Bank-derived carbonate sediment transport and dissolution in the Hawaiian Archipelago

This investigation used two approaches to examine the flux of bank-derived carbonate particles and determine the potential influence of benthic carbonate particle dissolution on the carbon chemistry of the waters around the Hawaiian Archipelago. First, the particle flux near several representative carbonate banks in the Hawaiian Archipelago was measured and compared with the flux at a distal site (ALOHA) approximately 100 km north of Oahu, Hawaii. The results of four sediment trap deployments on three carbonate banks in the Hawaiian Archipelago demonstrate that the flux of bank-derived carbonate particles are consistently one to two orders of magnitude higher than the fluxes at the distal station. Furthermore, the mineralogy of the carbonate flux near the banks, which includes very soluble bank-derived aragonite and magnesian calcite particles, is distinctly different from that of the distal fluxes. Second, the chemistry of the waters at each bank station along the archipelago was characterized and compared with the chemistry of the distal waters to determine if differences in the particle flux were reflected in the carbon chemistry. Higher alkalinity and carbonate ion concentrations were observed around all of the banks studied. The saturation state of these waters suggests that the dissolution of some magnesian calcite and aragonite phases could explain the higher alkalinity values. Calculations suggest that the dissolution of benthically-derived aragonite and magnesian calcite may be an important component of the North Pacific alkalinity budget and a potential sink for anthropogenic CO₂.     

Nearshore Carbonate Dissolution in the Hawaiian Archipelago?

Inorganic carbon measurements made in the late 1980s suggest that alkalinity in the waters surrounding the Hawaiian Archipelago is elevated relative to the oligotrophic waters of the North Pacific. These observations have been interpreted as evidence for a “halo” of elevated carbonate saturation state produced by the dissolution of highly soluble magnesium calcites and aragonite on the island platform or in the water column surrounding the islands. If present, this “halo” has implications for air–sea carbon dioxide exchange in Hawaiian waters and may impact the response of coral reef communities to the acidification of the surface waters of the global ocean. The purpose of this study was to assess the magnitude and extent of the elevated calcium carbonate saturation state observed on previous expeditions to this region. Transects were conducted near several atolls in the Northwestern Hawaiian Islands from shallow water adjacent to the forereef to the open ocean 15 km from the island. Hydrographic profiles were collected at each station, and discrete water samples were collected for the measurement of carbon system parameters necessary to compute calcium carbonate saturation state. Our data were compared with observations made at the Hawaii Ocean Time-series site at Station ALOHA and with hydrographic data collected on the WOCE lines in the North Pacific around the archipelago. We did not detect a carbonate dissolution halo around the islands. We conclude that the previously observed halo was probably an analytical artifact, or possibly a result of extreme variability in carbon chemistry surrounding the islands.     

Temperate shelf carbonate sediments in the Cenozoic of New Zealand

Shelf limestones are widely distributed in New Zealand Cenozoic sequences and are especially well developed in the Oligocene. Detailed field and laboratory work on several Oligocene occurrences, and reconnaissance field-work at most other sections have elucidated the major characteristics of the environment, texture, composition and diagenesis of these sediments. Several generalizations emerge which contrast with the commonly accepted characteristics of shallow marine carbonate sedimentation established from studies of tropical and subtropical deposits. The limestones are either calcarenites or, less commonly, calcilutites and, in general, these two lithologies are mutually exclusive, both in time and space. The allochems and interparticle carbonate mud (where developed) in calcarenitic limestones consist almost exclusively of fragmented skeletal material derived primarily from bryozoan, echinodermal, benthic foraminiferal, barnacle, brachiopod, bivalve and coralline red algal tests. The calcilutitic limestones consist mainly of whole and disintegrated tests of pelagic foraminifers and coccolithophorids. Non-skeletal carbonate components such as ooids, pellets and aggregates are conspicuously absent from both lithologies. Reefal structures are also absent or rare and are mainly oyster reefs. The limestones commonly contain a significant content of terrigenous material and/or glauconite and at the stratigraphic level the limestones are intimately associated with terrigenous formations. The distribution of the carbonate sediments has been governed mainly by rate of supply of river-derived terrigenous material, by subsequent dispersal patterns of this material over the shelf, and by current sorting. As a consequence of selective grain transport, bedding in the limestones is often defined by the cyclic alternation on a wide range of scales of carbonate units that are relatively enriched and relatively impoverished in terrigenous material. The primary (carbonate) mineralogy of the carbonate sediments was completely dominated by magnesium calcite and/or calcite with only small amounts of aragonite and no dolomite or associated evaporite minerals. The metastable magnesium calcite and aragonite grains were probably altered on, or close below, the shallow sea-floor. Among other factors, transformation was encouraged by the absorption of magnesium in pore waters by montmorillonitic clays and by the complete oxidation of all organic matter in the bottom sediments. Magnesium calcite grains were stabilized by texturally non-destructive incongruent dissolution, but aragonite was often dissolved without trace from the sediment, especially in grainstones. Thus submarine diagenesis has been characterized by selective dissolution phenomena. Cementation by granular and syntaxial rim orthosparite of calcite and/or ferroan calcite composition occurred mainly during shallow subsurface burial and was associated with the intergranular solution of calcitic skeletal fragments, especially at those levels in the sediment relatively enriched in terrigenous material. This lithification process has worked to accentuate and modify original litho-logic differences and sedimentary structures in the primary sediments and has produced a kind of rhythmic vertical alternation of less well cemented, microstylolitized, impure limestone beds (‘cement-donor’ beds) and well cemented, more open textured, purer limestone beds (‘cement-receptor’ beds). The New Zealand limestones formed between latitudes 60° S and 35° S under generally cool temperate to warm temperate climate conditions. Oxygen isotopes suggest that surface waters were mainly significantly cooler than 20°C, so that shelf waters may have experienced extended periods of undersaturation with respect to calcium carbonate. Generally open circulation patterns maintained near normal salinity values over the entire shelf platform. Calculated sedimentation rates for the New Zealand carbonate sediments are generally very low (< 5 cm/1000 years). Periods of more active deposition commonly alternated with longer periods of non-deposition and by-passing or erosion. It is concluded that many characteristics of the New Zealand shelf limestone occurrences are explained best by a temperate latitude model of shallow marine carbonate sedimentation.     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

Vanished evaporites and carbonate formation in the Neoarchaean Kogelbeen and Gamohaan formations of the Campbellrand Subgroup,South Africa

Field, petrographic and stable isotopic evidence indicate the former presence of widespread evaporites in the Neoarchaean Campbellrand Subgroup of South Africa. Calcitization of the vanished but once laterally-extensive evaporites was apparently driven by bacterial sulphate reduction of solid sulphate in association with organic diagenesis and pyrite precipitation within platform-wide microbialites and sapropels. This counters current interpretations that much of the calcite was precipitated directly on the seafloor or in primary voids in open marine conditions controlled by regional seawater chemistry. Rather, large-scale microbial mediation of ambient waters across a shallow to emergent platform raised carbonate alkalinity and removed kinetic inhibitors to carbonate formation.The low preservation potential of Precambrian solid sulphate is related in part to bacterial sulphate reduction within the microbially-dominated ecosystems of which cyanobacteria were a major component. Evidence for the former presence of solid sulphate in shallow Neoarchaean seas includes pseudomorphs after selenite, also recorded from the contemporaneous Carawine Dolomite of Australia, together with rock fabrics and textures typical of evaporite dissolution. Importantly, sulphur isotopes of pyrite samples from the Cambellrand carbonates show a wide range of values indicating biogenic fractionation of sulphate, a signature also seen in the Neoarchaean Belingwe Greenstone Belt of Zimbabwe, and the Mt McRae and Jeerinah shales of Western Australia.Mass microbial colonization across extensive Neoarchaean epeiric seas witnessed the microbiogeochemical transformation of the Earth’s hydrosphere, atmosphere and biosphere. The consequences for a reducing ocean would be the progressive oxidation of the major dissolved species in surface seawater, most notably of reduced sulphur and iron. Cyanobacterial photosynthetic oxidation of surface seawater drove formation of aqueous sulphate and permitted the precipitation of extensive evaporites in restricted basins, perhaps beginning the process of ridding the oceans of reduced sulphur. The first dramatic explosion of carbonate precipitation can be related to intense bacterial sulphate reduction in association with anoxic organic diagenesis and pyrite formation within the decaying interiors of microbialites and in sapropels.     

Hydrogeochemical factors effecting the scaling problem in Balçova geothermal field,İzmir, Turkey

Reservoir fluid compositions have been assessed from analytical data on water samples collected from thermal and cold waters in Balçova geothermal field. The results of mineral equilibrium modelling indicate that the waters, with some exceptions, are systematically supersaturated with respect to calcite, aragonite, dolomite, chalcedony and quartz, but undersaturated with respect to amorphous silica, celestite, anhydrite and gypsum and undersaturated or supersaturated with respect to barite, low-albite, K-feldspar, gibbsite and Fe(OH)₃(a). Calculation of mineral saturation states and geochemical analyses of scale and field observations show that carbonate minerals (calcite, aragonite and dolomite) are most likely to be precipitated as a scale type. Besides carbonates, scale formation risk of amorphous silica, Fe(OH)₃(a), anhydrite, barite and celestite minerals should be taken into account in some wells and surface equipment. Most of the waters, with some exceptions, have carbonate scaling risk at all temperatures, whereas the other scaling risks only exist over a limited temperature range. While silica, Fe(OH)₃(a) and barite show a scaling tendency at low temperatures, anhydrite and celestite scaling occurs at higher temperatures.     

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ^44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ^44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ^44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ^44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.     

Evolution of the composition of seawater through geologic time, and its influence on the evolution of life

The redox state of the surface environment of the early Earth is still controversial, and a detailed and quantitative estimate is still lacking. We carried out in-situ analyses of major, trace, and rare-earth elements of carbonate minerals in rocks with primary sedimentary structures in shallow and deep sea-deposits, in order to eliminate secondary carbonate and contamination of detrital materials, and to estimate the redox condition of seawater through time. Based on the Ce content and anomalies of the carbonate minerals at given parameters of atmospheric CO₂ content (pCO₂) and Ca content of seawater, we calculated the oxygen contents of shallow and deep seawater, respectively. The results show that the oxygen content of the deep sea was low and constant until at least 1.9 Ga. The oxygen content of shallow seawater increased after 2.7 Ga, but fluctuated. It became quite high at 2.5 and 2.3 Ga, but eventually increased after the Phanerozoic. In addition, the calculation of a high pCO₂ condition shows that seawater was more oxic even in the Archean than at present, suggesting a relatively low pCO₂ through geologic time.Our detailed calculations from compositions of carbonate minerals in Three Gorge area, south China show a low oxygen content of seawater after the Snowball Earth until the late Ediacaran, an increase in the late Ediacaran, and a significant decrease around the Precambrian–Cambrian and Nemakit/Daldynian–Tommotian boundaries. These variations were possibly caused by global regression and dissolution of methane hydrates.     

Chemical Composition and Geologic History of Saline Waters in Aux Vases and Cypress Formations, Illinois Basin

Seventy-six samples of formation waters were collected from oil wells producing from the Aux Vases or Cypress Formations in the Illinois Basin. Forty core samples of the reservoir rocks were also collected from the two formations. Analyses of the samples indicated that the total dissolved solids content (TDS) of the waters ranged from 43,300 to 151,400 mg/L, far exceeding the 35,400 mg/L of TDS found in typical seawater. Cl-Br relations suggested that high salinities in the Aux Vases and Cypress formation waters resulted from the evaporation of original seawater and subsequent mixing of the evaporated seawater with concentrated halite solutions. Mixing with the halite solutions increased Na and Cl concentrations and diluted the concentration of other ions in the formation waters. The elemental concentrations were influenced further by diagenetic reactions with silicate and carbonate minerals. Diagenetic signatures revealed by fluid chemistry and rock mineralogy delineated the water-rock interactions that took place in the Aux Vases and Cypress sandstones. Dissolution of K-feldspar released K into the solution, leading to the formation of authigenic illite and mixed-layered illite/smectite. Some Mg was removed from the solution by the formation of authigenic chlorite and dolomite. Dolomitization, calcite recrystallization, and contribution from clay minerals raised Sr levels significantly in the formation waters. The trend of increasing TDS of the saline formation waters with depth can be explained with density stratification. But, it is difficult to explain the combination of the increasing TDS and increasing Ca/Na ratio with depth without invoking the controversial 'ion filtration' mechanism.     

The redox chemistry of Pu(V)O2+ interaction with common mineral surfaces in dilute solutions and seawater

It has long been recognized that the Pu⁴⁺ ion can be readily adsorbed on solid surfaces, but it has been assumed that the generally more abundant Pu(V)O₂⁺ ion should have little affinity for surfaces. Our results indicate that Pu(V)O₂⁺ can be adsorbed from dilute solutions and seawater on goethite, aragonite, calcite, and δ-MnO₂. Adsorption on δ-MnO₂ is severely depressed in seawater, probably as a result of site competition with seawater cations.The sorption behavior of PuO₂⁺ is influenced by oxidation-reduction reactions occurring on the mineral surfaces. Adsorption on δ-MnO₂ results in oxidation of adsorbed Pu(IV) and Pu(V) to Pu(VI). However, adsorption on goethite results in a reaction in which Pu(IV) and Pu(VI) are formed on the mineral surface. The Pu(VI) is slowly reduced to Pu(IV), leaving Pu(IV) as the dominant surface Pu species. This reaction can be photochemically catalyzed. PuO₂⁺ adsorbed on carbonate minerals behaves similarly to Np(V)O₂⁺ and undergoes little change in oxidation state after adsorption.     

A pulsed oxygenation in shallow seawater recorded by the Mesoproterozoic Wumishan Formation,North China Platform

Oxygen is crucial for the origin and early evolution of eukaryotes. However,the oxygen levels in the atmosphere and shallow ocean of Mesoproterozoic have been poorly constrained,with varying viewpoints including persistent low(equals to <0.1%~1% of the present atmosphere level,PAL),relatively high(>4%~8% of PAL),and dynamic variation. In order to further constrain the redox conditions in shallow waters where eukaryotes inhabited,the Ce anomaly of the peritidal carbonates from lower Member 4 of the Mesoproterozoic Wumishan Formation in North China was investigated. The results show that the significant negative Ce anomalies(Ce/Ce^*=0.82±0.11,n=10)occurs in the carbonate of the lower Member 4 of the Wumishan Formation with the thickness of about 150 m. The carbonate formation with the significant negative Ce anomaly is interlayered between the carbonates with inconspicuous positive Ce anomalies,which may represent a pulsed oxygenation in shallow seawater with a duration of ~5 Ma(~1480-1475 Ma). It reflects that the redox conditions of Mesoproterozoic shallow seawater fluctuated greatly rather than stable at low or relatively high level of oxygen. The results are helpful to determine the evolution of redox state of the Mesoproterozoic shallow sea,and it provides important information for studying the influence of redox state of seawater on the evolution of early eukaryotes.     

华北地台中元古界雾迷山组浅海脉冲式增氧

氧气对真核生物的起源和早期演化至关重要,但是有关元古宙中期大气和浅海氧气浓度的限定却分歧很大,目前存在持续低氧(<0.1%~1%现代大气水平,PAL)、相对高氧(>4%PAL)和动态波动等多种观点。为了进一步揭示真核生物集中分布的浅海水体的氧化还原条件,文中选择华北中元古界雾迷山组四段下部环潮坪碳酸盐岩为研究对象,通过稀土Ce异常重建当时正常浪基面之上海水的氧化还原状态。结果表明,雾迷山组四段下部1段厚约150m的碳酸盐岩地层(~1480-1475Ma)具有明显的Ce负异常(Ce/Ce^*=0.82±0.11,n=10),而下伏和上覆地层均为具弱Ce正异常的碳酸盐岩,可能代表了1次持续时间约5Ma的浅海脉冲式增氧过程。该层段的脉冲式增氧可能表明元古宙中期浅海氧气浓度存在频繁波动,并非处于稳定的低氧或相对高氧平台状态。该研究成果有助于进一步确定元古宙中期浅海氧化还原状态和演变特征,并为探讨海水氧化还原状态对早期真核生物演化的影响提供重要信息。     

Diagenesis of the Khuff Formation (Permian–Triassic), northern United Arab Emirates

This diagenetic study (including fieldwork, petrographic, fluid inclusion, and stable isotope investigations) deals with the outcrop of Upper Permian–Lower Triassic carbonate rocks, which are equivalent to the Khuff Formation. The studied succession, which outcrops in the Ras Al Khaimah region, northern United Arab Emirates, comprises three formations, including the Bih, the Hagil, and the Ghail formations. The study focuses on unraveling the conditions and fluid compositions encountered during diagenesis of the succession. Emphasize is also made on linking diagenesis to major stratigraphic surfaces and to highlight reservoir property evolution and heterogeneity of the studied rocks. The evolution of fluids and related diagenetic products can be summarized as follows: (1) formation of near-surface to shallow burial, fine-crystalline dolomite (dolomite matrix) through pervasive dolomitization of carbonate sediments by modified marine pore waters; (2) formation of coarse-crystalline dolomite cement by highly evolved marine pore waters (13–23 wt.% NaCl eq.) at elevated temperatures (120–208°C), and (3) calcite cementation by highly saline fluid (20–23 wt.% NaCl eq.) at high temperature (170–212°C). A final calcite cement generation has been formed by the percolation of meteoric fluids during uplift. Fracture- and vug-filling diagenetic minerals are mainly restricted to the mid-Bih breccia marker level, suggesting preferential focused fluid flow through specific stratigraphic surfaces as well as along tectonic-related structures. Reservoir properties have been evolved as result of the interplay of the original sedimentary texture and the diagenetic evolution. Porosity is higher in the Bih Formation, which is dominated by dolomitized packstones and grainstones, than in the Hagil and Ghail formations, consisting mainly of dolomitized mudstones and wackestones. Image analyses were used to quantify the visual porosity in thin sections. The highest porosity values were measured in the Bih Formation, which is characterized by significant amounts of vug- and fracture-filling cements. This feature is attributed to the increase of porosity owing to substantial dissolution of abundant intergranular and vug-filling cements. In contrast, the Hagil and Ghail formations, which consist of finer-grained rock than the Bih Formation, were less cemented, and thus, the porosity enhancement by cement dissolution was insignificant.     

海水化学演化对生物矿化的影响综述

显生宙非骨屑碳酸盐矿物经历了文石海和方解石海的交替,主要造礁生物和沉积物生产者的骨骼矿物与非骨屑碳酸盐矿物具有同步变化的趋势。这种长期的变化趋势可以用海水化学Mg/Ca摩尔比的变化来解释。流体包裹体、同位素和微量元素等证据也证实了海水化学在地质历史中经历过剧烈的变化。虽然生物诱导矿化和生物控制矿化的相对重要性一直存在争议,但古生物地层记录和人工海水养殖实验结果都表明,海水化学演化对生物矿化有重要的影响,体现在造礁生物群落的兴衰、生物起源时对骨骼矿物类型的选择以及微生物碳酸盐岩在地质历史中的分布等。这些为研究前寒武纪海水化学演化、古气候和古环境的重建、同位素地层对比以及碳酸盐的沉积和成岩等问题提供了新的思路。     

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite–celestite veins (Oftringen borehole,Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ¹⁸O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56–68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ¹³C and ⁸⁷Sr/⁸⁶Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ¹³C, high ⁸⁷Sr/⁸⁶Sr, and low Sr content in the uppermost 50–150 m of the Jurassic profile (upper Oxfordian). The ⁸⁷Sr/⁸⁶Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.     

Using non-conservative tracers to characterise karstification processes in the Merinos-Colorado-Carrasco carbonate aquifer system (southern Spain)

The systematic sampling of the chemical composition of the groundwater from five karst springs (including an overflow spring) and one outflowing borehole have permitted to determine distinctive chemical changes in the waters that reflect the geochemical processes occurring in a carbonate aquifer system from southern Spain. The analysis of the dissolution parameters revealed that geochemical evolution of the karst waters basically depends on the availability of the minerals forming aquifer rocks and the residence time within the aquifers. In the three proposed scenarios in the aquifers, which include the preferential flow routines, the more important geochemical processes taking place during the groundwater flow from the recharge to the discharge zones are: CO₂ dissolution and exsolution (outgassing), calcite net dissolution, calcite and dolomite sequential dissolution, gypsum/anhydrite and halite dissolution, de-dolomitization and calcite precipitation. A detailed analysis of the hydrochemical data set, saturation indices of the minerals and partial pressure of CO₂ in the waters joined to the application of geochemical modelling methods allowed the elaboration of a hydrogeochemical model of the studied aquifers. The developed approach contributes to a better understanding of the karstification processes and the hydrogeological functioning of carbonate aquifers, the latter being a crucial aspect for the suitable management of the water resources.     

Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO₃ (mole fraction).If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg_0.03Ca_0.97CO₃ results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO₃ (K'_sp = 10?6.30).The surface layer precipitated on a synthetic Mg_0.08Ca_0.92CO₃ equilibrates finally with a carbonate more soluble than calcite (K'_sp = 10?5.94) corresponding to the seeds composition.Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible.By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.     

A Reconstruction and Discussion of the Effect of Diagenetic Environment on Hydrocarbon Generation Based on Diagenetic Mineral Assemblage in Mudstone

Inorganic minerals in mudstone are composed of clay minerals,carbonate and detrital minerals.Detrital minerals(such as quartz and feldspar)are mainly original deposit.However,clay minerals(kaolinite,illite,and chlorite)and carbonate(calcite and dolomite)are mostly diagenetic minerals.Furthermore,conversion of the four kinds of clay minerals are common.The formation of clay minerals and carbonate is controlled by temperature,pressure,p H,Eh and type of cations during diagenesis.Therefore mineral assemblage can indicate the characteristics and change of diagenetic environment.In addition to inorganic minerals,there are also organic matter of different sources and chemical properties in mudstone.Traditionally,it is considered that evolution of organic matter is controlled by thermal effect.Now studies show that inorganic and organic matter can interact with each other and form clay-organic complexes.This suggest that attention should be paid to the influence of diagenetic mineral assemblage and diagenetic environment on the evolution of organic matter* Samples of mudstone from 1500-4500m of the Palaeogene in the Dongying Depression,China,were collected to investigate the changes of mudstone diagenetic environment.XRD,thin section and SEM were used to detect diagenetic minerals and assemblage characteristics.Results showed that content of detrital minerals,which are floating in mud matrix or preserved as silt laminae,is basically unchanged from shallow to deep strata.Clay minerals which are gathered as argillaceous matrix or preserved as argillaceous laminae have growth and decline relation to carbonate which mainly appear as micropoikilitic ferriferous calcite and ferriferous dolomite.All these characteristics indicate that detrital minerals are exogenetic,whereas carbonate is diagenetic minerals.Based on the SEM analysis of the clay minerals,it was found that smectite present honeycomb and reticulate structure,while illite present filiform and schistose structure and there are growth and decline relationship between them.Nevertheless,hexagonal tabular and stratified kaolinite has the highest content from 2400m to3300m.Rosette and stratified chlorite shows increase trend when the burial depth is deeper than 3300m.These characteristics indicated that clay minerals are diagenetic minerals and there are conversions among the four types.Therefore form shallow to deep,three diagenetic mineral assemblage zones can be divided based on the characteristics of carbonate and clay minerals in mudstone.Namely,smectite+illite/smectite zone in the depth of 2000-2500m;kaolinite+illite/smectite zone in the depth of 2500-3300m and illite+chlorite+carbonate zone below 3300m.Previous studies showed that kaolinite is stable under acidic conditions,while other clay minerals and carbonate are stable under alkaline conditions.Hence according to mineral assemblages feature,it was inferred that diagenetic environment of mudstonehasundergonethechangeof alkaline-acid-alkaline.For the organic matter with different chemical properties in mudstone,the hydrocarbon generation will be different in the acidic and alkaline diagenetic environment even if the conditions of temperature and pressure are the same.Therefore,for hydrocarbon generation we should not only focus on thermal effect,but also pay more attention to the differences of diagenetic environment which have great significance for the understanding of hydrocarbon generation,hydrocarbon expulsion and reservoir formation in mudstone.     

Diagenetic alterations in temperate shelf carbonates from southeastern Australia

Temperate shelf carbonates form in cool marine waters and have skeletal and mineralogical compositions which are different from their tropical counterparts. They commonly lack non-skeletal grains and are often composed of low- and high-magnesium calcite with subordinate aragonite. Many of the aragonitic components found in tropical carbonates, such as corals, ooids, blue-green algae and lime mud, are absent.

Temperate shelf carbonates undergo diagenesis in marine waters with lower carbonate saturation than do tropical carbonates, and are exposed to cool climates with moderate to low rainfall. Marine cementation is rare because of low carbonate saturations in the surrounding waters. However, aragonite and high-magnesium calcite cements have been reported forming under specialized conditions associated with biogenic precipitation, submarine methane and sulphate-reducing bacteria, and more commonly in the intertidal environment where evaporation has increased carbonate concentrations.

In Pleistocene and Tertiary temperate shelf carbonates from southeastern Australia, evidence of marine diagenesis is rare to absent. Diagenetic stabilization of aragonite and high-magnesium calcite has taken from 80,000 y to 1 My, or longer, during subaerial exposure. This is slower than rates reported from tropical climates. A general lack of aragonite in some facies within these temperate carbonates leads to a lack of secondary porosity and only sparse low-magnesium calcite cement, even after prolonged fresh-water diagenesis. However, with lengthy exposure and under the right climatic conditions, karstic solution and calcrete precipitation can occur.

In sequences containing siliciclastic clays, pyrite and glauconite, abundant iron is present in interstitial waters leading to the precipitation of ferroan calcite cements in the phreatic and shallow burial environments, and to the substitution of iron for magnesium in stabilizing high-magnesium calcite skeletal material.

A unique void-filling, micritic internal sediment occurs in discrete layers in many of the Tertiary temperate shelf carbonate sequences in southeastern Australia. This internal sediment is localized as a pore-filling material above permeability barriers such as fine-grained sediments or volcanics, and above paleo-water tables which formed during periods of subaerial exposure. It is a feature of the vadose zone and lithifies to form a dense micritic low-magnesium calcite cement with characteristic pink/brown coloration, often associated with erosion surfaces and nodule beds.

Dolomite is uncommon in the southeastern Australian temperate shelf carbonates. It forms associated with preferential fluid pathways or mixing zones. Ferroan dolomite forms in siliciclastic clay-rich carbonates in the shallow burial environment. The ubiquitous fine, evaporite-related dolomite so common in tropical carbonates is absent.