Climatic control on the growth of gigantic gypsum crystals within hypogenic caves (Naica mine, Mexico)?

Garofalo, Pietro; Fricker, Mattias B.; Günther, Detlef; Forti, Paolo; Mercuri, Anna Maria; Loreti, Mara; Capaccioni, Bruno

doi:10.1016/j.epsl.2009.11.057

Cited by 36 publications

(35 citation statements)

References 20 publications

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“…S1). This lack of reactivity can be understood in terms of growth kinetics, due to the high activation barrier [70.7 AE 5.0 kJ∕mol (18)] for incorporation of molecules in the f010g face, at 20°C the step kinetic coefficient of the f010g face of gypsum is only 5.1 × 10 −3 cm∕s (19), and in the case of a pure solution (CaSOA 4 dissolved in H 2 O) with a supersaturation index of 0.01 a step velocity of <0.03 nm∕s is expected (19). Taking into account that the lateral resolution limit of the PSI system is theoretically ≈1.3 μm, although in a practical sense this resolution limit is more likely around 3 μm due to intrinsic noise in the PSI images, more than 1,500 min of observation would be necessary to unmistakably discern any step movement.…”

Section: Resultsmentioning

confidence: 99%

Ultraslow growth rates of giant gypsum crystals

Driessche

García-Ruiz

Tsukamoto

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Mineralogical processes taking place close to equilibrium, or with very slow kinetics, are difficult to quantify precisely. The determination of ultraslow dissolution/precipitation rates would reveal characteristic timing associated with these processes that are important at geological scale. We have designed an advanced high-resolution white-beam phase-shift interferometry microscope to measure growth rates of crystals at very low supersaturation values. To test this technique, we have selected the giant gypsum crystals of Naica ore mines in Chihuahua, Mexico, a challenging subject in mineral formation. They are thought to form by a self-feeding mechanism driven by solution-mediated anhydritegypsum phase transition, and therefore they must be the result of an extremely slow crystallization process close to equilibrium. To calculate the formation time of these crystals we have measured the growth rates of the f010g face of gypsum growing from current Naica waters at different temperatures. The slowest measurable growth rate was found at 55°C, 1.4 AE 0.2 × 10 −5 nm∕s, the slowest directly measured normal growth rate for any crystal growth process. At higher temperatures, growth rates increase exponentially because of decreasing gypsum solubility and higher kinetic coefficient. At 50°C neither growth nor dissolution was observed indicating that growth of giant crystals of gypsum occurred at Naica between 58°C (gypsum/anhydrite transition temperature) and the current temperature of Naica waters, confirming formation temperatures determined from fluid inclusion studies. Our results demonstrate the usefulness of applying advanced optical techniques in laboratory experiments to gain a better understanding of crystal growth processes occurring at a geological timescale.phase shifting interferometry | mineral growth D uring the last decade, the field of mineral growth has experienced important advances in analytical instrumentation (1). The development of state-of-the-art methods for nanometric observation, such as high-resolution atomic force microscopy (2), or advanced optical microscopy techniques like laser confocal differential interference contrast microscopy (3) and phase-shift interferometry (4, 5), have allowed the study at nanoscopic levels of the different growth mechanisms exhibited by crystals, emphasizing the direct relation between the morphology and the growth processes taking place on each crystal face. For example, the application of in situ nanoscale observation of calcite crystal growth in the lab have revealed the microscopic causes of the large morphological variety exhibited by natural occurring calcite crystals (6-8). These, and other works (9-11) have demonstrated the power of laboratory crystal growth studies for sharpening the picture of crystallization occurring in nature.Recently, a very striking crystal growth problem in earth sciences has emerged: the existence of giant crystals of gypsum (CaSO 4 :2H 2 O), in particular those found in the range of Naica, Mexico (12, 13). Large gypsum cryst...

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Section: Resultsmentioning

confidence: 99%

Ultraslow growth rates of giant gypsum crystals

Driessche

García-Ruiz

Tsukamoto

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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“…Once the samples were in position a mixture of water and CO 2 was introduced in the chamber as a fine fog. The aim of this procedure was to rapidly produce an aggressive attack over the crystal surface and the possible deposition of a calcium carbonate layer [7]. To ensure the maximum production of carbonic acid, the CO 2 were dissolved by bubbling it into distilled water at room temperature.…”

Section: -2mentioning

confidence: 99%

“…The conditions at which the structures have developed have been analyzed by several research groups, emphasizing on the fact that this unique conditions are not likely to repeat somewhere around the world [6]. In addition, new structures like a candle shaped ones, have been described derived from the novel hydric conditions of the caves [7].…”

Section: Introductionmentioning

confidence: 99%

Characterization of gypsum crystals exposed to a high CO2 concentration fog using x-ray

Carreño-Márquez

Castillo-Sandoval

Ponce

et al. 2015

AIP Conference Proceedings

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Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials AIP Conference Proceedings 1671, 020008 (2015) Abstract.In Chihuahua State, a little town called Naica has the largest gypsum single crystals in the world. The growth of these structures has been described as a long and stable process developed over thousands of years. Due to the change in the environmental conditions, these crystals could suffer alterations on their surface. In this project we study the cause of possible deterioration of the giant crystals and intend to suggest measures for their preservation. For this sake, our first experiment consists on several gypsum crystals that have been subjected in a climate chamber to a fog at high CO 2 concentration and 51 °C for a period of time of six months, extracting two crystals every 15 days. Then the crystals have been characterized through Grazing Incidence X-Ray Diffraction using a diffractometer PanAlytical X'PertPro with two different detectors; Xe-filled proportional detector and a Pixel 3D detector. The results were compared to determine which technique is the most suitable to study the degradation of gypsum single crystals. In the two cases, we have identified only the gypsum phase, but with different crystal plane orientations.

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“…2); t�us t�e average yearly deposition corresponds to 0.0097 g/cm 2 yr, w�ic� is equivalent to an average linear growt� rate of 0.042 mm/yr or 0.058 mM/cm 2 yr. At any rate, t�is value cannot be directly used to evaluate t�e age of t�e largest crystals, because a fundamental parameter affecting t�e crystal growt� rate �as not yet been considered: t�e temperature inside t�e vessel. In fact t�e present temperature inside t�e device is lower t�an t�at w�ic� c�aracterized t�e caves during t�e growt� of t�eir giant crystals: 51 °C in t�e presentday t�ermal spring instead of 57 °C in t�e past inside t�e caves (Garofalo et al 2010). The an�ydrite/gypsum solubility difference is 0.2 mM/L at 57 °C, w�ereas it increases to a value of 2.2 mM/L at 51 °C (Fig.…”

Section: Fig 5: Correlation Between Measured Gypsum Overgrowth and Tmentioning

confidence: 98%

“…However t�e extrapolated data from t�e first TIMS measurement suffer from a rat�er large uncertainty, because t�ey are related to crystal growt� during a period (t�e last 40,000 years) in w�ic� t�e groundwater level inside t�e Naica ridge started oscillating as strong differences in t�e p�ysico-c�emical (mainly temperature and salinity) parameters of t�e fluid inclusions seem to indicate (Garofalo et al 2010).…”

Section: Fig 5: Correlation Between Measured Gypsum Overgrowth and Tmentioning

confidence: 99%

Preliminary U/Th dating and the evolution of gypsum crystals in Naica caves (Mexico)

Sanna

Forti

Lauritzen

2011

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Lauritzen: Predhodni rezultati datiranja z metodo U-Th in razvoj sadrinih kristalov v jami Naica (Mehika) Izvor, razvoj in me�anizmi rasti veliki� selenitni� kristalov v jama� Naica, so del raziskav v okviru mednarodnega projekta »Naica«. V okviru te� smo določali natančen čas začetka nukleacije sadre in stalnost rasti kristalov v času. Prvi podatki datiranj z uran-torijevo metodo kažejo na pomembne razlike v starosti kristalov sadre ( med 191 ± 13 ky za kristale v jami Ojo de la Reina in 57±1.7 ky v korenu kristala Espada) in veliko časovno obdobje rasti. Hitrost rasti kristalov je med 0,56 in 1,22 mm/ky, kar se odlično ujema z eksperimentalnimi rezultati v trenutni� pogoji� v najglobljem delu rudnika. Rezultati podpirajo tezo o več stopenjskem izločanju kristalov (prvotno v jama� gornjega nivoja, kjer je bila sadra naknadno raztopljena in kasneje v stabilni� razmera� globoko v vodonosniku) in omogočajo nove interpretacije speleogeneze na obravnavanem območju. Ključne besede: Datiranje z metodo U-Th, sadra, jame v rudniku, �itrost rasti kristalov, Naica, Me�ika. The origin and t�e evolution of giant selenite crystals in Naica caves, toget�er wit� t�e understanding of t�eir growt� mec�a-nisms, is one of t�e aims of t�e international multidisciplinary researc�, called t�e "Naica Project". In t�is context, t�e exact timing of w�en t�e gypsum nucleation started and w�et�er its growt� �as been constant over time, �ave been investigated. The preliminary data obtained wit� t�e U-Th disequilibrium met�od s�ow significant differences in ages for gypsum (between 191 ± 13 kyr for one of t�e Ojo de la Reina cave crystals and 57 ± 1.7 kyr for t�e base of Espadas cave's spar) and �ave produced a coarse c�ronological interval of growt�. The crystal depositional rates vary from 0.56 to 1.22 mm/kyr, in excellent agreement wit� t�e laboratory tests for gypsum deposition under present conditions performed in t�e deepest part of t�e mine. These results are also consistent wit� a multistage precipitation started at different times in t�e Naica caves (first in caves at t�e upper level, w�ere gypsum was subsequently dissolved, and only later in t�e deeper part of t�e aquifer under stable conditions) and allow us to improve t�e knowledge on t�e speleogenetic evolution of t�ese caves.

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Climatic control on the growth of gigantic gypsum crystals within hypogenic caves (Naica mine, Mexico)?

Cited by 36 publications

References 20 publications

Ultraslow growth rates of giant gypsum crystals

Ultraslow growth rates of giant gypsum crystals

Characterization of gypsum crystals exposed to a high CO2 concentration fog using x-ray

Preliminary U/Th dating and the evolution of gypsum crystals in Naica caves (Mexico)

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