An experimental and modeling study of Na-rich hydrothermal alteration

Sodic alteration assemblages including clinoptilolite, mordenite, analcime and Na‐montmorillonite were locally observed in sediments in the eastern part of the Hachimantai geothermal region, northeast Japan. This study investigated the mechanisms of sodic enrichment in the sediments during alteration. Kinetic results for water/rock interaction experiments are reported here. Batch‐type experiments were conducted at 150–250°C under saturated vapor pressure. Pyroclastic rocks dissolved incongruently in these experiments, and the solubility and dissolution rates among elements varied as follows: the apparent steady‐state concentrations of major elements are Si > Na ? K > Ca > Al and the order of the dissolution rates is Si > Al > Na ? K > Ca. Na had the highest steady‐state concentration and fastest dissolution rate of the alkali and alkali earth metal ions. Based on surface analysis of plagioclase, dissolution was effected via a reaction layer of Na‐montmorillonite on the mineral surface. Additionally, a reaction model constructed based on the experimentally observed reaction mechanism quantitatively explains the dissolution behavior. These results show that Na‐montmorillonite can be precipitated by pyroclastic rock/meteoric water interactions without seawater involvement: the Na is derived from the host rocks.     

Chemical modification of pyroclastic rock by hot water: an experimental investigation of mass transport at the fluid–solid interface

Hydrothermal water–(pyroclastic) rock interactions were examined using flow-through experiments to deduce the effect of mass transport phenomena on the reaction process. A series of experiments were conducted over the temperature range 75–250°C, with a constant temperature for each experiment, and at saturated vapour pressure, to estimate the apparent rate constants as a function of temperature.
Based on the chemistry of analysed solutions, the water–rock interaction in the experiments was controlled by diffusion from the reaction surface and by the existence of a surface layer at the rock–fluid interface, which regulated the chemical reaction rate. The reaction progress depended to a high degree on flow velocity and temperature conditions, with element abundances in the fluid significantly affected by these factors. Mass transport coefficients for diffusion from the rock surface to the bulk solution have been estimated. Ca is selectively depleted under lower temperature conditions ( T  < 150°C), whereas Na is greatly depleted under higher temperature conditions ( T  > 150°C), and K reaction rates are increased when flow velocity increases. Using these conditions, specific alkali and alkali earth cations were selectively leached from mineral surfaces. The 'surface layer' comprised a 0.5–1.8 mm boundary film on the solution side (the thickness of this layer has no dependence on chemical character) and a reaction layer. The reaction layer was composed of a Si, Al-rich cation-leached layer, whose thickness was dependent on temperature, flow velocity and reaction length. The reaction layer varied in thickness from about 10⁻⁴ to 10⁻⁷ mm under high temperature/low fluid velocity and low temperature/high fluid velocity conditions, respectively.     

Decay of Limestone Statues at Mount Nemrut (Adiyaman,Turkey)

Mount Nemrut is a 2,206 m high mountain located in Adiyaman, Turkey. A number of monumental statues, a 50-m high tumulus, and a lion horoscope were constructed at the top of the mountain by King Antiochos I (69–36 bc) of the Commagene Kingdom. The site was included in the UNESCO World Heritage List in 1987 due to its unique character. However, the limestone statues located on both the east and the west terraces of the site are getting deteriorated. This study investigates the weathering of the limestone at Mount Nemrut based on field and laboratory studies. It is found that the dissolution occurs along microcracks developed in the limestone during geological time. It is more pronounced in the east terrace where freezing-thawing cycles are more than the west terrace. Furthermore, dissolution is more effective for the faces of the statues exposed to direct atmospheric contact. Due to harsh atmospheric conditions with dominant wetting-drying and freezing-thawing processes at the site, it is recommended that direct rain and snow contact with the statues should be minimized.     

Organic–inorganic rock–fluid interactions in stylolitic micro‐environments of carbonate rocks: a FIB‐TEM study combined with a hydrogeochemical modelling approach

Stylolites and the interfaces to the host limestone have been investigated by means of a multidisciplinary analytical approach (thin section microscopy, FIB‐TEM, organic geochemistry and petrography). Carbonate dissolution assuming different boundary conditions was simulated by applying a generic hydrogeochemical modelling approach. It is the conceptual approach to characterize and quantify traceable organic–inorganic interactions in stylolites dependent on organic matter type and its thermal maturity, and to follow stylolite formation in carbonates as result of organic matter reactivity rather than pressure solution as a main control. The investigated stylolite samples are of Upper Permian (Lopingian, Zechstein), Middle Triassic (Muschelkalk) and Late Cretaceous (Maastrichtian) age and always contain marine organic matter. The thermal maturity of the organic matter ranges from the pre‐oil generation zone (0.4–0.5% R_r) to the stage of dry gas generation (>1.3% R_r). The results of the generic hydrogeochemical modelling indicate a sharp increase of calcite dissolution and the beginning of stylolite formation at approximately 40°C, which is equivalent to a depth of less than 800 m under hydrostatic conditions considering a geothermal gradient of 30°C and a surface mean temperature of 20°C. This temperature corresponds to the pre‐oil window when kerogens release an aqueous fluid enriched in carbon dioxide and organic acids. This aqueous fluid may change the existing pore water pH or alkalinity and causes dissolution of carbonate, feldspar and quartz, and clay mineral precipitation along the stylolite. Dissolution of limestone and dolostone leads to reprecipitation of calcite or dolomite opposite of the dissolution side, which indicates only localized mass redistribution. All these integrated hydrogeochemical processes are coupled to the generation of water during organic matter maturation. In all of the calculated hydrogeochemical scenarios, H₂O is a reaction product and its formation supports the suggested hypothesis.     

Apatite grain boundary morphology and its response to low-temperature fluid infiltration in crystalline basement

Apatite grain boundaries on fractured rock surfaces have been examined in an amphibolite facies regional metamorphic granite gneiss from the central Swiss Alps. The morphology of apatite has been characterized using a scanning electron microscope and matched to surface textures in adjoining silicates. Apatites show a wide variety of different surface features ranging from planar crystal faces, to small-scale ridges and dimples, to extensive irregular pitting. Many of these features form in response to the periodic infiltration of fluids along open grain boundaries during the cooling history of the gneiss. Apatite shows evidence of both dissolution and re-precipitation that is controlled by the nature of the grain boundary, the structure of the adjoining silicate phase and the alteration of the host rock. Fracturing occurs in a range of retrograde conditions and is common both within the apatite and along grain boundaries. This coupled to the evidence of fluid interaction with mineral surfaces suggests that extensive permeable networks may be typical of cooling crystalline basement rocks. Grain boundary textures have the potential to reveal a unique record of fluid infiltration in the crust that would be very difficult to decipher using traditional petrographic methods.     

Geometry‐coupled reactive fluid transport at the fracture scale: application to CO2 geologic storage

Water acidification follows CO₂ injection and leads to reactive fluid transport through pores and rock fractures, with potential implications to reservoirs and wells in CO₂ geologic storage and enhanced oil recovery. Kinetic rate laws for dissolution reactions in calcite and anorthite are combined with the Navier‐Stokes law and advection–diffusion transport to perform geometry‐coupled numerical simulations in order to study the evolution of chemical reactions, species concentration, and fracture morphology. Results are summarized as a function of two dimensionless parameters: the Damköhler number Da which is the ratio between advection and reaction times, and the transverse Peclet number Pe defined as the ratio between the time for diffusion across the fracture and the time for advection along the fracture. Reactant species are readily consumed near the inlet in a carbonate reservoir when the flow velocity is low (low transverse Peclet number and Da > 10^?1). At high flow velocities, diffusion fails to homogenize the concentration field across the fracture (high transverse Peclet number Pe > 10^?1). When the reaction rate is low as in anorthite reservoirs (Da < 10^?1), reactant species are more readily transported toward the outlet. At a given Peclet number, a lower Damköhler number causes the flow channel to experience a more uniform aperture enlargement along the length of the fracture. When the length‐to‐aperture ratio is sufficiently large, say l/d > 30, the system response resembles the solution for 1D reactive fluid transport. A decreased length‐to‐aperture ratio slows the diffusive transport of reactant species to the mineral fracture surface, and analyses of fracture networks must take into consideration both the length and slenderness of individual fractures in addition to Pe and Da numbers.     

The hydrogeochemistry of subsurface brines in and west of the Jordan–Dead Sea Transform fault

This study is based on 113 analyses of brines with Cl > 0.57 mol l^?1 (modern seawater), which were collected and analysed mostly during several decades of exploration for gas and oil in Israel. Based on critical evaluation of correlations of elements and ionic ratios and on spider patterns, six different brine events or source brines were identified in the Phanerozoic: the Triassic, Lower Cretaceous and the Mio/Pliocene brine families which were identified in boreholes Sdom‐1, Sdom Deep‐1 and Ha'on, and the Holocene Dead Sea brines. The Triassic brines are nowadays also encountered in under‐ and overlying rock units such as the Paleozoic Negev‐Yam Suf and the Jurassic Arad Groups, respectively. The southern Jordan–Dead Sea Transform (also known as the Rift) hosts the Mio‐Pliocene Sdom Deep and Sdom brine families. Brine bodies not sufficiently isolated by impervious sedimentary layers were flushed out during the Pliocene when the southern Valley drained north‐ and westwards through the Yizre'el Valley to the Mediterranean Sea. In the northern Rift Miocene to Pliocene seawater evaporated and infiltrated into the Rift sediments and into adjacent rocks. Further diluted by freshwater, it emerges as the Ha'on brine. Together with its derivatives, they form the Ha'on family. The derivatives of the Holocene Dead Sea brine family occur along the shoreline of the recent Dead Sea. Apart of all these evaporation brines, brines deriving from dissolution of evaporites locally occur in the area. The time‐bound chemical composition of paleoseawater is considered when discussing the ionic ratios of brines generated during different geological periods. Spider patterns of each brine family are compared and, where necessary, the relationship of brines to distinct families of brines is supported by inverse modelling.     

Morphological evolution of three‐dimensional chemical dissolution front in fluid‐saturated porous media: a numerical simulation approach

This paper is concerned with the morphological evolution of three‐dimensional chemical dissolution fronts that occur in fluid‐saturated porous media. A fully coupled system between porosity, pore‐fluid flow and reactive chemical species transport is considered to describe this phenomenon. Using the newly presented concept of the generalized dimensionless pore fluid pressure‐gradient, which can be used to represent the interaction between solute advection, solute diffusion, chemical kinetics and the shape factor of the soluble mineral, a theoretical criterion has been established to assess the likelihood of instability at a chemical dissolution front in the reactive transport system. To simulate the chemical dissolution front evolution in a three‐dimensional fluid‐saturated porous medium, a numerical procedure combining both the finite difference method and the finite element method has been proposed. As the problem belongs to a complex system science problem, a small randomly generated perturbation of porosity is added to the initial porosity of a three‐dimensional homogeneous domain to trigger instability of a planar chemical dissolution front during its propagation within the fluid‐saturated porous medium. To test the correctness and accuracy of the proposed numerical procedure, a three‐dimensional benchmark problem has been constructed and the related analytical solution has been derived. This enables using the proposed numerical procedure for simulating the morphological evolution of a three‐dimensional chemical dissolution front from a stable, planar state into an unstable, fingering state. The related numerical results demonstrate that the proposed numerical procedure is useful for, and capable of, simulating the morphological instability of a three‐dimensional chemical dissolution front within a fluid‐saturated porous medium.     

Characterization and damage assessment of stones used in the Pasargadae World Heritage Site,Achaemenian period

The architectural remains at Pasargadae were built of three different stones classified according to their colors (beige, dark-gray, and green-gray). The stones show different macroscopic features, such as texture and decay patterns. The aim of this study is to identify the composition of the stones and to evaluate the main decay factors through petrographic studies in order to make conservation decisions more compatible. Petrochemical analyses show that the stones are in fact limestones with different features; two of them have a compact texture (beige and dark-gray stones), while the third has a fairly porous structure (green-gray stone). In some beige stone samples, dolomite was identified. Despite the fact that the presence of salt is a possible decay factor, X-ray diffraction analysis did not report any salt. According to SEM observations, the main reasons for decay in dark-gray and green-gray stones are the dissolution of calcite crystals and the swelling of clay minerals. The main decay factor in the beige stone, by contrast, is dissolution induced by microorganism activity. However, a patina formed by lichens on the surface of the beige stone, although aesthetically detrimental, protects it against further decay.     

Chemical durability of lead-bearing glazes in sulphuric acid solutions — Laboratory experiments performed on Zsolnay architectural ceramics from Budapest (Hungary)

This study aims to simulate the long-term deterioration of architectural glazes exposed to open air in a highly polluted urban environment. A laboratory experiment—a 14-day long accelerated weathering test—on glazed roof tiles has been performed to reveal the damaging influence of contacting acid solutions originating from dissolved gaseous pollutants, mainly SO₂. The studied tiles are made by the Hungarian Zsolnay factory and applied on two buildings in Budapest in the 19th and 20th century. The ceramics were covered mainly by lead glazes in the construction and lead-bearing alkali glazes in the renovation periods.

The solution of pH2 induced a greater dissolution, especially of alkali and alkaline earth metals (up to 2886 ppm), but less lead (up to 21 ppm) from the lead glazes of the construction periods. Newly formed lead sulphate (anglesite) on the corroded glaze parts precipitated on some lead-bearing alkali glazes, with moderate dissolution of alkali and alkaline earth metals (up to 396 ppm) accompanied by higher amount of lead (28–39 ppm). Based on the results, the main determining factor in the durability of glazes is mostly their chemical composition and less their preliminary degradation state.