Oxygen isotope fractionation during the dolomitization of calcium carbonate

The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO₃ between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ⁸O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the $\text{Sr}\text{(Mg + Ca)}$ ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10^?5 liters (out of 5 × 10^?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 Inα_D-H2O = 3.06 × 10⁶T^?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).     

A study of strontium in core 119K,Discovery deep,Red Sea

The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic ⁸⁷Sr and of volcanogenic material of basaltic composition and low ⁸⁷Sr abundance. The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the shells of foraminifers and pteropods, expressed as δ ⁸⁷Sr‰ relative to 0.70904 for seawater, decrease from $\text{?0.23 ± 0.17‰}$ at 90 cm to $\text{?0.82 ± 0.17‰}$ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ ⁸⁷Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

Selected geochemical factors influencing diagenesis of eocene carbonate rocks,peninsular Florida,U.S.A.

The geochemical significance of three selected ions (Mg²⁺, Na⁺, and Sr²⁺) supports a model of dolomitization by brackish groundwater. This groundwater zone contains sufficient quantities of Mg²⁺ to facilitate dolomitization ($\text{Mg}\text{Ca}\text{ratios 1}$). Rising and falling of sea level and fluctuations of the phreatic zone related to climatic variations account for the thickness of the dolomite layers and the chemical distributions within these layers. Sodium concentrations in the calcite are 70–185 ppm, indicating formation in brackish water. Dolomite has sodium concentrations between 50–1400 ppm, suggesting formation in waters of similar salinity.Strontium in calcite ranges from 320–600 ppm, suggesting diagenesis in slightly saline waters in an open system. Dolomite contains 241 ppm Sr²⁺ on the average and calcite has 418 ppm Sr²⁺. The Sr²⁺ concentrations of the dolomite are characteristic of diagenesis in water less saline than sea water. Average strontium concentrations in the dolomite occur in two distinct groups, 260 ppm for dolomite with 39–43 mole-% MgCo₃ and 195 ppm for the dolomite with 44–50 mole-% MgCO₃. The difference in the Sr²⁺ concentrations of the two dolomite groups indicates the higher mole-% MgCO₃ dolomite recrystallized in a less saline environment than the lower mole-% MgCO₃ dolomite. These different environments are attributed to a relatively more saline coastal environment and a less saline inland environment.The more nearly stoichiometric dolomite (44–50 mole-% MgCO₃) has less scatter when mole-% MgCO₃ is plotted against Sr²⁺ and Na⁺. This suggests a greater approach to equilibrium with the dolomitizing fluid than the lower mole-% MgCO₃ (39–43) dolomite. The more saline environment has higher Mg/Ca ratios and promotes more calcium-rich dolomite during diagenesis because of the inhibition from competing foreign ions and because it is thermodynamically a more favorable environment which causes more rapid crystallization. The less saline waters allow recrystallization to proceed more slowly, producing better ordering in the dolomites, textural preservation and development of subhedral to euhedral rhombic crystals.     

Strontium isotopic composition of several oilfield brines from Kansas and Colorado

The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of several oilfield brines associated with Paleozoic dolomites, cherty dolomites and sandstones from Kansas and Colorado range from 0.7113 to 0.7341. Two brines in the Mississippian dolomites from Colorado were found to contain the most radiogenic strontium. The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of brines in a small oilfield in eastern Kansas are constant, and the ratios may suggest that in this field there may be only one oil pool. The isotopic composition of strontium in subsurface waters could be useful in determining hydrologic continuity among reservoirs and for obtaining additional information on the origin and migration of these fluids.     

The circumvention of the natural biopurification of calcium along nutrient pathways by atmospheric inputs of industrial lead

Biopurification factors for Ca with respect to Sr, Ba, and natural, uncontaminated Pb were measured for different nutrient-consumer pairs in a remote subalpine ecosystem. The factor for Sr is expressed as: (nutrient $\text{Sr}\text{Ca}$) ÷ (consumer $\text{Sr}\text{Ca}$). Similar expressions were used for $\text{Ba}\text{Ca}$ and $\text{Pb}\text{Ca}$. It was found that Ca was biopurified of Sr 3-fold, of Ba 16-fold, and of Pb 100-fold in going from rock to sedge leaves. In going from sedge leaf to vole, Ca was biopurified of Sr 4-fold, of Ba 8-fold, and of Pb 16-fold. In going from meadow vole to pine marten, Ca was biopurified of Sr 6-fold, of Ba 7-fold, and of Pb 1.1-fold. Similar ranges of values for these factors were obtained for detrital and amphibian food chains. Fluxes of industrial lead entering the ecosystem as precipitation and dry deposition were measured and it was found that 40% of the lead in soil humus and soil moisture, 82% of the lead in sedge leaves, 92% of the lead in vole, and 97% of the lead in marten was industrial. The natural skeletal $\text{Pb}\text{Ca}$ ratio in carnivores (4 × 10^?8) was determined by means of corrections for inputs of industrial lead, food chain relationships, and measured biopurification factors for the ecosystem studied. This represents a 1700-fold reduction of the average $\text{Pb}\text{Ca}$ ratio in igneous rocks at the earth's surface (6.4 × 10^?5) by the compounding of successive Pb biopurification factors in transferring Ca from rock to carnivore. The natural ratio is similar to the value of 6 × 10^?8 observed for $\text{Pb}\text{Ca}$ in the bones of Peruvians who lived 2000 years ago but is 1/900th of the value of about 3.5 × 10^?5 for the skeletal $\text{Pb}\text{Ca}$ ratio found in present day Americans.This study shows experimentally how the $\text{Ba}\text{Ca}$ ratio in average surface igneous rock (3 × 10^?3) has been reduced 800-fold through compounding of successive biopurification steps to provide the skeletal $\text{Ba}\text{Ca}$ ratio of about 4 × 10^?6 observed in humans. It also provides biopurification factors for Sr and Ba among a number of nutrient-consumer pairs which anthropologists can use to delineate degrees of herbivory in diets of hominids within the last 10,000 years.     

SrCa and MgCa ratios in polygenetic carbonate allochems from a Michigan marl lake

Rapid accumulation of CaCO₃ is occurring in Littlefield Lake, a marl lake located in central Michigan. The sediment, which is 95% CaCO₃, primarily consists of eight different genetic groups of carbonate allochems. These include calcite muds, sands, algal oncoids and Chara encrustations, as well as the dominant aragonitic gastropods Valvota tricarinota. Gyraulus deflectus and Amnicola integra. and the dominant aragonitic pelecypod Sphaerium partumeium. Samples of each of these groups were analyzed for Ca, Sr and Mg. Molar $\text{Mg}\text{Ca}$ ratios are primarily controlled by allochem mineralogy, with calcitic forms having $\text{Mg}\text{Ca}$ ratios 5–10 times larger than aragonitic (shelled) forms. The $\text{Sr}\text{Ca}$ ratios are primarily controlled by biochemical fractionation, and are significantly lower than $\text{Sr}\text{Ca}$ ratios of inorganically precipitated aragonite from other settings. Partition coefficients were determined for both Sr and Mg for each carbonate allochem group and, based on comparisons with results reported by other workers, the partition coefficients determined here are generally considered ‘typical’ or representative values for biogeneous freshwater carbonates. An analysis of variance of the data indicates that most genera and species of carbonate-secreting organisms in marl lakes have highly characteristic $\text{Sr}\text{Ca}$ and $\text{Mg}\text{Ca}$ ratios. These ratios can potentially serve as geochemical tracers in future investigations of lacustrine carbonate diagenesis. Both Sr and Mg are influenced by grain size and/or surface area, probably due to the presence of these elements in non-lattice-held (exchangeable) positions.     

The geochemical evolution of the Pleistocene Lake Lisan-Dead Sea system

The geochemical history of Lake Lisan, the Pleistocene precursor of the Dead Sea, has been studied by geological, chemical and isotopic methods.Aragonite laminae from the Lisan Formation yielded (equivalent) Sr/Ca ratios in the range 0.5 × 10^?2?1 × 10^?2, Na/Ca ratios from 3.6 × 10^?3 to 9.2 × 10^?3, $\text{δ}{}^{18}\text{O}{}_{\mathrm{PDB}}$ values between 1.5 and 7%. and $\text{δ}{}^{13}\text{C}{}_{\mathrm{PDB}}$ from ?7.7 to 3.4%..The distribution coefficient of Na⁺ between aragonite and aqueous solutions, $\text{λ}{}^{\mathrm{A}}{}_{\mathrm{Na}}$, is experimentally shown to be very sensitive to salinity and nearly temperature independent. Thus, Na/Ca in aragonite serves as a paleosalinity indicator.Sr/Ca ratios and $\text{δ}{}^{18}\text{O}$ values in aragonite provide good long-term monitors of a lake's evolution. They show Lake Lisan to be well mixed, highly evaporated and saline. Except for a diluted surface layer, the salinity of the lake was half that of the present Dead Sea (15 vs 31%).Lake Lisan evolved from a small, yet deep, hypersaline Dead Sea-like, water body. This initial lake was rapidly filled-up to its highest stand by fresh waters and existed for about 40,000 yr before shrinking back to the present Dead Sea. The chemistry of Lake Lisan at its stable stand represented a material balance between a Jordan-like input, an original large mass of salts and a chemical removal of aragonite. The weighted average depth of Lake Lisan is calculated, on a geochemical basis, to have been at least 400, preferably 600 m.The oxygen isotopic composition of Lake Lisan water, which was higher by at least 3%. than that of the Dead Sea, was probably dictated by a higher rate of evaporation.Na/Ca ratios in aragonite, which correlate well with $\text{δ}{}^{13}\text{C}$ values, but change frequently in time, reflect the existence of a short lived upper water layer of varying salinity in Lake Lisan.     

Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen,carbon and strontium

Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (δ ¹⁸O(SMOW) = +9.14 to +11.82%₀) were deposited from waters enriched in ¹⁶O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (δ ¹³C(PDB) = ?15.6 to ?16.9%₀) was derived in part from the coal (δ ¹³C(PDB) = ?23.5 to ?26.7%₀) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.71318–0.72392)}$ originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup.Calcite cleats in the Kittaning No. 6 coal seam of Ohio (δ ¹⁸O(SMOW) = +26.04 to +27.79%₀) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (δ ¹³C(PDB) = 0.9 to +2.4%₀) is enriched in ¹³C even though that cleats were deposited in coal that is highly enriched in ¹²C and apparently originated from marine carbonates. Strontium in the cleats ($\text{Sr}\text{87}$ 0.71182–0.71260) is not of marine origin but contains varying amounts of radiogenic ⁸⁷Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past.     

Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites

Significant amounts of SO₄^2?, Na⁺, and OH^? are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO₄^2?. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na⁺, but very low concentrations of SO₄^2?. The SO₄^2? content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na⁺ and SO₄^2? increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO₄^2? beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO₄^2? is the same as that of aragonite. Na⁺ appears to have very little effect on the solubility product of calcites. The amounts of Na⁺ and SO₄^2? incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ($\text{D}$) of SO₄^2? in calcite at 25.0°C and 0.50 molal NaCl is described by the equation $\text{D = k}{}_0\text{+ k}{}_1\text{R}$ where $\text{k}{}_0$ and $\text{k}{}_1$ are constants equal to $\text{6.16 × 10}{}^{\mathrm{?6}}$ and $\text{3.941 × 10}{}^{\mathrm{?6}}$, respectively, and $\text{R}$ is the rate of crystal growth of calcite in mg·min^?1·g^?1 of seed. The data on Na⁺ are consistent with the hypothesis that a significant amount of Na⁺ occupies interstitial positions in the calcite structure. The distribution of Na⁺ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na⁺ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na⁺ contents of calcites are not very accurate indicators of environmental salinities.     

Uptake of fluoride by aragonite

The uptake of F by aragonite is attributed to the ion-exchange process, in which one CO₃^2? ion in the structure is replaced by two F^? ions. Under the equilibrium condition at 15° C and 1 atm., the partition of F between aragonite and aqueous solution is described by:

$\text{log}\text{(}\text{[}\text{F}\text{]}\text{a}{}_{\mathrm{<mtext>F</mtext>}}\text{)=1.95 + 0.54}\text{log}\text{a}{}_{\mathrm{<mtext>Ca</mtext>}}$

were [F] denotes the F content of aragonite in mol/g, and a_F and a_Ca are the aqueous activities of F^? and Ca²⁺, respectively. The equation was successfully applied to estimating the F content of marine aragonite.     

Interstellar organic matter in meteorites

Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The $\text{D}\text{H}$ ratios of hydrogen in the organic matter vary from 8 × 10^?5 to 170 × 10^?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10^?5 for terrestrial hydrogen and 2 × 10^?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose $\text{D}\text{H}$ ratios are greater than 30 × 10^?5. If the $\text{D}\text{H}$ ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having $\text{D}\text{H}$ ratios above 50 × 10^?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed $\text{D}\text{H}$ ratios in organic compounds in interstellar clouds are typically 180 × 10^?5 and range between about 40 × 10^?5 and 5000 × 10^?5. The $\text{D}\text{H}$ values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their $\text{D}\text{H}$ ratios.In contrast, the $\text{D}\text{H}$ ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10^?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H₂O with H₂ in the solar nebula at temperatures of about 200 K and higher.The ${}^{13}\text{C}{}^{12}\text{C}$ ratios of organic matter, irrespective its $\text{D}\text{H}$ ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high $\text{D}\text{H}$ ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.     

Strontium-calcium ratios in Cenozoic planktonic foraminifera

The $\text{Sr}\text{Ca}$ ratio and other parameters have been measured in fossil planktonic foraminifera from the Atlantic and Pacific Ocean basins in order to evaluate the $\text{Sr}\text{Ca}$ ratio of seawater during the last 75 million years. Results on well-preserved samples indicate that the ratio has increased to its present value by 10–15% during the Cenozoic, and that minima occurred between 55-45 Ma and 10-5 Ma, when the ratio was 15–25% less than at present. The long-term increase may reflect either decreasing deposition of aragonite with a high $\text{Sr}\text{Ca}$ ratio in shallow seas, or decreasing seafloor spreading rates and consequently decreasing hydrothermal supply of Ca during the Cenozoic. Other geologic evidence suggests that the Eocene minimum (near 50 Ma) may have resulted from increased aragonite sedimentation, while the Late Miocene minimum (between 10-5 Ma) may have been caused by an increased rate of seawater-basalt exchange when seafloor spreading rates increased on the East Pacific Rise near 10 Ma.     

A fundamental equation for calcite dissolution kinetics

A fundamental rate equation for the dissolution of calcite in a pure 0.7 M KC1 solution has been determined. Between pH 8.0 and 10.1 the kinetics of the dissolution reaction can be expressed by the equation

$\text{d[Ca}{}^{\mathrm{2+}}\text{]/dt = kA(C-[Ca}{}^{\mathrm{2+}}\text{]}\text{1}\text{2}\text{[CO}{}_3{}^{\mathrm{2?}}\text{]}\text{1}\text{2}\text{)}$

, where d[Ca²⁺]/dt is the rate in mole cm^?3s^?1, k is the apparent rate constant in s^?1 cm^?2, A is the calcite surface area and C is the square root of the calcite solubility constant. The apparent rate constant at 20°C is 9.5 × 10^?6s^?1cm^?2. The apparent activation energy for the reaction between 5 and 50°C is 8.4 kcal mole^?1.The reaction rate is pH independent above pH = 7.5. At pH values less than 8, [CO₃^2?] becomes negligible, and the rate becomes fast and should be dependent on the calcite surface area alone, if there is no change in mechanism.The stirring coefficient between 2.8 and 11.1 rev s^?1 is 0.33. This, together with the relatively high activation energy, indicates that the reaction is mainly chemically controlled.Interpolation of the experimental results into seawater systems gives a computed rate several magnitudes greater than the observed rate, but considerably less than that calculated for a diffusion-controlled reaction.     

A strontium isotopic study of Smackover brines and associated solids,southern Arkansas

The isotopic composition of Sr has been measured in brine samples from the Upper Jurassic Smackover Formation in southern Arkansas; ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios range from 0.7071 to 0.7101. With one exception, the 32 Smackover brines contain Sr which is significantly more radiogenic than the Sr in Late Jurassic sea water, indicating sizable Sr contributions from detrital sources. Isotopic analyses of core samples from rock units associated with the brines and regional stratigraphic relationships suggest that the radiogenic Sr was released from detrital minerals in Bossier shale to interstitial fluids expelled from the underlying Louann Salt in the North Louisiana salt basin. These fluids migrated through the Bossier Formation updip to the South Arkansas shelf, where they entered the upper Smackover carbonate grainstone. The radiogenic fluids mixed with Sr-rich interstitial marine waters that had the isotopic composition of Late Jurassic sea water; mixing in variable proportions resulted in the random distribution pattern of variable ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios that is observed in Smackover brines within the 5000 km² study area. Isotopic analyses of nonskeletal carbonate grains and coexisting coarse calcspar cement from the upper Smackover grainstone imply that the grains were diagenetically stabilized in the presence of interstitial marine waters, whereas the calcspar cement is a relatively late diagenetic phase precipitated after the arrival of radiogenic fluids.     

Li,Sr, Mg,and Na in foraminiferal calcite shells from laboratory culture,sediment traps,and sediment cores

Constant-temperature laboratory culture experiments of the planktonic foraminiferal species Globigerinoides sacculifer (Brady) suggest that the ratios of Li and Sr to Ca in the shells are a function of these ratios in the culture solutions. $\text{Mg}\text{Ca}$ and $\text{Na}\text{Ca}$ in the shells did not vary with changes of these ratios in the culture solution. These are the first direct determinations of the relationship between foraminiferal shell chemistry and solution composition.The possibility of temperature dependence for the minor elemental composition of foraminiferal shells was also investigated in the laboratory and by analysis of several planktonic and one benthic foraminiferal species from sediment trap and sediment core samples. The $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios in the natural samples roughly correlate with calcification temperature, whereas differences in the Li/Ca ratios are small and not systematically related to temperature. However, laboratory culture experiments at 20°C and 30°C showed no variation in the $\text{Li}\text{Ca}$, $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios with calcification temperature for the planktonic foraminifera G. sacculifer and Orbulina universa. Therefore, observed differences in the $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios for the sediment trap and core foraminiferal samples cannot be ascribed to direct effects of calcification temperature, but may be due to some other environmental factor which is correlated with temperature.     

Carbon and oxygen isotopes in epigenetic hydrothermal rocks from Hamam-el-Farun,Sinai

Rock samples from an Eocene cliff above the thermal spring of Hamam-el-Farun (west coast of Sinai) show various degrees of dolomitization and calcitization ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios indicate that dolomite and secondary calcite precipitated from hot brines.     

Americium interaction with calcite and aragonite surfaces in seawater

Observations of the distribution of ²⁴¹Am in the marine environment indicate that Am has a high affinity for solid surfaces. The adsorption of Am onto calcite and aragonite surfaces from seawater and related solutions has been studied, in order to establish the interaction of Am with a major component of many marine sediments. Results indicate that Am is rapidly and strongly adsorbed. This occurs even when both dissolved Am concentrations and solid to solution ratios are low. The minimum value for $\text{K}{}_{\mathrm{D}}$ determined is 2 × 10⁵. Measurements of reaction kinetics established that Am is adsorbed from seawater at 40 times the rate per unit surface area on synthetic aragonite that it is on synthetic calcite. Approximately 15% of the difference is attributable to epitaxial influences, with the remainder being due to enhanced site competition by Mg on calcite relative to aragonite. The adsorption rate is first order with respect to Am concentration, but follows approximately the square root of the solid surface area to solution volume ratio.Adsorption rate of Am on biogenic aragonite and Mg-calcites are, within a given particle size range, close to equal. It is not possible to normalize these adsorption rates to surface area due to the differing microporous structure of biogenic carbonates. The Am adsorption rates on a shallow water calcium carbonate-rich sediment gave results which were predicted from, its mineralogie mixture of components.     

Aragonite from deep sea ultramafic rocks

Aragonite mineralization was observed in serpentinized peridotites from the Romanche and Vema Fracture Zones in the Atlantic and the Owen Fracture Zone in the Indian Ocean, either in veins or as radial aggregates in cavities within the serpentinites. Evidence of incipient dissolution of the aragonite crystals was observed in one case. The aragonites tend to have lower Mg content (< 0.03%) and higher Sr content (> 0.95%) relative to other marine aragonites. Their ${}^{18}\text{O}{}^{16}\text{O}$, ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}$ isotopic ratios suggest the aragonite was deposited at ocean floor temperatures from solutions derived from sea water circulating in fissures and fractures within the ultramafic rocks. The ${}^{18}\text{O}{}^{16}\text{O}$ ratios of the serpentines indicate serpentinization occurred at higher temperatures, probably deeper in the crust. Low-T reactions between circulating seawater and Mg-silicates (primarily serpentine and pyroxenes) caused high pH and enrichment of Mg and Ca in the solution, conditions favoring carbonate precipitation. Aragonite was formed rather than calcite presumably because the high Mg²⁺ concentration in the solution inhibited calcite precipitation. The high Sr content of the aragonites is probably related, at least in part, to their low temperature of formation. Opaque mineral grains containing over 8% NiO and over 40% MnO were observed concentrated along the margins of some of the aragonite veins, suggesting that Ni is one of the elements mobilized during reactions between ultramafic rocks and circulating seawater.