Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Early dolomitisation of the Lower-Middle Ordovician cyclic carbonates in northern Tarim Basin,NW China

High-frequency metre-scale cycles are present within the Lower-Middle Ordovician carbonate successions in northern Tarim Basin, NW China. These metre-scale cycles were variably dolomitised from top to bottom. Three types of replacive dolomites were recognised, including dololaminite(very finely to finely crystalline, planar-s to nonplanar-a dolomite;type-1), patterned dolomite(finely crystalline, planar-s dolomite; type-2), and mottled dolomite(finely to medium crystalline,nonplanar-a(s) dolomite; type-3). Petrographic evidence indicate these dolomites were primarily deposited in supratidal to restricted subtidal environments, and formed in near-surface to shallow burial realms. Geochemically, all types of dolomites have similar δ13C and 87Sr/86 Sr ratios comparable to calcite precipitated in equilibrium with the Early-Middle Ordovician seawater. These geochemical attributes indicate that these dolomites were genetically associated and likely formed from connate seawater-derived brines. Of these, type-1 dolomite has δ18O values(.4.97‰ to.4.04‰ VPDB) slightly higher than those of normal seawater dolomite of the Early-Middle Ordovician age. Considering the absence of associated evaporites within type-1 dolomite, its parental fluids were likely represented by slightly evaporated(i.e., mesosaline to penesaline) seawater with salinity below that of gypsum precipitation. More depleted δ18O values(.7.74‰ to.5.20‰ VPDB) of type-2 dolomite and its stratigraphic position below type-1 dolomite indicate the generation of this dolomite from mesosaline to penesaline brines at higher temperatures in near-surface to shallow burial domains. Type-3 dolomite yields the most depleted δ18O values(–9.30‰to –7.28‰ VPDB), pointing to that it was most likely formed from coeval seawater-derived brines at highest temperatures in a shallow burial setting. There is a downward decreasing trend in δ18O values from type-1 through type-2 to type-3 dolomites, and in abundance of dolomites, indicating that the dolomitising fluids probably migrated downward from above and persisted into shallow burial conditions.     

Isotopic evidence for local derivation of strontium in deep-seated, fracture-filling calcite from granitic rocks in drill hole GT-2, Los Alamos scientific laboratory dry hot rock program

Fracture-filling calcites from GT-2 Drill Core (LASL-DHR Program) yield ⁸⁷Sr/⁸⁶Sr ranging from 0.724 to 0.734. These data indicate derivation of Sr in the calcite from 1.7 ± 0.1 b.y. old granitic basement rocks at depth and not from the overlying Madera Formation (Pennsylvanian) which possesses high Sr content with ⁸⁷Sr/⁸⁶Sr near 0.709. This, in turn, indicates that meteoric waters did not transport significant amounts of Sr from the Madera Formation into the Precambrian basement rocks to great depth.     

Formation of phreatic caves in an eogenetic karst aquifer by CO2 enrichment at lower water tables and subsequent flooding by sea level rise

Formation of extensive phreatic caves in eogenetic karst aquifers is widely believed to require mixing of fresh and saltwater. Extensive phreatic caves also occur, however, in eogenetic karst aquifers where fresh and saltwater do not mix, for example in the upper Floridan aquifer. These caves are thought to have formed in their modern settings by dissolution from sinking streams or by convergence of groundwater flow paths on springs. Alternatively, these caves have been hypothesized to have formed at lower water tables during sea level low‐stands. These hypotheses have not previously been tested against one another. Analyzing morphological data and water chemistry from caves in the Suwannee River Basin in north‐central Florida and water chemistry from wells in the central Florida carbonate platform indicates that phreatic caves within the Suwannee River Basin most likely formed at lower water tables during lower sea levels. Consideration of the hydrological and geochemical constraints posed by the upper Floridan aquifer leads to the conclusion that cave formation was most likely driven by dissolution of vadose CO₂ gas into the groundwater. Sea level rise and a wetter climate during the mid‐Holocene lifted the water table above the elevation of the caves and placed the caves tens of meters below the modern water table. When rising water tables reached the land surface, surface streams formed. Incision of surface streams breached the pre‐existing caves to form modern springs, which provide access to the phreatic caves. Phreatic caves in the Suwannee River Basin are thus relict and have no causal relationship with modern surficial drainage systems. Neither mixing dissolution nor sinking streams are necessary to form laterally extensive phreatic caves in eogenetic karst aquifers. Dissolution at water tables, potentially driven by vadose CO₂ gas, offers an underappreciated mechanism to form cavernous porosity in eogenetic carbonate rocks. Copyright © 2012 John Wiley & Sons, Ltd.     

Anomalous drip in the Punkva caves (Moravian Karst): relevant implications for paleoclimatic proxies

The anomalous drip in the Punkva caves (Moravian Karst) shows specific hydrogeochemical properties such as low SI_calcite ~ 0.14 ± 0.11 (standard deviation), low mineralization (4.53 ± 0.42) × 10^?3 mol l^?1, and enhanced values of δ¹³C (?7.85 to ?8.35‰ VPDB), Mg/Ca × 1000 ratio (45.7 ± 3.3), and Sr/Ca × 1000 ratio (0.65 ± 0.06). By these properties, the anomalous drip significantly differs from other regular drips in the same cave and other caves in the region. The study suggests that the anomalous drip properties are a consequence of prior calcite precipitation or/and water mixing along the water flow path. As the former processes are spatially controlled, the knowledge of dripwater flow path seems to be necessary for correct paleoclimatic/paleoenvironmental reconstructions. Copyright © 2015 John Wiley & Sons, Ltd.     

The hydrothermal karstification and its effect on Ordovician carbonate reservoir in Tazhong uplift of Tarim Basin,Northwest China

With a detailed study on petrology, mineralogy and geochemistry of some important Ordovician carbonate well core samples in Tazhong uplift of Tarim Basin, the distinguishing symbols of hydrothermal karstification are first put forward as the phenomena of rock hot depigmentation, hot cataclasm and the appearance of typical hydrothermal minerals such as fluorite, barite, pyrite, quartz and sphalerite. The main homogenization temperatures of primary fluid inclusions in fluorite are from 260 to 310°C, indicating the temperature of hydrothermal fluid. The fluid affected the dissolved rocks and showed typical geochemistry features with low contents of Na and Mg, and high contents of Fe, Mn and Si. The ratio of ³He/⁴He is 0.02R _a, indicating the fluid from the typical continental crust. The hydrothermal fluid karstification pattern may be described as follows: the hot fluid is from the Permian magma, containing dissolving ingredients of CO₂ and H₂S, and shifts along fault, ruptures and unconformity, and dissolves the surrounding carbonates while it flows. The mechanism of hydrothermal karstification is that the mixture of two or more fluids, which have different ion intensity and pH values, becomes a new unsaturated fluid to carbonates. The hydrothermal karstification is an important process to form hypo-dissolved pinholes in Ordovician carbonates of Tazhong uplift of Tarim Basin, and the forming of hydrothermal minerals also has favorable influence on carbonate reservoirs.

     

The hydrothermal karstification and its effect on Ordovician carbonate reservoir in Tazhong uplift of Tarim Basin,Northwest China

With a detailed study on petrology, mineralogy and geochemistry of some important Ordovician carbonate well core samples in Tazhong uplift of Tarim Basin, the distinguishing symbols of hydrothermal karstification are first put forward as the phenomena of rock hot depigmentation, hot cataclasm and the appearance of typical hydrothermal minerals such as fluorite, barite, pyrite, quartz and sphalerite. The main homogenization temperatures of primary fluid inclusions in fluorite are from 260 to 310°C, indicating the temperature of hydrothermal fluid. The fluid affected the dissolved rocks and showed typical geochemistry features with low contents of Na and Mg, and high contents of Fe, Mn and Si. The ratio of ³He/⁴He is 0.02R _a, indicating the fluid from the typical continental crust. The hydrothermal fluid karstification pattern may be described as follows: the hot fluid is from the Permian magma, containing dissolving ingredients of CO₂ and H₂S, and shifts along fault, ruptures and unconformity, and dissolves the surrounding carbonates while it flows. The mechanism of hydrothermal karstification is that the mixture of two or more fluids, which have different ion intensity and pH values, becomes a new unsaturated fluid to carbonates. The hydrothermal karstification is an important process to form hypo-dissolved pinholes in Ordovician carbonates of Tazhong uplift of Tarim Basin, and the forming of hydrothermal minerals also has favorable influence on carbonate reservoirs.     

Diagenetic fluid evolution and water-rock interaction model of carbonate cements in sandstone: An example from the reservoir sandstone of the Fourth Member of the Xujiahe Formation of the Xiaoquan-Fenggu area,Sichuan Province,China

Carbonate cement is the most abundant cement type in the Fourth Member of the Xujiahe Formation in the Xiaoquan-Fenggu area of the West Sichuan Depression. Here we use a systematic analysis of carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and enclosure homogenization temperatures to study the precipitation mechanism, pore fluid evolution, and distribution of different types of carbonate cement in reservoir sand in the study area. Crystalline calcite has relatively heavy carbon and oxygen isotope ratios(δ13C = 2.14‰, δ18O = -5.77‰), and was precipitated early. It was precipitated directly from supersaturated alkaline fluid under normal temperature and pressure conditions. At the time of precipitation, the fluid oxygen isotope ratio was very light, mainly showing the characteristics of a mixed meteoric water-seawater fluid(δ18O = -3‰), which shows that the fluid during precipitation was influenced by both meteoric water and seawater. The calcite cement that fills in the secondary pores has relatively lighter carbon and oxygen isotope ratios(δ13C = -2.36‰, δ18O = -15.68‰). This cement was precipitated late, mainly during the Middle and Late Jurassic. An important material source for this carbonate cement was the feldspar corrosion process that involved organic matter. The Ca2+, Fe3+ and Mg2+ ions released by the clay mineral transformation process were also important source materials. Because of water-rock interactions during the burial process, the oxygen isotope ratio of the fluid significantly increased during precipitation, by about 3‰. The dolomite cements in calcarenaceous sandstone that was precipitated during the Middle Jurassic have heavier carbon and oxygen isotope ratios, which are similar to those of carbonate debris in the sandstone(δ13C = 1.93‰, δ18O = -6.11‰), demonstrating that the two are from the same source that had a heavier oxygen isotope ratio(δ18O of about 2.2‰). The differences in fluid oxygen isotope ratios during cement precipitation reflect the influences of different water-rock interaction systems or different water-rock interaction strengths. This is the main reason why the sandstone containing many rigid particles(lithic quartz sandstone) has a relatively negative carbon isotope ratio and why the precipitation fluid in calcarenaceous sandstone has a relatively heavier oxygen isotope ratio.     

Heterogeneous distributions of CO2 may be more important for dissolution and karstification in coastal eogenetic limestone than mixing dissolution

Mixing dissolution, a process whereby mixtures of two waters with different chemical compositions drive undersaturation with respect to carbonate minerals, is commonly considered to form cavernous macroporosity (e.g. flank margin caves and banana holes) in eogenetic karst aquifers. On small islands, macroporosity commonly originates when focused dissolution forms globular chambers lacking entrances to the surface, suggesting that dissolution processes are decoupled from surface hydrology. Mixing dissolution has been thought to be the primary dissolution process because meteoric water would equilibrate rapidly with calcium carbonate as it infiltrates through matrix porosity and because pCO₂ was assumed to be homogeneously distributed within the phreatic zone. Here, we report data from two abandoned well fields in an eogenetic karst aquifer on San Salvador Island, Bahamas, that demonstrate pCO₂ in the phreatic zone is distributed heterogeneously. The pCO₂ varied from less than log ?2.0 to more than log ?1.0 atm over distances of less than 30 m, generating dissolution in the subsurface where water flows from regions of low to high pCO₂ and cementation where water flows from regions of high to low pCO_2. Using simple geochemical models, we show dissolution caused by heterogeneously distributed pCO₂ can dissolve 2.5 to 10 times more calcite than the maximum amount possible by mixing of freshwater and seawater. Dissolution resulting from spatial variability in pCO₂ forms isolated, globular chambers lacking initial entrances to the surface, a morphology that is characteristic of flank margin caves and banana holes, both of which have entrances that form by erosion or collapse after cave formation. Our results indicate that heterogeneous pCO₂, rather than mixing dissolution, may be the dominant mechanism for observed spatial distribution of dissolution, cementation and macroporosity generation in eogenetic karst aquifers and for landscape development in these settings. Copyright © 2015 John Wiley & Sons, Ltd.     

Organic carbon inputs,common ions and degassing: rethinking mixing dissolution in coastal eogenetic carbonate aquifers

Caves deliver freshwater from coastal carbonate landscapes to estuaries but how these caves form and grow remains poorly understood. Models suggest fresh and salt water mixing drives dissolution in eogenetic limestone, but have rarely been validated through sampling of mixing waters. Here we assess controls on carbonate mineral saturation states using new and legacy geochemical data that were collected in vertical profiles through three cenotes and one borehole in the Yucatan Peninsula. Results suggest saturation states are primarily controlled by carbon fluxes rather than mixing. Undersaturation predicted by mixing models that rely on idealized end members is diminished or eliminated when end members are collected from above and below actual mixing zones. Undersaturation due to mixing is limited by CO₂ degassing from fresh water in karst windows, which results in calcite supersaturation. With respect to saline groundwater, controls on capacity for mixing dissolution were more varied. Oxidation of organic carbon increased pCO₂ of saline groundwater in caves (pCO₂ = 10^–2.06 to 10^–0.96 atm) relative to matrix porosity (10^–2.39 atm) and local seawater (10^–3.12 atm). The impact of increased pCO₂ on saturation state, however, depended on the geochemical composition of the saline water and the magnitude of organic carbon oxidation. Carbonate undersaturation due to mixing was limited where gypsum dissolution (Cenote Angelita) or sulfate reduction (Cenote Calica) increased concentrations of common ions (Ca²⁺ or HCO₃^?, respectively). Maximum undersaturation was found to occur in mixtures including saline water that had ion concentrations and ratios similar to seawater, but with moderately elevated pCO₂ (Cenote Eden). Undersaturation, however, was dominated by the initial undersaturation of the saline end member, mixing was irrelevant. Our results add to a growing body of literature that suggests oxidation of organic carbon, and not mixing dissolution, is the dominant control on cave formation and enlargement in coastal eogenetic karst aquifers. Copyright © 2016 John Wiley & Sons, Ltd.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Hydrogeochemical evolution of Ordovician limestone groundwater in Yanzhou,North China

Major‐ion compositions of groundwater are employed in this study of the water–rock interactions and hydrogeochemical evolution within a carbonate aquifer system. The groundwater samples were collected from boreholes or underground tunnels in the Ordovician limestone of Yanzhou Coalfield where catastrophic groundwater inflows can be hazardous to mining and impact use of the groundwater as a water supply. The concentration of total dissolved solid (TDS) ranged from 961 to 3555 mg/l and indicates moderately to highly mineralized water. The main water‐type of the middle Ordovician limestone groundwater is Ca‐Mg‐SO₄, with SO₄^2‐ ranging from 537 to 2297 mg/l, and average values of Ca²⁺ and Mg²⁺ of 455.7 and 116.6 mg/l, respectively. The water samples were supersaturated with respect to calcite and dolomite and undersaturated or saturated with respect to gypsum. Along the general flow direction, deduced from increases of TDS and Cl^‐, the main water–rock interactions that caused hydrogeochemical evolution of the groundwater within the aquifer were the dissolution of gypsum, the precipitation of calcite, the dissolution or precipitation of dolomite, and ion exchange. Ion exchange is the major cause for the lower mole concentration of Ca²⁺ than that of SO₄^2‐. The groundwater level of Ordovician aquifer is much higher than that of C‐P coal‐bearing aquifers, so the potential flow direction is upward, and the pyrite in coal is not a possible source of sulfate; additional data on the stable sulfur and oxygen isotopic composition of the sulfate may be helpful to identify its origin. Although ion exchange probably accounts for the higher mole concentration of Na⁺ than that of Cl^‐, the dissolution of aluminosilicate cannot be ruled out. The data evaluation methods and results of this study could be useful in other areas to understand flow paths in aquifers and to provide information needed to identify the origin of groundwater. Copyright © 2012 John Wiley & Sons, Ltd.     

Influence of Ordovician carbonate reservoir beds in Tarim Basin by faulting

The quality of the Ordovician carbonate reservoir beds in the Tarim Basin is closely related to the development of secondary pores,fractures and cavities. Karstification is important in improving the properties of reservoir beds,and karstification related to unconformity has caught wide attention. Compared with the recent research on the unconformity karst reservoir bed improvement,this paper shows a new way of carbonate reservoir bed transformation. Based on field survey,core and slices observation,transformation of Ordovician carbonate reservoir beds by faulting can be classified into three types: (1) Secondary faults and fracturs generated by faulting improved carbonate reservoir bed properties,which were named the Lunnan or Tazhong82 model; (2) upflow of deep geothermal fluids caused by faulting,with some components metasomatizing with carbonate and forming some secon-dary deposit,such as fluorite. It can improve carbonate reservoir bed properties obviously and is named the Tazhong 82 model; and (3) the faulting extending up to the surface increased the depth of supergene karstification and the thickness of reservoir bed. It is named the Hetianhe model. Trans-formation effect of carbonate reservoir beds by faulting was very significant,mainly distributed on the slopes or on the edge or plunging end of the uplift.     

Limestone Dissolution Processes in Beke Doline Aggtelek National Park,Hungary

Aggtelek National Park, Hungary, is a limestone karst upland characterized by karren, dolines and river caves. For a period of two years, climatic and carbonate dissolution variables were monitored at four depths in a 7·5 m shaft through the soil fill in the floor of a typical large (150 m diameter) doline. Results are compared to other monitoring stations in the shallow soils on side slopes. Runoff and groundwater flow are focused into the base of the doline soil fill, where moisture is maintained at 70–90 per cent field capacity and temperatures permit year-round production of soil CO₂. The capacity to dissolve calcite (limestone) ranges from c. 3 g m⁻² per year beneath thin soils on the driest slopes to 17–30 g m⁻² per year in the top 1–2 m of doline fill and at its base 5–7 m below. © 1997 John Wiley & Sons, Ltd.     

Strontium isotope geochemistry of the Lemachang independent silver ore deposit, northeastern Yunnan, China

Sr isotope geochemical studies (the 87Sr/86Sr and ?18O-87Sr/86Sr systems) on the wall rocks and ores from the Lemachang independent Ag deposit in northeastern Yunnan provide strong evidence that the ore-forming fluids had flown through radiogenetically Sr-enriched rocks or strata prior to their entry into the locus of ore precipitation, and water-rock interaction is the main mechanism of Ag ore precipitation. The radiogenetically Sr-enriched source region may be the Proterozoic basement (the Kunyang and Hekou groups). Moreover, the theoretical modeling of the Sr isotopic system indicates that the ore-forming fluids contain as much as 3×10?6 Sr with isotopic composition of Sr being 0.750 and that of oxygen 7.0‰. The ore-forming temperatures were estimated at 150-250℃ for the carbonate rock-type ores and at 200-260℃ for the clastic rock-type.     

Petrogenesis of the Ulsan carbonate rocks from the south-eastern Kyongsang Basin, South Korea

Abstract The petrogenesis of the Ulsan carbonate rocks in the Mesozoic Kyongsang Basin of South Korea, which have previously been interpreted as limestone of Paleozoic age, is reconsidered in the present study. Within the Kyongsang Basin, a small volume of carbonate rocks, containing a magnetite deposit and spatially associated ultramafic rocks, is surrounded by sedimentary, volcanic and granitic rocks of the Mesozoic age. The simple cross‐cutting relationships and other outcrop features of the area indicate that the carbonate rocks are an intrusive phase and younger than the other surrounding Mesozoic rocks. The Ulsan carbonates have low concentrations of rare earth elements (REE) and trace elements with the carbon and oxygen isotope values in the range of δ¹³C_PDB = 2.4 to 4.0‰ and δ¹⁸O_SMOW = 17.0 to 19.5‰. Outcrop evidence and geochemical signatures indicate that the Ulsan carbonates were formed from crustal carbonate melts, which were generated by the melting/fluxing of crustal carbonate materials, caused by the emplacement‐related processes of alkaline A‐type granitic rocks. Compared to typical mantle‐derived carbonatites associated with silica‐undersaturated, strongly peralkaline systems, the relatively small size and geochemical characteristics of the Ulsan carbonates reflect carbonatite genesis in a silica‐saturated, weakly alkali intrusive system. Major deep‐seated tectonic fractures formed by the collapse of the cauldron or the rift system associated with the opening of the East Sea (Japan Sea) might have facilitated the ascent of the crustal carbonate melts.     

The influence of the carbonate dissolution rate on the growth and composition of Co-rich ferromanganese crusts from Central Pacific seamount areas

The metal composition of oceanic ferromanganese deposits occurring in seamount regions (Line Islands chain and Mid-Pacific Mountains) varies with water depth and age. The results of metal determinations of carbonate plankton samples suggest that carbonate dissolution in the water column might have an important influence on the accretion and composition of hydrogenetic precipitates. Two ferromanganese crust generations of different age have been observed The precipitation of the older crust took probably place during early Oligocene, the younger crust began to form during middle Miocene. Between the two crust generations periods of carbonate sedimentation and of phosphorite deposition occur. The hydrogenetic formation of the crusts is controlled by the metal supply from the water column, according to the laws of colloidal surface chemistry.Dissolution experiments with carbonate plankton samples show that the main Fe source for the hydrogenetic crust formation are colloidal Fe-hydroxide particles being released in the water column from the dissolution of carbonate plankton skeletons. In the case of Mn, maximum dissolved Mn occurs in the oxygen minimum zone as the result of in-situ break-down of organic matter and the in-situ reduction of Mn-bearing solid phases. Closely beneath the oxygen minimum zone a Fe supply, mobilized within the oxygen minimum zone, has also to be taken into account. In the water column below the oxygen minimum zone, a mixture of colloidal particles of MnFe-oxyhydroxide and colloidal AlFe-silicate, precipitate together on the surface of substratum rocks. The mixing ratio of these colloidal phases controlling the metal composition of the ferromanganese precipitates, is depth-dependent and shows also temporal variations. In general, Mn/Fe ratio, Ni, and Co contents decrease with depth down to the calcite compensation depth.The most probable mechanism for the ultimate removal of Co and Ni from the water column might be a surface reaction. δ-MnO₂ is specifically able to absorb hydrous Co²⁺ and Ni²⁺ ions. Because of the surface enrichment of Co and the strong electrical field of Mn(IV), a subsequent oxidation of Co²⁺ to Co³⁺ takes place leading to higher enrichment of Co in comparison to Ni. The most important factor governing the high Co enrichment in the ferromanganese crusts is the growth rate: the lower the growth rate, the higher the Co content. Maximum values of up to 2% Co occurring in samples from water depths between 1500 and 1100 m [1] are related to lower carbonate dissolution rates and corresponding lower Fe supply.The metal supply from the water column is strongly related to distinct environmental factors such as bio-productivity, range of lysocline and calcite compensation depth, rate of carbonate dissolution, and activity of the Antarctic bottom water. Thus, our model shows that the growth periods and the metal composition of hydrogenetic seamount crusts are controlled by changes in the paleoceanography and reflect distinct environmental conditions.     

Oxygen isotopic compositions of Central Andean plutonic and volcanic rocks,latitudes 26°–29° south

Oxygen isotope data are reported for 27 igneous rocks of Mesozoic to Quaternary age from the Central Andes. 26–29°S. The plutonic rocks, and most of the volcanics, have δ¹⁸O values between 6.2 and 8.3‰.The whole-rock δ¹⁸O values show a weak correlation with initial⁸⁷Sr/⁸⁶Sr data. This O-Sr array differs from documented trends for calc-alkaline plutonic suites from California, Scotland and northern Italy, but overlaps with data for volcanic and plutonic rocks from Ecuador, northern Chile and southern Perú.The oxygen isotope results indicate that the magmas evolved without significant contamination from supracrustal rocks (e.g., rocks that experienced¹⁸O enrichment during surficial weathering). The available O, Sr and Pb isotopic data for these rocks are best explained by magma generation in the upper mantle or lower crust. From the Late Mesozoic on, the⁸⁷Sr/⁸⁶Sr values were modified at depth by isotopic exchange between the magma and a continually thickening crust of plutonic rocks of Late Precambrian to early Mesozoic age.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.