Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England     

M.L Coleman  R Raiswell 《Geochimica et cosmochimica acta》1981,45(3):329-340

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.  相似文献   

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones     

R. Raiswell  S. H. Bottrell  S. P. Dean  J. D. Marshall†  A. Carr‡  & D. Hatfield 《Sedimentology》2002,49(2):237-254

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.  相似文献   

Nature and origin of arsenic carriers in shallow aquifer sediments of Bengal Delta,India     

S.?SenguptaEmail author  P.?K.?Mukherjee  T.?Pal  S.?Shome 《Environmental Geology》2004,45(8):1071-1081

Sediments from shallow aquifers in Bengal Delta, India have been found to contain arsenic. Rivers of Ganga-Brahmaputra system, responsible for depositing these sediments in the delta, have created a store of arsenic. Geomorphological domains with different depositional styles regulate the pattern of distribution of zones with widely different content of groundwater arsenic. The high arsenic zones occur as narrow sinuous strips confined to channel deposits. A few iron-bearing clastic minerals and two post-depositional secondary products are arsenic carriers. Secondary siderite concretions have grown on the surface of the clastic carriers in variable intensity. The quantity of arsenic in all clastic carriers is in excess of what is generally expected. Excess arsenic is contributed by the element adsorbed on the concretion grown on the surface of the carriers, which adds up to the arsenic in the structure of the minerals. Variable abundance of concretions is responsible for the variable quantity of arsenic in the carriers and the sediment samples. Fe²⁺ for the growth of siderite concretions is obtained from the iron-bearing clastic carriers. The reaction involves reduction of trivalent iron to bivalent and the required electron is obtained by transformation of As³⁺ to As⁵⁺. It is suggested that oxidation of As³⁺ to As⁵⁺ is microbially mediated. In the Safe zone arsenic is retained in the carriers and groundwater arsenic is maintained below 0.05 mg/l. In the Unsafe zone sorbed arsenic is released from the carriers in the water through desorption and dissolution of concretion, thereby elevating the groundwater arsenic level to above 0.05 mg/l.  相似文献   

Composition,nucleation, and growth of iron oxide concretions     

W.T. Parry 《Sedimentary Geology》2011,233(1-4):53-68

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.  相似文献   

Growth mechanisms and geochemistry of carbonate concretions from the Cambrian Wheeler Formation (Utah,USA)          下载免费PDF全文

Robert R. Gaines  John S. Vorhies 《Sedimentology》2016,63(3):662-698

Carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments. Typically, they form in organic‐rich mudstones, where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments. As a result, carbonates that comprise concretions are usually characterized by broad ranges in δ¹³C and include values that are significantly depleted relative to seawater. This article reports results from a physical, petrographic and geochemical analysis of 238 concretions from the Wheeler Formation (Cambrian Series 3), Utah, USA, which are unusual in several respects. Most prominently, they formed in organic‐poor mudstones (total organic carbon = 0·1 to 0·5%) and are characterized by a narrow range of δ¹³C that onlaps the range of contemporaneous seawater values. Subtle centre to edge trends in δ¹³C demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments, but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters. The large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix, which occurred via both displacive and replacive carbonate precipitation during early diagenesis. Stable isotope data from cogenetic pyrite (δ³⁴S) and silica (δ¹⁸O) phases provide insight into the evolution of biogeochemical processes during concretion growth, and suggest that concretions were formed almost entirely during sulphate reduction, with only minor modification thereafter. Concretions of the Wheeler Formation appear to represent an end‐member system of concretion formation in which rapid growth was promoted by ions supplied from sea‐water. As such, they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments.  相似文献   

Formation of siderite-Mg-calcite-iron sulphide concretions in intertidal marsh and sandflat sediments, north Norfolk, England   总被引：2，自引：0，他引：2  

K. PYE  J. A. D. DICKSON†  N. SCHIAVON†  M. L. COLEMAN‡  M. COX‡ 《Sedimentology》1990,37(2):325-343

Concretions cemented mainly by siderite, Mg-calcite and iron monosulphide are common in late Holocene marsh and sandflat sediments on parts of the north Norfolk coast. Field experiments have shown that the concretions are actively forming in reduced sediments in which sulphate-reducing bacteria are active. δ¹³C values ranging from ?3 to ?11·8% (mean ?5·9%0) suggest that the carbonate in the concretions is derived partly from marine sources and partly from microbial degradation of organic matter. δ¹⁸O values ranged from ?6·4% to + 0·8% (mean ?1·0%) suggesting that carbonate precipitated in porewaters ranging from pure sea water to-sea water diluted with meteoric water. Chemical analysis of porewaters showed no evidence of significant sulphate depletion at the depth of concretion formation. Some concretions have formed around fragments of wood or metal, but others contain no apparent nucleus. In field experiments siderite, FeS and Mg-calcite were precipitated around several different nuclei within a period of six months. We suggest that siderite may form wherever the rate of iron reduction exceeds the rate of sulphate reduction, such that insufficient dissolved sulphide is available to precipitate all the available dissolved ferrous iron.  相似文献   

Jurassic septarian concretions from NW Scotland record interdependent bacterial, physical and chemical processes of marine mudrock diagenesis   总被引：3，自引：0，他引：3  

JAMES P. HENDRY  MICHAEL J. PEARSON†  NIGEL H. TREWIN‡  ANTHONY E. FALLICK§ 《Sedimentology》2006,53(3):537-565

Septarian concretions in the Staffin Shales Formation (Kimmeridgian, Isle of Skye) allow controls on concretion rheology and septarian cracking to be investigated. Stratabound concretions consist of anhedral ferroan calcite microspar enclosing clay and minor pyrite. Intergranular volumes range from 77% to 88%, and calcite δ¹³C and δ¹⁸O values in most concretion bodies range from ?10·0‰ to ?17·3‰ and +0·3‰ to ?0·6‰ respectively, consistent with rapid and pervasive cementation in marine pore fluids. Septarian rupture occurred during incipient cementation, with a sediment volume reduction of up to 43%. Crack‐lining brown fibrous calcite records pore fluid re‐oxygenation during a depositional hiatus, followed by increasing Fe content and δ¹³C related to bacterial methanogenesis. Brown colouration results from an included gel‐like polar organic fraction that probably represents bacterially degraded biomass. A new hypothesis for concretion growth and septarian cracking argues that quasi‐rigid ‘proto‐concretions’ formed via binding of flocculated clays by bacterial extracellular polysaccharide substances (EPS). This provided rheological and chemical conditions for tensional failure, subcritical crack growth, volume contraction, calcite nucleation, and incorporation of degraded products into crack‐lining cements. Bacterial decay of EPS and syneresis of host muds provided internal stresses to initiate rupture at shallow burial. Development of septarian (shrinkage) cracks in muds is envisaged to require pervasive in situ bacterial colonization, and to depend on rates of carbonate precipitation versus EPS degradation and syneresis. Subsequent modification of septarian concretions included envelopment by siderite and calcite microspar, hydraulic fracturing associated with Cretaceous shallow burial or Palaeogene uplift; and cementation by strongly ferroan, yellow sparry calcite that records meteoric water invasion of the host mudrocks. An abundance of fatty acids in these spars indicates aqueous transport of organic breakdown products, and δ¹³C data suggest a predominantly methanogenic bicarbonate source. However, the wide δ¹⁸O range for petrographically identical cement (?1·3‰ to ?15·6‰) is difficult to explain.  相似文献   

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ¹⁸O of Early Palaeozoic sea water     

Reinhard Hesse  Jehangir Shah†  Shafiul Islam‡ 《Sedimentology》2004,51(3):601-625

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.  相似文献   

Two populations of carbonate in ALH84001: geochemical evidence for discrimination and genesis     

John M. Eiler  John W. ValleyColin M. Graham  John Fournelle 《Geochimica et cosmochimica acta》2002,66(7):1285-1303

We present major and trace-element, oxygen isotope, textural, and structural data for carbonates and related phases in the SNC meteorite ALH84001. These data document the existence of at least two distinct carbonate populations: one composed of finely zoned, chemically and isotopically heterogeneous concretions of magnesio-siderite with distinct white magnesite rims, and a second composed of relatively homogeneous, isotopically and compositionally simple domains of ankeritic carbonate and intimately intergrown glass and fine-grained pyroxene. We suggest on the basis of textural evidence and geochemical systematics that the first population consists of low-temperature aqueous precipitates, and the second is produced by shock melting of the first. Values of δ¹⁸O and Sr/Ca ratios are correlated with one another in magnesio-siderite concretions; the trend formed by these data is consistent with the predicted relationship for inorganic precipitation of carbonate from a solution of constant composition between temperatures of ∼190°C (for concretion cores) to 20°C (for magnesite-rich concretion rims). Given the assumptions inherent in this temperature estimate, the aqueous fluid parental to carbonate concretions is constrained to have a δ¹⁸O of −5‰ VSMOW (significantly mass fractionated compared with expected juvenile martian volatiles) and minor-element abundances broadly similar to terrestrial seawater.  相似文献   

Evidence for surface reaction-controlled growth of carbonate concretions in shales     

R. RAISWELL 《Sedimentology》1988,35(4):571-575

Estimates for the rate of concretionary growth in shales are based on models which assume that growth is diffusion-controlled. However, laboratory and field studies of CaCO₃ precipitation in organic carbon-rich sediments indicate that surface reactions control growth, due to inhibition by various dissolved species. The spatial distribution of carbonate concretions in the Jet Rock (Lower Jurassic, England) is also inconsistent with diffusion-controlled precipitation of CaCO³ into concretions, and growth must have been at least partly surface reaction-controlled.  相似文献   

Strontium isotope composition of the lower proterozoic carbonate concretions: The Zaonega Formation,Southeast Karelia     

A. B. Kuznetsov  I. M. Gorokhov  V. A. Melezhik  N. N. Mel’nikov  G. V. Konstantinova  T. L. Turchenko 《Lithology and Mineral Resources》2012,47(4):319-333

The middle part of the volcanosedimentary Zaonega Formation of the Ludikovian Suprahorizon (approximately 2.0 Ga) includes large carbonates concretions and lenses in shungite layers. Carbonate lenses and concretions are primarily elongated and flattened, and their thickness varies from tens of centimeters to a few meters. Some lenses retain relicts of lamination. Concretions are composed of calcite or dolomite. They contain abundant organic matter, as well as mica, talc, chlorite, quartz, and pyrite crystals. The calcite concretions contain some dolomite admixture (Mg/Ca = 0.011?0.045) and differ from sedimentary limestones by a low Fe/Mn value (0.3–2.1). The Sr content is as much as 385–505 μg/g in most samples and is low (86 μg/g) only in one sample. The Rb-Sr systematics of carbonate concretions was studied with the stepwise dissolution procedure, which included processing with the ammonium acetate solution (AMA fraction) to partially remove the secondary carbonate material, with dissolution of the residue in acetic acid (ACA fraction). In individual calcite samples, discrepancy between the measured ⁸⁷Sr/⁸⁶Sr values in the AMA and ACA calcite fractions shows a variation range of 0.0008–0.0033. The initial ⁸⁷Sr/⁸⁶Sr ratio in the ACA fractions of the studied samples varies from 0.7053 to 0.7162. The ratio shows a positive correlation with Mg/Ca and the proportion of siliciclastic admixture and negative correlation with the Mn content. The concretions were formed when the sediments subsided, probably, during the transition from a zone with “mild” reductive conditions to zones with active sulfate reduction and methanogenesis. In the sulfate reduction zone, where most pyrite-bearing concretions were formed, the sediment was not geochemically exchaged with the bottom water and was evolved into a closed or semiclosed system. Processes of diagenesis in this zone promoted the release of the radiogenic ⁸⁷Sr from the associated siliciclastic minerals, resulting in growth of the initial ⁸⁷Sr/⁸⁶Sr in concretions up to 0.7108–0.7162. Some calcite concretions, which lacked pyrite (or contained its minimal amount) were likely formed in a thin surficial sediment layer located above the sulfate reduction zone. Therefore, they precipitated Sr in isotope equilibrium with Sr of the bottom water. However, large concretions and carbonate lenses with an insignificant siliciclastic admixture could retain the signature of early diagenesis or even sedimentation. The initial ⁸⁷Sr/⁸⁶Sr ratio in one of such samples with the siliciclastic admixture of 6.2% makes it possible to estimate the maximal value of this ratio (0.7053) in the Ludikovian paleobasin.  相似文献   

磷块岩结核的显微结构和生成特点          下载免费PDF全文

赵东旭 《地质科学》1988,(1):57-67

磷酸盐结核主要由磷质凝块、藻类碎屑和纤柱状磷灰石组成。呈特殊的栉壳状结构。结核中的凝块和藻屑与围岩中的氧化硅、粘土是同时在海底沉积的。纤状磷灰石则是在成岩期间从孔隙水中沉淀的。这些磷酸盐结核是由于纤状磷灰石在碱性微环境中不断淀积增长而成。  相似文献   

Interstitial water chemistry of the Santa Barbara Basin sediments     

Edward Sholkovitz 《Geochimica et cosmochimica acta》1973,37(9):2043-2073

  相似文献   

Hydrogeochemical investigation and groundwater quality assessment of Pratapgarh district,Uttar Pradesh   总被引：3，自引：0，他引：3  

Ashwani Kumar Tiwari  Abhay Kumar Singh 《Journal of the Geological Society of India》2014,83(3):329-343

Hydogrochemical investigation of groundwater resources of Paragraph district has been carried out to assess the solute acquisition processes and water quality for domestic and irrigation uses. Fifty-five groundwater samples were collected and analyzed for pH, electrical conductivity, total dissolved solids, hardness, major anions (F^?, Cl^?, NO₃, HCO₃ ^?, SO₄ ^2?) and cations (Ca²⁺, Mg²⁺, Na⁺, K⁺). Study results reveal that groundwater of the area is alkaline in nature and HCO₃ ^?, Cl^?, Mg²⁺, Na⁺ and Ca²⁺ are the major contributing ions to the dissolved solids. The hydrogeochemical data suggest that weathering of rock forming minerals along with secondary contributions from agricultural and anthropogenic sources are mainly controlling the groundwater composition of Pratapgarh district. Alkaline earth metals (Ca²⁺+Mg²⁺) exceed alkalis (Na⁺+K⁺) and weak acid (HCO₃ ^?) dominate over strong acids (Cl^?+SO₄ ^2?) in majority of the groundwater samples. Ca-Mg-HCO₃ and Ca-Mg-Cl-HCO₃ are the dominant hydrogeochemical facies in the groundwater of the area. The computed saturation indices demonstrate oversaturated condition with respect to dolomite and calcite and undersaturated with gypsum and fluorite. A comparison of groundwater quality parameters in relation to specified limits for drinking water shows that concentrations of TDS, F^?, NO₃ ^? and total hardness exceed the desirable limits in many water samples. Quality assessment for irrigation uses reveal that the groundwater is good for irrigation. However, values of salinity, sodium adsorption ratio (SAR), residual sodium carbonate (RSC), %Na and Kelley index are exceeding the prescribed limit at some sites, demanding adequate drainage and water management plan for the area.  相似文献   

The diagenetic history of some septarian concretions from the Kimmeridge Clay, England     

T. R. ASTIN  I. C. SCOTCHMAN 《Sedimentology》1988,35(2):349-368

ABSTRACT
Large septarian concretions from the Kimmeridge Clay, up to 1.2 m in diameter, have centres comprising anhedral calcite microspar passing into margins of radiating fibrous calcite microspar, with a pyrite-rich zone at the transition. Septarian veins formed and were lined with brown calcite synchronously with fibrous matrix growth, with white calcite precipitated in septarian cavities after concretion growth ceased. Septarian veins, filled only with white calcite, formed later, at the same time as the outermost calcite microspar crystals were enlarged.
The concretions were buried in the Late Jurassic to about 130 m, and in the Late Cretaceous to about 550 m, with uplift between. Oxygen isotopes show that the concretion grew throughout the first burial, with septarian veins forming from about 30 m depth onwards. Later septarian veins formed between about 200 and 500 m during the second burial.
Carbon isotopes show that the compact inner matrix grew in the sulphate reduction zone, the end of which is marked by the pyrite-enriched zone. Dissolving shells, and possibly minor methanogenic carbonate, slowly diluted sulphate reduction-zone carbonate during deeper burial. During early concretion growth, Mg and Sr were depleted in the pore water. During later stages of the first burial, Mg, Sr, Mn and Fe all increased, especially after concretion growth ceased. During the second burial, Fe, Mn and Mg decreased as calcite precipitated, implying relatively closed systems for these elements.
Synchronous formation of septarian fractures and fibrous calcite matrix shows that the Kimmeridge Clay became overpressured during the later stages of both burials.  相似文献   

Metal release from dolomites at high partial-pressures of CO2     

《Applied Geochemistry》2013

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.  相似文献   

Petrography and geochemistry of septarian carbonate concretions from the Boom Clay Formation (Oligocene,Belgium)     

De Craen  M.  Swennen  R.  Keppens  E. 《Geologie en Mijnbouw》1998,77(1):63-76

The septarian carbonate concretions from the Boom Clay (Belgium) consist mainly of authigenic minerals such as micrite ( 70% bulk volume) and pyrite framboids ( 3%). These mineral phases occur between detrital grains and fossils. The septarian cracks are lined with calcite, which is sometimes covered with pyrite. The preservation of delicate sedimentological features in the concretion matrix (hardly compacted faecal pellets, burrows and uncrushed shells) points to an early origin of the concretions. Systematic geochemical variations from concretion centre to edge suggest that growth continued during shallow burial. The13C values (–17.5 to –20.5) of the concretionary carbonate show that bacterial sulphate-reduction processes were dominant. Sulphate-reduction-derived HCO3- was diluted by marine-related HCO3-, derived from dissolved bioclasts. A slight enrichment in 13C during growth is caused by the decreasing influence of sulphate reduction because of the progressive closure of the diagenetic system due to shallow-burial compaction. The 18O values (–0.5 to +1.0) of the concretionary carbonate point to a marine origin. The slightly 18O-depleted signature with respect to time-equivalent marine-derived carbonate relates to the incorporation of an 18O-depleted component, originating from sulphate and organic matter. The slight decrease in 18O during growth relates to an increasing influence of this component and to a decreasing influence of seawater-derived oxygen during early diagenesis.  相似文献   

Sedimentmikrobioiogie und ihre geologischen Aspekte     

Dr. Wolfgang E. Krumbein 《International Journal of Earth Sciences》1971,60(2):438-471

The influence of bacteria on recent sediments was first discussed in 1885, whenFischer andGazert were discussing the cycle of substances in the sea as well as in sediments. The influence of bacteria on the cycling of C, N, S, P in recent sediments and the open sea was soon accepted by marine geologists. Nevertheless, only very few experiments have, so far, shown more than qualitative and quantitative data collection in various restricted areas. This is due to the extensive and complicated chain of reactions on the surface of sediments and in the sediment itself. Biologists are asking for the amount of organic and inorganic matter which is reworked and released to the sea. Geologists usually emphasize the amount of substances which are sedimentated. For biologists the sediment is only part of their dominant ecosystem (the sea). While, for geologists the “sea” is only furnishing and influencing their first range system sediment. How much then, are bacteria involved in the slow process of conversion from a recent sediment to sedimentary rocks? Bacteria influence more or less strongly and to a more or less advanced degree of diagenesis:

1. The organic matter in sediments and the final form in which it is found.
2. The anions CO₃ ^2?, NO₃ ^?, OH-, SO₄ ^2?, PO₄ ^3? as well as their intermediate stages and the resulting minerals.
3. The cations H⁺, NH₄ ⁺, Ca²⁺, Fe²⁺, Fe³⁺, and a series of metals which are dissolved or precipitated by microbial activities as for example Fe, Mn, Cu, Ag, V, Co, Mo, Ni, U, Se, Zn.
4. The equilibrium of silicium. At least diatoms and radiolarians are precipitating silica, while other reactions which have been proved are not yet shown to influence marine sediments.
5. p_H-values and oxidation-reduction potentials of the sediment.
6. The composition of interstitial waters.
7. The surface activity of minerals, since bacteria are growing especially on particle surfaces.
8. The energy content and temperature of sediments.
9. The texture of fine grained sediments.
10. The fossilization of microfauna, macrofauna and trace fossils.

Sedimentology and mineralogy may also influence the bacterial activities and the composition of the microflora within sediments. Methods and problems of sediment microbiology are demonstrated by some investigations in the German Bay (North Sea) in connection with the first German Underwater Station (UWL). Ecological work proves to be difficult in various directions. The main cause of difficulties in microbiological work on sediments are the great variety of different factors influencing the environment (microbial, chemical, physical, mineralogical), the difficulty of taking representative samples, and the small amount of data which has been collected so far.  相似文献   

Importance of different types of marine particles for the scavenging of heavy metals in the deep-sea bottom water     

《Applied Geochemistry》2003,18(5):693-710

In experiments of 7 days duration using voltammetric and radiotracer measurement techniques, the role of different particle types in the sorption of dissolved metal species in a disturbed deep-sea bottom seawater system were investigated. Resuspension of oxic to suboxic surface sediment into the bottom water in the deep sea (either by natural events or industrial activities like Mn nodule mining) has been shown to be followed quickly by scavenging of dissolved heavy metals, e.g. released from interstitial water, on the resuspended particles. Compared to other deep-sea particles (like clay minerals, calcite and apatite), Mn and Fe oxides and oxyhydroxides were found to be by far the most important phases in scavenging many dissolved heavy metals. Only Pb was sorbed strongly on all particles used, with highest affinity to carbonate fluorapatite. Caesium⁺ was significantly scavenged only by clay minerals like illite. The sorption experiments support a simple electrostatic model: Hydrated cations and labile cationic chloro-complexes in seawater like Mn²⁺, MnCl⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ba²⁺, and PbCl⁺, are preferentially adsorbed or ion-exchanged on the negatively charged surfaces of Mn oxides. In contrast, oxyanions and neutrally or negatively charged complexes like HVO₄²⁻, MoO₄²⁻, HAsO₄²⁻, UO₂(CO₃)₂²⁻, and PbCO₃⁰ associate with neutral to slightly positive amphoteric Fe oxyhydroxide particles. Metals forming strong chloro-complexes in seawater like Cd (CdCl₂⁰), are less readily sorbed by oxides than others. A comparison of the results of voltammetric and radiotracer techniques revealed that after fast sorption within the first hour, isotopic exchange dominated reactions on MnO₂-rich particles in the following days. This was especially pronounced for Mn and Co which are bound to the Mn oxide surface via a redox transformation.  相似文献   

Thermodynamic Modelling of Ore-Forming Mechanism of the Changkeng Gold-Silver Deposits in Guangdong Province     

Zhang Sheng  Li Tongjin  Wang LiankuiGuangzhou Institute of Geochemistry  Chinese Academy of SciencesWushan  Guangzhou 《《地质学报》英文版》1997,71(4):433-445

The Changkeng gold-silver deposits consist of a sediment-hosted, disseminated gold deposit and a replacement-type silver deposit. The mineralizations of gold and silver are zoned and closely related to the silicification of carbonate and clastic rocks, so that siliceous ores dominate in the deposit. The mineralizing temperature ranges mainly from 300 to 170℃, and K+, Na+, Ca2+, Mg2+, and Cl- are the major ions in the ore-forming fluid. Calculations of distribution of metal complexes show that gold is mainly transported by hydrosulphide complexes, but chloride complexes of silver, iron, lead, and zinc, which are transformed into hydroxyl and hydrosulphide complexes under neutral to weak-alkaline circumstances in the late stage, predominate in the ore-forming solutions. Water-rock interaction is confirmed to be the effective mechanism for the formation of silver ores by computer modelling of reaction of hydrothermal solution with carbonate rocks. The solubility analyses demonstrate that the precipitation  相似文献