Deposition Of Carbonate Minerals Research Articles

PROCEDURE FOR DETERMINING THE NATURE OF CALCIUM CARBONATE FORMATION ON OILFIELD EQUIPMENT

In the article, the authors propose to use the method of X-ray diffraction analysis (XRD) to establish the nature of the formation of oilfield deposits using of calcium carbonate as an example. It was shown for the first time that comparative diffraction patterns of natural and technogenic carbonate mineral deposits of oilfield equipment differ significantly in the physical broadening of diffraction reflections. In addition, it has been established that the diffraction reflections of technogenic calcite are characterized by shifts to the region of large scattering angles. These facts are taken as the basis for establishing the nature of the formation of carbonate deposits using X-ray diffraction analysis. It has been shown that natural (core) carbonate minerals are characterized by narrow reflections with good resolution of doublet lines, while in minerals formed under borehole conditions, the diffraction maxima are much broader, and low-intensity reflections are not resolved. Precision analysis of diffraction patterns showed that the reasons for such atypical broadenings and shifts of reflections in technogenic mineral deposits are the relatively small sizes of grains — crystallites and high microdistortions of the crystal lattice compared to their natural analogues. It is shown that in order to establish the nature of carbonate deposits of oilfield equipment, it is necessary to measure diffraction patterns of natural and technogenic minerals under the same shooting conditions. Subsequently, the obtained diffraction patterns are analyzed and X-ray diffraction data on the microstructure of the studied minerals are determined. It has been established that in technogenic calcite the crystallite sizes in all arbitrarily selected directions (hkl) are more than 1.6 times smaller than in its natural analogue. The X-ray diffraction method has shown that the average value of microdistortion of the crystal lattice of technogenic calcite is 1.7 times greater than that of its natural analogue. As a result of comparing X-ray diffraction data on the fine structure of mineral deposits of oilfield equipment with those obtained from core material, the nature of the formation of the analyzed minerals is established. To confirm the XRD results, visual studies using scanning electron microscopy (SEM) were also carried out.

The incorporation of chlorine and cosmogenic 36Cl into speleothem carbonate

AbstractCave carbonate mineral deposits (speleothems) contain trace elements that are intensively investigated for their significance as palaeoclimate and environmental proxies. However, chlorine, which is abundant in marine and meteoric waters, has been overlooked as a potential palaeo-proxy, while cosmogenic 36Cl could, in principle, provide a solar irradiance proxy. Here, total Cl concentrations analysed from various speleothems were low (3–14 mg/kg), with variations linked to crystal fabrics. High-resolution synchrotron radiation micro X-ray fluorescence (μ-XRF) trace element mapping showed Cl often associated with Na, Si, and Al. We propose that speleothems incorporate Cl in two fractions: (1) water soluble (e.g., fluid inclusions) and (2) water insoluble and strongly bound (e.g., associated with detrital particulates). However, disparities indicated that alternate unidentified mechanisms for Cl incorporation were present, raising important questions regarding incorporation of many trace elements into speleothems. Our first measurements of 36Cl/Cl ratios in speleothems required large samples due to low Cl concentrations, limiting the potential of 36Cl as a solar irradiance proxy. Critically, our findings highlight a knowledge gap into how Cl and other trace elements are incorporated into speleothems, how the incorporation mechanisms and final elemental concentrations are related to speleothem fabrics, and the significance this may have for how trace elements in speleothems are interpreted as palaeoclimate proxies.

Spatiotemporal quantification of organic matter accumulation in the Eocene Green River Formation, Bridger Basin, Wyoming

It has long been recognized that lakes can bury large amounts of organic carbon (CORG) in their sediment, with important consequences for conventional and unconventional petroleum resources and potentially for the global carbon cycle. The detailed distribution of lacustrine organic carbon through space and time is important to understanding its commercial and climatic implications, but has seldom been documented in detail. The Green River Formation offers a unique opportunity to improve this understanding, due to extensive Fischer assay analyses of its oil generative potential and to recently published radioisotopic age analyses of intercalat ed volcanic tuffs. Fischer assay analyses reveal distinctly different patterns of organic matter enrichment that correlate with different lacustrine facies associations. Histograms of oil generative potential for evaporative facies of the Wilkins Peak Member exhibit an approximately exponential distribution. This pattern is interpret ed to result from episodic expansion and contraction of Eocene Lake Gosiute across a low-gradient basin floor that experienced frequent desiccation. In contrast, histograms for fluctuating profundal facies of the upper Rife Bed of the Tipton Member and the lower LaClede Bed of the Laney Member exhibit an approximately normal or log normal distribution, with modes as high as 16–18 gallons per ton. This pattern is interpreted to reflect generally deeper conditions when the lake often intersected basin-bounding uplifts. Within the Bridger basin, burial of CORG was greatest in the south during initial Wilkins Peak Member deposition, reflecting greater rates of accommodation near the Uinta uplift. The locus of CORG burial shifted north during upper Wilkins Peak Member deposition, coincident with a decrease in differential accommodation. CORG burial during deposition of the upper Rife and lower LaClede Beds was greatest in the southeast, due either to greater accommodation or localized influx of river-borne nutrients. Average CORG burial fluxes are consistently ~4-5 g/m2 yr for each interval, which is an order of magnitude less than fluxes reported for small Holocene lakes in the northern hemisphere. Maximum rates of CORG burial during deposition of organic-rich mudstone beds (oil shale) were likely similar to Holocene lakes however. Deposition of carbonate minerals in the Bridger basin resulted in additional, inorganic carbon burial. Overall it appears that carbon burial by Eocene lakes could have influenced the global carbon cycle, but only if synchronized across multiple lake systems.

Evaluation of groundwater geochemical characteristics and quality in the central and Northern Shaanxi Province, China

Groundwater is of vital importance to many aspects of ecosystem services, especially in the central and northern Shaanxi Provence, China,— an area covered by loess deposits and short of water resources. We studied the solute geochemistry and water quality of groundwater in this area to improve the understanding of hydrogeochemical processes in loess deposits area. The results showed that the average pH of groundwaters was 8.03 ± 0.36 (1 SD) with large ranges (324 − 83,379 mg/L) of the total dissolved solids (TDS). The cations and anions followed the order of Na+ > Ca2+ > Mg2+ > K+ > SiO2 and HCO3− > Cl− > SO42− > F− > NO3−. Most groundwater samples show the HCO3−–Na+–Ca2+ water type and a small number of samples the Na+–Cl− type. Irrigation water quality assessments showed that 40% of the groundwater has good water quality, 42% moderate water quality, and 18% (the upper reaches of Wuding River and Wei River) poor water quality with very high salinity. About 40% of groundwater samples were not suitable for drinking due to the high TDS, fluoride, sulfide, and chloride. Gibbs plot and stoichiometry analysis showed that carbonate weathering is the main source of groundwater chemistry in central Shaanxi Province while evaporite dissolution dominates in northern Shaanxi Provence. The loess weathering significantly influences the dissolved solutes of groundwater in the Loess Plateau. The ion-exchange between Mg2+ and Ca2+ in groundwater and Na+ in clay minerals and the deposition of carbonate minerals increased Na+ but decreased the Ca2+ in groundwater. Our research results improve our understanding of hydrogeochemical processes that affect the solutes chemistry of groundwater in the loess area and provide essential data to the global groundwater database.

Authigenic titanite in weathered basalts: Implications for paleoatmospheric reconstructions

The stability of titanite is sensitive to temperature and partial pressure of CO2. The finding of authigenic titanite grains in weathering regolith formed on Paraná basalts, Brazil, under tropical climatic conditions, reveals the thermodynamically-driven conversion from calcite to titanite at elevated ambient temperatures. Being unusual nowadays, this phase transition provides important implications for the understanding of silicate weathering in earlier geological epochs.Two types of secondary titanites were identified in the weathering profile of the study area. The tiny grains of 10 ​μm are forming in the microscopic voids in the rock. Also, large fractures filled with Fe-rich clay minerals contain bigger specimens of up to 170 ​μm. The titanites of second type often coexist with chalcedony and barite. No carbonate minerals were found in the weathering profile. Weathering sphene can be discriminated from other titanite types by its strong positive Eu anomaly, increased Al2O3 content and low content of trace elements. Its specific chemical composition and reactive transport modeling link this secondary mineral with dissolution of plagioclase. The titanite precipitation is controlled by slow diffusion in poorly-aerated, highly-alkaline pore fluids.The subaerial weathering of basaltic rocks provides a significant reservoir for atmospheric CO2. However, the deposition of carbonate minerals is thermodynamically avoided at the stability field of titanite. We demonstrate a complex feedback between CO2 and soil carbonates. The rise in pCO2 triggers the precipitation of calcite in the weathering regolith, but the greenhouse effect increasing the temperature can cease carbonate deposition. Secondary titanites were found in several paleosols and at least a part of them can be of weathering origin.

Microbially induced palygorskite-sepiolite authigenesis in modern hypersaline lakes (Central Spain)

Abstract This study gives insight into the mechanisms of formation of palygorskite-sepiolite minerals that have remained elusive for many years. The occurrence of palygorskite-sepiolite and minor smectite in association with a variety of authigenic sulphates and Ca-Mg carbonate mineral deposits was identified in silicon-poor, saline to hypersaline ephemeral lakes in Central Spain. By a combination of sedimentological, mineralogical and petrological techniques (XRD, SEM, FEGSEM and TEM) it is shown that very small, poorly ordered palygorskite-sepiolite crystals resulted from the aggregation of nanocrystals within the matrix of the microbial mats (EPS) as it dehydrates. The Mg-rich clays nucleated on Mg-enriched EPS that also contain variable amounts of Si, Mg, Al and Fe, mostly derived from the degradation of siliciclastic minerals. The crystals have a broad compositional and textural range, from poorly ordered palygorskite laths to pure sepiolite bundles, suggesting that they grow through successive stages. Changes in the chemical composition of the fibers occur even at microscale, which is explained by the variability of the biogeochemical conditions prevailing in the microenvironments where the crystals grow. The overall results provide evidence for a biomediated-crystallization of palygorskite-sepiolite in microbial sediments.

Ore petrology, hydrothermal alteration, fluid inclusions, and sulfur stable isotopes of the Milin Kamak intermediate sulfidation epithermal Au-Ag deposit in Western Srednogorie, Bulgaria

The Milin Kamak gold-silver deposit is located in Western Srednogorie zone, 50km west of Sofia, Bulgaria. This zone belongs to the Late Cretaceous Apuseni-Banat-Timok-Srednogorie magmatic and metallogenic belt. The deposit is hosted by altered trachybasalt to andesitic trachybasalt volcanic and volcanoclastic rocks with Upper Cretaceous age, which are considered to be products of the Breznik paleovolcano. Milin Kamak is the first gold-silver intermediate sulfidation type epithermal deposit recognized in Srednogorie zone in Bulgaria. It consists of eight ore zones with lengths ranging from 400 to 1000m, widths from several cm to 3–4m, rarely to 10–15m, an average of 80–90m depth (a maximum of 200m) and dip steeply to the south. The average content of gold is 5.04g/t and silver – 13.01g/t. The styles of alteration are propylitic, sericite, argillic, and advanced argillic. Ore mineralization consists of three stages. Quartz-pyrite stage I is dominated by quartz, euhedral to subhedral pyrite, trace pyrrhotite and hematite in the upper levels of the deposit. Quartz-polymetallic stage II is represented by major anhedral pyrite, galena, Fe-poor sphalerite; minor chalcopyrite, tennantite, bournonite, tellurides and electrum; and trace pyrrhotite, arsenopyrite, marcasite. Gangue minerals are quartz and carbonates. The carbonate-gold stage III is defined by deposition of carbonate minerals and barite with native gold and stibnite.Fluid inclusions in quartz are liquid H2O-rich with homogenization temperature (Th) ranging from 238 to 345°C as the majority of the measurements are in the range 238–273°C. Ice-melting temperatures (Tm) range from −2.2 to −4.1°C, salinity – from 3.7 to 6.6wt.% NaCl equiv. These measurements imply an epithermal environment and low- to moderate salinity of the ore-forming fluids.δ34S values of pyrite range from −0.49 to +2.44‰. The average calculated δ34S values are 1.35‰. The total range of δ34S values for pyrite are close to zero suggesting a magmatic source for the sulfur.

Syn- and postkinematic cement textures in fractured carbonate rocks: Insights from advanced cathodoluminescence imaging

In calcite and dolomite deposits in fractures, transmitted light and optical cathodoluminescence methods detect crack-seal texture in some fractures, but scanning electron microscope-based cathodoluminescence (SEM-CL) combined with secondary-electron images and element maps, reveals crack-seal and cement growth textures where previous SEM-CL imaging methods found massive or featureless deposits. In a range of fractured carbonate rocks, patterns and textures of calcite and dolomite cements precipitated during and after fracture growth resemble complex accumulation patterns found in quartz in sandstone fractures, suggesting that some apparent differences between carbonate mineral and quartz deposits in fractures reflect the limits of previous imaging methods. Advances in delineating textures in widespread carbonate mineral deposits in fractures provide evidence for growth and occlusion of fracture porosity.

Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates.

Do carbonate karst terrains affect the global carbon cycle?

Carbonate minerals comprise the largest reservoir of carbon in the earth’s lithosphere, but they are generally assumed to have no net impact on the global carbon cycle if rapid dissolution and precipitation reactions represent equal sources and sinks of atmospheric carbon. Observations of both terrestrial and marine carbonate systems indicate that carbonate minerals may simultaneously dissolve and precipitate within different portions of individual hydrologic systems. In all cases reported here, the dissolution and precipitation reactions are related to primary production, which fixes atmospheric CO2 as organic carbon, and the subsequent remineralization in watersheds of the organic carbon to dissolved CO2. Deposition of carbonate minerals in the ocean represents a flux of CO2 to the atmosphere. The dissolution of oceanic carbonate minerals can act either as a sink for atmospheric CO2 if dissolved by carbonic acid, or as a source of CO2 if dissolved through sulfide oxidation at the freshwater-saltwater boundary. Since dissolution and precipitation of carbonate minerals depend on ecological processes, changes in these processes due to shifts in rainfall patterns, earth surface temperatures, and sea level should also alter the potential magnitudes of sources and sinks for atmospheric CO2 from carbonate terrains, providing feedbacks to the global carbon cycle that differ from modern feedbacks.Keywords: Global carbon cycle, carbonate terrains, organic carbon fixation, remineralization, carbonate mineral dissolution, carbonate mineral precipitation.DOI: 10.3986/ac.v42i2-3.660

Influence of the diversion of Bear River into Bear Lake (Utah and Idaho) on the environment of deposition of carbonate minerals

Bear River, the largest river in the Great Basin, had some of its flow diverted into Bear Lake through a series of canals constructed between 1911 and 1918, turning Bear Lake into a reservoir. The prediversion lake had an unusually high Mg2+:Ca2+ ratio (38 by weight), which resulted in precipitation of CaCO3 as aragonite. The amount and mineralogy of the carbonate did not change immediately after the diversion, but during the middle of the 20th century, high‐Mg calcite began to precipitate. In contrast, at the time of diversion there were very distinct changes in the isotopic composition of the carbonate that clearly define the time of diversion within the sediments. Sedimenttrap studies show that the CaCO3 polymorph that precipitates in the epilimnion of the lake today is high‐Mg calcite. Samples in sediment traps placed 2 m above the bottom of the lake in 45 m of water (bottom traps) contain predominantly aragonite and quartz, with lesser amounts of high‐Mg and low‐Mg calcite and dolomite. Isotopic evidence from the sediments shows that the aragonite that accumulated in the bottom sediment traps and that constitutes the bulk of postdiversion sediments is reworked and redistributed from shallow sites to deep sites.

Geochemical models of metasomatism in ultramafic systems: serpentinization, rodingitization, and sea floor carbonate chimney precipitation

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300°C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25°C and w/r less than ∼32, conditions are sufficiently reducing to yield H 2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH − production by olivine and pyroxene dissolution in the absence of counterbalancing OH − consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg 2+ and Ca 2+ to accumulate in the aqueous phase in exchange for H +. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300°C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg°. In serpentinization by seawater at 300°C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300°C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside.

Kerolite in Carbonate-Rich Speleothems and Microbial Deposits From Basaltic Caves, Kauai, Hawaii

AbstractThe occurrence of kerolite in association with various secondary Ca-Mg carbonate mineral deposits (speleothems) was identified in basaltic sea caves on the island of Kauai, Hawaii. Kerolite is the dominant clay mineral in the deposits. X-ray diffraction (XRD) peaks of the kerolite are characteristically broadened indicating its extremely poor crystallinity. Few changes were observed in the XRD patterns of this kerolite when it was subjected to various humidity, temperature and ethylene-glycol treatments. The crystals appear as flaky masses with irregular or jagged edges in scanning (SEM) and transmission electron microscopy (TEM). Electron probe and energy dispersive X-ray (EDX) microanalysis show that the clay material is dominated by Mg-Si-O, with minor amounts of Al and Ca in some samples. The chemical composition, thermal analysis and TEM observations suggest that smaller amounts of an amorphous serpentine-like phase are mixed with the kerolite. Kerolite is often the only mineral associated with poorly mineralized, actively-growing microbial mats in these caves and it is common in completely lithified microbial mats. The latter commonly have microstromatolitic structures with kerolite as a dominant phase. These features suggest that kerolite formation is at least in part a result of microbial activity. The abundant extracellular polymers of the mat-forming bacteria bind and concentrate ions (Mg2+, silica) from solution and serve as nucleation sites for kerolite precipitation. Conditions within the mats also probably lead to formation of Mg-Si-gels, amorphous Mg-silicate precursors and ultimately kerolite. Evaporation of the cave solutions may also contribute to kerolite formation.

The carbon cycle and carbon dioxide over Phanerozoic time: the role of land plants

A model (GEOCARB) of the long–term, or multimillion year, carbon cycle has been constructed which includes quantitative treatment of (1) uptake of atmospheric CO 2 by the weathering of silicate and carbonate rocks on the continents, and the deposition of carbonate minerals and organic matter in oceanic sediments; and (2) the release of CO 2 to the atmosphere via the weathering of kerogen in sedimentary rocks and degassing resulting from the volcanic–metamorphic–diagenetic breakdown of carbonates and organic matter at depth. Sensitivity analysis indicates that an important factor affecting CO 2 was the rise of vascular plants in the Palaeozoic. A large Devonian drop in CO 2 was brought about primarily by the acceleration of weathering of silicate rock by the development of deeply rooted plants in well–drained upland soils. The quantitative effect of this accelerated weathering has been crudely estimated by present–day field studies where all factors affecting weathering, other than the presence or absence of vascular plants, have been held relatively constant. An important additional factor, bringing about a further CO 2 drop into the Carboniferous and Permian, was enhanced burial of organic matter in sediments, due probably to the production of microbially resistant plant remains (e.g. lignin). Phanerozoic palaeolevels of atmospheric CO 2 calculated from the GEOCARB model generally agree with independent estimates based on measurements of the carbon isotopic composition of palaeosols and the stomatal index for fossil plants. Correlation of CO 2 levels with estimates of palaeoclimate suggests that the atmospheric greenhouse effect has been a major factor in controlling global climate over the past 600 million years.

Mars volatile evolution: Evidence from stable isotopes

Constraints on the history of the Martian volatile system can be determined by using observations of the ratios 18O/ 16O, 17O/ 16O, 13C/ 12C, and D/H in atmospheric species and in various components of the SNC meteorites which are thought to be pieces of the Martian surface. These observations are compared with the variations expected from processes which can fractionate the different isotopes—thermal escape to space, nonthermal escape to space, formation of carbonate mineral deposits from atmospheric CO 2, and condensation of CO 2 or H 2O ice from the atmosphere. All of the available observations and models are synthesized for the first time, along with other observations of the Martian surface and atmosphere, in order to provide a coherent view of the evolution of both CO 2 and H 2O over geologic time. While no scenarios for atmospheric evolution can be absolutely and uniquely ruled out, a strongly favored scenario does exist. In this favored model, fractionation of oxygen by escape to space is diluted by the exchange with a nonatmospheric reservoir; it is unlikely that there is sufficient CO 2 adsorbed in the regolith to serve this function, so the polar water-ice deposits must be exchanging with the atmospheric water over geologic time. Exchange of oxygen between atmospheric CO 2 and H 2O probably provides the observed fractionation between those species. While the observed fractionation of D/H suggests a significant loss of water to space, the timescale on which this loss occurred is uncertain; the results can be reconciled with the oxygen results by invoking time-dependent models (which are consistent with what we know about the Mars climate). Additional observations and numerical modeling efforts which would help eliminate some of the uncertainties in the results are suggested.

Discovery of sublacustrine hydrothermal activity and associated massive sulfides and hydrocarbons in the north Tanganyika trough, East African Rift

Massive sulfides and carbonate mineral deposits associated with sublacustrine thermal springs were recently discovered along the Zaire side of the north Tanganyika trough, western branch of the East African Rift. This hydrothermal activity, investigated by scuba diving at a maximum depth of 20 m, is located at the intersection of major north-south normal faults and northwest-southeast faults belonging to the Tanganyika-Rukwa-Malawi (TRM) strike-slip fault zone. The preliminary results presented here come from analyses of sulfide deposits, hydrothermal fluids, and associated hydrocarbons that result from geothermal activity in this part of the East African Rift filled by a thick pile of sediment, the north Tanganyika trough.

A negative feedback mechanism for the long‐term stabilization of Earth's surface temperature

We suggest that the partial pressure of carbon dioxide in the atmosphere is buffered, over geological time scales, by a negative feedback mechanism in which the rate of weathering of silicate minerals (followed by deposition of carbonate minerals) depends on surface temperature, and surface temperature, in turn, depends on carbon dioxide partial pressure through the greenhouse effect. Although the quantitative details of this mechanism are speculative, it appears able partially to stabilize earth's surface temperature against the steady increase of solar luminosity believed to have occurred since the origin of the solar system.