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1.
Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca2+ and Mg2+ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.  相似文献   

2.
The solid‐state reaction magnesite (MgCO3) + calcite (aragonite) (CaCO3) = dolomite (CaMg(CO3)2) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO2 to the overlying mantle wedge.  相似文献   

3.
The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg2+/Ca2+ ratios to the local bedrock lithology and the HCO3 ? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg2+/Ca2+ ratio of the main channel of the Sava River indicates that the HCO3 ? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg2+/Ca2+ mole ratio of 0.33). The HCO3 ? concentration and pCO2 values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO3 ? from the alpine to the dinaric karst regions. Streams in general do not change in HCO3 ?, Mg2+/Ca2+, or Mg2+/HCO3 ? concentrations down course, but warming and degassing of CO2 produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km2-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO3 ?, Ca2+, and Mg2+ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.  相似文献   

4.
青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊.以青海湖水和除菌青海湖水作为载体,以CaCl2和MgCl2·6 H2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg2+参与下的钙质沉淀物,探讨Mg2+浓度对沉淀物类型的影响.仅添加CaCl2时,青海湖...  相似文献   

5.
Surface carbonate and land-derived deposits in the sea off southern Chile were investigated for their mineralogical and geochemical composition. The data were related to environmental features and compared with those of similar temperate and polar carbonate deposits from Tasmania, New Zealand, Arctica, and Antarctica. The mineralogy of the siliciclastic fraction is typical of cold areas and is mainly composed of chlorite, mica, quartz, feldspars and amphibole. The CaCO3 content varies from 30 to 90%; carbonate mineralogy is made up of low-Mg calcite, high-Mg calcite and minor amounts of aragonite. The Ca, Mg, Sr, Fe, and Mn contents of bulk carbonates and some selected skeletal hard parts are comparable to those of carbonates from Tasmania. The elemental composition is mainly related to carbonate mineralogy, skeletal components, and seawater conditions. The δ13C and δ18O values of carbonates are positive, and their field falls between the “seafloor diagenesis” and “upwelling water” trend lines, because the sediments are likely to be in equilibrium with waters of Antarctic origin. The mineralogical, elemental, and isotopic compositions of carbonates from southern Chile show better similarities with the “temperate” carbonates from Tasmania and New Zealand than with the “polar” carbonates from Arctica and Antarctica. Carbonate deposition is allowed by the low terrigenous input, the low SPM concentration and, probably, the upwelling of seawater from Antarctica.  相似文献   

6.
ABSTRACT Recent dolomitic sediment samples from Lagoa Vermelha, Brazil, were examined microscopically to study the process of bacterial fossilization in carbonate sediments. Bacteria‐like bodies were intimately associated with carbonate mineral surfaces, and coatings on the former demonstrate the calcification of single bacterial cells. The bacterial fossilization process in Lagoa Vermelha sediments was simulated in the laboratory by cultivation of mixed and pure cultures of sulphate‐reducing bacteria, which were isolated from the Lagoa Vermelha sediments. These cultures produced carbonate minerals that were studied to provide insight into the initiation of the fossilization process. In mixed culture experiments, bacterial colonies became calcified, whereas in pure culture experiments, single bacterial cells were associated with dolomite surfaces. Dolomite nucleated exclusively in bacterial colonies, intimately associated with extracellular organic matter and bacterial cells. Electrophoretic mobility measurements of the bacterial cells in electrolyte solutions demonstrated the specific adsorption of Ca2+ and Mg2+ onto the cell surfaces, indicating the role of the bacterial surface in carbonate nucleation and bacterial fossilization. The affinity of the cells for Mg2+ was related to the capability of the strains to mediate dolomite formation. Combined with sulphate uptake, which dissociates the [MgSO4]0 ion pair and increases the Mg2+ availability, the concentration of Mg2+ ions in the microenvironment around the cells, where the conditions are favourable for dolomite precipitation, may be the key to overcome the kinetic barrier to dolomite formation. These results demonstrate that bacterial fossilization is a consequence of the cell surface involvement in carbonate precipitation, implying that fossilized bacterial bodies can be used as a tool to recognize microbially mediated carbonates.  相似文献   

7.
Instead of having been more or less constant, as once assumed, it is now apparent that the major ion chemistry of the oceans has varied substantially over time. For instance, independent lines of evidence suggest that calcium concentration ([Ca2+]) has approximately halved and magnesium concentration ([Mg2+]) approximately doubled over the last 100 million years. On the other hand, the calcite compensation depth, and hence the CaCO3 saturation, has varied little over the last 100 My as documented in deep sea sediments. We combine these pieces of evidence to develop a proxy for seawater carbonate ion concentration ([CO32−]) over this period of time. From the calcite saturation state (which is proportional to the product of [Ca2+] times [CO32−], but also affected by [Mg2+]), we can calculate seawater [CO32−]. Our results show that [CO32−] has nearly quadrupled since the Cretaceous. Furthermore, by combining our [CO32−] proxy with other carbonate system proxies, we provide calculations of the entire seawater carbonate system and atmospheric CO2. Based on this, reconstructed atmospheric CO2 is relatively low in the Miocene but high in the Eocene. Finally, we make a strong case that seawater pH has increased over the last 100 My.  相似文献   

8.
Dolomitization often plays a critical role in the pore network development of platform carbonates, with implications for reservoir quality distribution. Understanding both the hydrological system driving dolomitization and the chemistry of the fluids involved is fundamental to constrain predictions of the geometry and the petrophysical properties of dolomite bodies. Here, the role of secular variations in seawater Mg/Ca as a control on dolomitization and early porosity modification was evaluated using one‐dimensional reactive transport models and fluids based on modern (aragonite sea), Mississippian and Aptian (calcite sea) seawaters. The sensitivity of dolomitization to a range of extrinsic controls (brine salinity, temperature, fluid flow rate and pCO2) and to intrinsic reactivity of the sediments (effective reactive surface area) was also explored. Simulations suggest faster calcite replacement by dolomite for seawaters with higher Mg/Ca, indicating that dolomitization potential is determined more by Mg/Ca rather than saturation index. Increasing evaporative concentration enhances reaction rate independent of the effect of enhanced density‐driven fluid flux. In addition to brine composition, effective surface area of precursor sediments and temperature exert a critical control on replacement rate, while secular variations of pH and carbonate alkalinity associated with changes in pCO2 are only secondary controls. Above flow rates of 0·01 m yr?1 replacive dolomitization is reaction‐limited rather than flux limited, favouring alteration of fine‐grained carbonates and suggesting that preferential alteration of grainstone units is rare unless head gradients are low. Post‐replacement dolomite cementation is flux dependent, and thus favoured in areas of high head gradient and high permeability sediments and, contrary to replacement, supersaturation is a more important driver than Mg/Ca. While uncertainties remain regarding low‐temperature dolomitization kinetics, the capability of numerical simulations to decouple individual controls provides new insights which can be used, in conjunction with traditional comparative sedimentology, to generate more rigorous conceptual models for individual reservoir settings.  相似文献   

9.
There are 59 springs at the Gevas–Gurp?nar–Güzelsu basins, 38 of these springs emerge from the fractured karst aquifers (recrystallized limestone and travertine) and 21 emerge from the Yuksekova ophiolites, K?rkgeçit formation and alluvium. The groundwater samples collected from 38 out of the total of 59 springs, two streams, one lake and 12 wells were analyzed physico-chemically in the year 2002. EC and TDS values of groundwater increased from the marble (high altitude) to the ophiolites and alluvium (toward Lake Van) as a result of carbonate dissolution and connate seawater. Five chemical types of groundwater are identified: Ca–Mg–HCO3, Mg–Ca–HCO3, Mg–Na–HCO3, Na–Ca–HCO3 and Mg–Ca–Na–HCO3. The calculations and hydrochemical interpretations show that the high concentrations of Ca2+, Mg2+ and HCO3 ? as predominant ions in the waters are mainly attributed to carbonate rocks and high pCO2 in soil. Most of the karst springs are oversaturated in calcite, aragonite and dolomite and undersaturated in gypsum, halite and anhydrite. The water–rock interaction processes that singly or in combination influence the chemical composition of each water type include dissolution of carbonate (calcite and dolomite), calcite precipitation, cation exchange and freshening of connate seawater. These processes contribute considerably to the concentration of major ions in the groundwater. Stable isotope contents of the groundwater suggest mainly direct integrative recharge.  相似文献   

10.
The rates of grain growth of stoichiometric dolomite [CaMg(CO3)2] and magnesite (MgCO3) have been measured at temperatures T of 700–800°C at a confining pressure P c of 300 MPa, and compared with growth rates of calcite (CaCO3). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO3)2, MgCO3, and CaCO3, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO3)2, MgCO3, and CaCO3, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10−5 μm3/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.  相似文献   

11.
Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ18O and δ13C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997  相似文献   

12.
《International Geology Review》2012,54(11):1350-1362
ABSTRACT

Recent studies show that crustal carbonates recycled into the mantle can be traced using Mg isotopes of basalts. However, the species of recycled carbonates are poorly constrained. Carbonates have lower δ26Mg values and higher 87Sr/86Sr ratios relative to the mantle, but different carbonate species display different mixing curves with the mantle in the Mg-Sr isotopic diagram because of differences in their Sr and Mg contents. Thus a combined study of Mg-Sr isotopes can constrain the species of deeply recycled carbonates. Here, we present newly determined 87Sr/86Sr ratios of the <110 Ma basalts from Eastern China, and together with published Mg isotopic data we evaluate the species of recycled carbonates in the mantle and discuss their implication. The <110 Ma basalts display low δ26Mg values of ?0.60 to ?0.30‰ and relatively low initial 87Sr/86Sr ratios of 0.70328 to 0.70537, suggesting that their mantle source was hybridized by recycled carbonates with a light Mg isotopic composition which had more significant effects on Mg than Sr isotope ratios. Mg-Sr isotopic data indicate that the recycled carbonates consist of magnesite and aragonite, but the possibility of calcite and dolomite cannot be eliminated. Based on the carbonated peridotite solidus, the equilibrium line between dolomite and magnesite + aragonite, as well as the mantle adiabat, the initial melting depth of the carbonated mantle, the source region of the studied basalts, was constrained at ~300–360 km. Thus, the subducted depth of the west Pacific slab underlying the carbonated mantle and supplying recycled carbonates should be greater than ~300–360 km, consistent with the seismic tomography result that the west Pacific slab now stagnates in the mantle transition zone.  相似文献   

13.
Late Devonian (Famennian) marine successions globally are typified by organic-rich black shales deposited in anoxic and euxinic waters and the cessation of shelf carbonate sedimentation. This global ‘carbonate crisis’, known as the Hangenberg Event, coincides with a major extinction of reef-building metazoans and perturbations to the global carbon cycle, evidenced by positive carbon-isotope excursions of up to 4‰. It has been suggested that authigenic carbonate, formed as cements in sedimentary pore spaces during early burial diagenesis, is a significant mass fraction of the total global carbon burial flux, particularly during periods of low oxygen concentration. Because some authigenic carbonate could have originated from remineralization of organic carbon in sediments, it is possible for this reservoir to be isotopically depleted and thereby drive changes in the carbon isotopic composition of seawater. This study presents bulk isotopic and elemental analyses from fine-grained siliciclastics of the Late Devonian–Early Mississippian Bakken Formation (Williston Basin, USA) to assess the volume and isotopic composition of carbonates in these sediments. Carbonate in the Bakken black shales occurs primarily as microscopic disseminated dolomite rhombs and calcite cements that, together, comprise a significant mass-fraction (ca 9%). The elemental composition of the shales is indicative of a dynamic anoxic to sulphidic palaeoenvironment, likely supported by a fluctuating chemocline. Despite forming in an environment favourable to remineralization of organic matter and the precipitation of isotopically depleted authigenic carbonates, the majority of carbon isotope measurements of disseminated carbonate fall between −3‰ and +3‰, with systematically more depleted carbonates in the deeper-water portions of the basin. Thus, although there is evidence for a significant total mass-fraction of carbonate with contribution from remineralized organic matter, Bakken authigenic carbonates suggest that Famennian black shales are unlikely to be sufficiently 13C-depleted relative to water column dissolved inorganic carbon to serve as a major lever on seawater isotopic composition.  相似文献   

14.
The paper presents the results of the statistical and thermodynamic analysis of hydrogeochemical information on the genesis of F-bearing waters in the Carboniferous deposits of the Moscow artesian basin. The F concentration is demonstrated to increase with increasing salinity of the aqueous solution. As follows from the analysis of mineral equilibria, the saturation concentrations of the aqueous phase with respect to fluorite in association with calcite and gypsum is less than 2–3 mg of F/l. At the saturation of the aqueous phase with respect to fluorite in association with dolomite, the equilibrium concentration of F increases with increasing Mg concentration and decreasing equilibrium partial CO2 pressure and can reach 8–10 mg of F/l. The main reason for this enrichment of the aqueous phase in F is certain features of mineral equilibria in the system of aqueous solution with Ca and Mg carbonates. An increase in the Mg2+ concentration in the aqueous phase decreases the Ca2+ concentration in the solubility equilibrium of dolomite, and this, in turn, decreases the F? concentration in the solubility equilibrium of fluorite.  相似文献   

15.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

16.
Some species of sulphate‐reducing bacteria (SRB) are known to mediate the formation of dolomite and Mg‐calcite. However, their exact role in the mineralization process remains elusive. Here, we present the result of a laboratory experiment that was designed to test whether formation of carbonate minerals by SRB can occur in the absence of living cells, through passive mineralization of their exopolymeric substances (EPS). SRB capable of mediating dolomite were cultivated in the laboratory, allowing them to secrete EPS. Microbial activity within the cultures was subsequently inhibited with antibiotics. Only after this step, Ca2+ and Mg2+ were added to the solution and carbonate minerals could form. Mg‐calcite and disordered Ca‐dolomite precipitated in association with EPS. The mol.% of Mg2+ in the crystals increased with longer incubation times. This result demonstrates that organic compounds produced by SRB can mediate the formation of Ca‐Mg carbonates in the absence of an active metabolism.  相似文献   

17.
A significant portion of calcium carbonate is deposited in lake sediments as a result of biological processes related to the photosynthetic activity of phytoplankton in the pelagic realm and, in addition, macrophytes in the littoral zone. Lake Wigry, one of the largest lakes in Poland (north‐east Poland), is characterized by: (i) carbonate sediments with a CaCO3 content exceeding 80% within the littoral zone; and (ii) large areas of submerged vegetation dominated by charophytes (macroscopic green algae, Characeae family). It is claimed that charophytes are highly effective in utilizing HCO3? and forming thick CaCO3 encrustations. Thus, this study was aimed at evaluating the CaCO3 production by dense Chara stands overgrowing the lake bottom reaching a depth of 4 m. In late July 2009, the fresh and dry mass of plants, the percentage contribution of calcium carbonate and the production of CaCO3 per 1 m2 were investigated along three transects at three depths (1 m, 2 m and 3 m, with each sample area equal to 0·0625 m2) per transect. The composition and structure of phytoplankton and the physico‐chemical properties of the water analysed in both the littoral and pelagic zones served as the environmental background and demonstrated moderately low fertility in the lake. The greatest dry plant mass exceeded 1000 g m?2 and CaCO3 encrustations constituted from 59% to over 76% of the charophyte dry weight. Thus, the maximum and average values of carbonates precipitated by charophytes were 685·5 and 438 g m?2, respectively, which exceeded previously reported results. A correlation of carbonate production with the depth of Chara stands was detected, and intermediate depths offered the most favourable conditions for carbonate precipitation (589 g m?2 on average). As precipitated carbonates are ultimately stored in bottom deposits, the results highlight the significance of charophytes in lacustrine CaCO3 sedimentation.  相似文献   

18.
Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater   总被引：3，自引：0，他引：3  
The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO3. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg2+ and Ca2+ ions. The increase was 5 times greater for Ca2+ than Mg2+. The effects ofCa2+ and Mg2+ are diminished with the addition of SO4 2- apparently due to the formation of MgSO4 and CaSO4 complexes in solution and/or SO4 2- adsorption on the surface of CaCO3. The adsorbed Ca2+ and Mg2+ on CaCO3 (at carbonate sites) may act as bridges to PO4 3- ions. The bridging effect of Ca2+is greater than Mg2+ apparently due to the stronger interactions of Ca2+ with PO4 3-.The apparent effect of salinity on the adsorption of PO4 was largely due to changes in the concentration of HCO3 - in the solutions. An increase in the concentration of HCO3 - caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO3 - (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO4]ad = KmCm[PO4]T/(1 +Km [PO4]T) , ]where [PO4]ad and [PO4]T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of Cm (the maximum monolayer adsorption capacity, (mol/g) and Km (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ Cm = 17.067 + 0.1707t - 0.4693S + 0.0082S2 ( = 0.7) ][ ln Km = - 2.412 + 0.0165t - 0.0004St - 0.0008S2 ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO4]ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO4 left on the CaCO3 is close to the equilibrium adsorption. The release of PO4 from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.  相似文献   

19.
Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active CH4bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanetrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (δ13Cav =−28.9%0) of carbon dioxide produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (δ18Oav = 5%0) in carbonates is inherited from seawater sulfate. A rapid sulfate reduction (up to 12 mg S dm−3 day−1) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this, carbonates can only be formed in surface sediments near the water-bottom interface. Authigenic carbonates occurring within sediments occur do notin situ. Salinity, as well as CO 3 2− /Ca and Mg/Ca ratios, correspond to the field of nonmagnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. The radiocarbon age of carbonates is about 10000 yr.  相似文献   

20.
Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H2S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ13C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ13C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.  相似文献   

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