Precipitation kinetics of calcite in the system CaCO3H2OC02: The conversion to CO2 by the slow process H++HCO3− → CO2+H2O as a rate limiting step

Dreybrodt, Wolfgang; Eisenlohr, Laurent; Madry, B.; Ringer, Simon P.

doi:10.1016/s0016-7037(97)00201-9

Cited by 134 publications

(72 citation statements)

References 35 publications

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“…Dissolution of CaCO 3 in the system H 2 O -CO 2 -CaCO 3 is controlled by three molecular processes: dissolution at the mineral surface, mass transport by diffusion, and the slow Reaction (R4) which have been modelled by Buhmann and Dreybrodt (Buhmann and Dreybrodt, 1985) with Reaction (R4) being rate limiting (Dreybrodt et al, 1997):…”

Section: Experimental Set Up and Detectionmentioning

confidence: 99%

The heterogeneous chemical kinetics of N2O5 on CaCO3 and other atmospheric mineral dust surrogates

2006

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Abstract.Uptake experiments of N 2 O 5 on several mineral dust powder samples were carried out under continuous molecular flow conditions at 298±2 K. At [N 2 O 5 ] 0 =(4.0±1.0)×10 11 cm −3 we have found γ ss values ranging from (3.5±1.1)×10 −2 for CaCO 3 to (0.20±0.05) for Saharan Dust with γ ss decreasing as [N 2 O 5 ] 0 increased. The uptake coefficients reported in this work are to be regarded as upper limiting values owing to the fact that they are based on the geometric (projected) surface area of the mineral dust sample. We have observed delayed production of HNO 3 upon uptake of N 2 O 5 for every investigated sample owing to hydrolysis of N 2 O 5 with surface-adsorbed H 2 O. Arizona Test Dust and Kaolinite turned out to be the samples that generated the largest amount of gas phase HNO 3 with respect to N 2 O 5 taken up. In contrast, the yield of HNO 3 for Saharan Dust and CaCO 3 is lower. On CaCO 3 the disappearance of N 2 O 5 was also accompanied by the formation of CO 2 . For CaCO 3 sample masses ranging from 0.33 to 2.0 g, the yield of CO 2 was approximately 42-50% with respect to the total number of N 2 O 5 molecules taken up. The reaction of N 2 O 5 with mineral dust and the subsequent production of gas phase HNO 3 lead to a decrease in [NO x ] which may have a significant effect on global ozone.

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Section: Experimental Set Up and Detectionmentioning

confidence: 99%

The heterogeneous chemical kinetics of N2O5 on CaCO3 and other atmospheric mineral dust surrogates

2006

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“…Since the thickness of the boundary layer decreases with flow rate, this provides a mechanism for a causal link between flow rate and precipitation rate (Buhmann & Dreybrodt 1985). This idea has been confirmed experimentally (Liu & Dreybrodt 1997;Dreybrodt et al 1997) and by comparison with field measurements (Dreybrodt et al 1992;Liu et al 1995). Wooding (1991) presents a particularly interesting analysis of the growth of individual travertine and ice terraces, using a similar conceptual model.…”

Section: Mechanisms For Precipitation Localizationmentioning

confidence: 76%

Travertine terracing: patterns and mechanisms

Hammer

Dysthe

Jamtveit

2010

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Travertine terracing is one of the most eye-catching phenomena in limestone caves and around hydrothermal springs, but remains fairly poorly understood. The interactions between water chemistry, precipitation kinetics, topography, hydrodynamics, carbon dioxide degassing, biology, erosion and sedimentation constitute a complex, dynamic pattern formation process. The processes can be described and modeled at a range of abstraction levels. At the detailed level concerning the physical and chemical mechanisms responsible for precipitation localization at rims, a single explanation is probably insufficient. Instead, a multitude of effects are likely to contribute, of varying importance depending on scale, flux and other parameters.

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“…Here, experimental data are scarce, and only the precipitation rates for limestone are based on laboratory work (Buhmann & Dreybrodt 1985b;Dreybrodt & Buhmann 1991;Dreybrodt et al 1997). For precipitation rates of anhydrite and gypsum, we assumed a linear relation, but we also discuss potential non-linearities later.…”

Section: Chemical Propertiesmentioning

confidence: 99%

Fracture evolution in soluble rocks: From single-material fractures towards multi-material fractures

Kaufmann

Romanov

Gabrovšek

2017

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IzvlečekUDK 551.435.8 Georg Kaufmann, Franci Gabrovšek & Douchko Romanov: Odvisnost kraškega razvoja razpoke od vrste in zaporedja vodotopnih kamnin, skozi katere poteka Z numeričnim modelom smo raziskovali razvoj sekundarne poroznosti v enodimenzionalni razpoki v apnencu, sadri in anhidridu. Cilji raziskav so bili: 1) ugotoviti razlike med razvojem plitvih in globokih razpok v različnih kamninah; 2) oceniti učinek morebitnega izločanja enega od mineralov v razpoki in 3) dinamika rasti razpoke, ki gre skozi plasti različnih kamnin. Rezultati kažejo na primerljiv razvoj razpok v apnencu in sadri, pri čemer je čas razvoja v obeh kamninah precej različen. V anhidridu je zaradi drugačne kinetike raztapljanja razvoj še hitrejši. Izločanje ob spreminjajočih se geokemičnih pogojih lahko hitro zamaši razpoke in posebej v večjih globinah spremeni poti razvoja mreže kraških prevodnikov. V primeru, ko so razpoke v apnencu prekrite s plastjo sadre, kar v naravi pogosto opažamo, je hitrost širjenja najhitrejša, kar daje vodnim potem vzdolž takih razpok izrazito primerjalno prednost pri zajemanju razpoložljivega toka. Ključne besede: vodotopne kamnine, enostavna razpoka, raztapljanje in izločanje, incepcijski horizont. We employ a numerical model describing the evolution of secondary porosity in a single fracture embedded in soluble rock (limestone, gypsum, and anhydrite) to study the evolution of isolated fractures in different rock types. Our main focus is three-fold: The identification of shallow versus deep flow paths and their evolution for different rock types; the effect of precipitation of the dissolved material in the fracture; and finally the complication of fracture enlargement in fractures composed of several different soluble materials. Our results show that the evolution of fractures composed of limestone and gypsum is comparable, but the evolution time scale is drastically different. For anhydrite, owing to its difference from calcite in the kinetical rate law describing the removal of soluble rock, the evolution is even faster. Precipitation of the dissolved rock due to changes in the hydrochemical conditions can clog fractures fairly fast, thus changing the pattern of preferential pathways in the soluble aquifer, especially with depth. Finally, limestone fractures coated with gypsum, as occasionally observed in caves, will result in a substantial increase in fracture enlargement with time, thus giving these fractures a hydraulic advantage over pure limestone fractures in their competition for capturing flow.

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Precipitation kinetics of calcite in the system CaCO3H2OC02: The conversion to CO2 by the slow process H++HCO3− → CO2+H2O as a rate limiting step

Cited by 134 publications

References 35 publications

The heterogeneous chemical kinetics of N<sub>2</sub>O<sub>5</sub> on CaCO<sub>3</sub> and other atmospheric mineral dust surrogates

The heterogeneous chemical kinetics of N<sub>2</sub>O<sub>5</sub> on CaCO<sub>3</sub> and other atmospheric mineral dust surrogates

Travertine terracing: patterns and mechanisms

Fracture evolution in soluble rocks: From single-material fractures towards multi-material fractures

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Precipitation kinetics of calcite in the system CaCO3H2OC02: The conversion to CO2 by the slow process H++HCO3− → CO2+H2O as a rate limiting step

Cited by 134 publications

References 35 publications

The heterogeneous chemical kinetics of N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; on CaCO&lt;sub&gt;3&lt;/sub&gt; and other atmospheric mineral dust surrogates

The heterogeneous chemical kinetics of N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; on CaCO&lt;sub&gt;3&lt;/sub&gt; and other atmospheric mineral dust surrogates

Travertine terracing: patterns and mechanisms

Fracture evolution in soluble rocks: From single-material fractures towards multi-material fractures

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The heterogeneous chemical kinetics of N<sub>2</sub>O<sub>5</sub> on CaCO<sub>3</sub> and other atmospheric mineral dust surrogates

The heterogeneous chemical kinetics of N<sub>2</sub>O<sub>5</sub> on CaCO<sub>3</sub> and other atmospheric mineral dust surrogates