, and the ionic radius of the background ions in the solution. Overall, these results provide new evidence supporting the hypothesis that pre-nucleation cluster dehydration is the rate-controlling step for calcium carbonate precipitation.

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Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

Cited by 64 publications

References 32 publications

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

Growth and Dissolution of Calcite in the Presence of Adsorbed Stearic Acid

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

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