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.     

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.     

Evidence of evaporite deposition in the Lower Carboniferous Main Limestone Series of South Wales,U.K.

Petrographic examination of the dolomitized Main Limestone Series cropping out in the south, east and northeast corners of the South Wales Coalfield Basin shows evidence of the earlier presence of evaporite minerals. However, it is believed that lack of extensive evaporite deposits in these rocks may be due to the active diagenetic dissolution and oncoming humid coal conditions of post Main Limestone time.The evaporite minerals in the Main Limestone rocks seem to be overwhelmingly early diagenetic in origin in the light of the following observations: (1) calcite or dolomite pseudomorphs after gypsum crystals associated with a fine pelmicrite matrix; (2) association of such pseudomorphs with oolitic pelsparite; and (3) evaporite solution breccia texture.     

Behaviour of strontium in subsurface calcium chloride brines: Southern Israel and Dead Sea rift valley

Calcium chloride brines are, as a rule, relatively rich in strontium, but the enrichment is usually limited and is found to be related to the concentration of calcium. The limiting mechanisms were evaluated as a model which comprises simple interactions between minerals and solutions. Based on the known ranges of strontium concentration in minerals, mineral solubilities and partition coefficients of strontium (both poorly known in certain cases), six fields of $\text{Sr}\text{Ca}$ molar ratios were defined in terms of participating minerals and processes: (a) 0.38?1.56 × 10^{? 3} by dolomitization of calcite; (b) 1.5?2.2 × 10^{? 2} due to dolomitization of aragonite; (c) 0.4?1.4 × 10^{? 2} as a result of solution-reprecipitation of calcite; (d)0.12?0.20 through transformation of aragonite to calcite; (e)0.10?0.60 through equilibrium of the pair calcite-strontianite; and (f)0.01?0.08 by equilibrium with gypsum and celestite.The model was applied to the analysis of two groups of brines from southern Israel which are originated in the coastal plain (group C) and in the rift valley (group R). The low $\text{Mg}\text{Ca}$ ratios of both water groups point to dolomitization as the main subsurface modifying process. $\text{Sr}\text{Ca}$ ratios of brines belonging to group C are consistent with dolomitization of aragonitic surface sediments at the beginning of their evolution. Brines of group R bear evidence to a similar pathway at the beginning of their evolution, but most of them were further affected by interaction with limestone.     

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.     

塔里木盆地东部地区寒武系白云岩成因类型*

塔里木盆地东部地区（简称塔东地区）寒武系白云岩主要有泥-粉晶白云岩、细晶白云岩和中-粗晶白云岩。通过岩石学特征、有序度、碳氧同位素、锶同位素比值、阴极发光和微量元素等分析,认为该地区有4种成因的白云岩,即深水回流准同生白云岩、潮坪蒸发泵准同生白云岩、回流渗透白云岩以及深埋藏白云岩。不同类型的白云岩,其岩性及地球化学特征不同。深水回流准同生白云岩为泥-粉晶白云岩,分布在塔东盆地中,是附近的碳酸盐岩台地上蒸发浓缩形成的咸化海水在重力作用下沿海底回流到深水盆地中并使刚沉积不久的灰泥发生白云化而形成的。潮坪蒸发泵准同生白云岩亦为泥-粉晶白云岩,形成于台地潮坪环境。回流渗透白云岩为细晶白云岩,发育于潮坪准同生白云岩和蒸发岩之下。深埋藏白云岩为中-粗晶白云岩,是石灰岩在地下深处由循环流动的富含Mg²⁺、Ca²⁺的地层水白云化形成的,Mg²⁺、Ca²⁺主要来自于已经存在的白云岩的溶蚀,而非来自页岩压实排替出来的地层水。     

Associated chemical and carbon isotopic composition variations in diamonds from Finsch and Premier kimberlite,South Africa

The carbon isotopic composition of 66 inclusion-containing diamonds from the Premier kimberlite, South Africa, 93 inclusion-containing diamonds and four diamonds of two diamond-bearing peridotite xenoliths from the Finsch kimberlite, South Africa was measured. The data suggest a relationship between the carbon isotopic composition of the diamonds and the chemical composition of the associated silicates. For both kimberlites similar trends are noted for diamonds containing peridotite-suite inclusions (P-type) and for diamonds containing eclogite-suite inclusions (E-type): Higher δ¹³C P-type diamonds tend to have inclusions lower in SiO₂ (ol), Al₂O₃ (opx, gt), Cr₂O₃, MgO, $\text{Mg}\text{(Mg + Fe)}$ (ol, opx, gt) and higher in FeO (ol, opx, gt) and CaO (gt). Higher δ¹³C E-type diamonds tend to have inclusions lower in SiO₂, Al₂O₃ (gt, cpx), MgO, $\text{Mg}\text{(Mg + Fe)}$ (gt), Na₂O, K₂O, TiO₂ (cpx) and higher in CaO, $\text{Ca}\text{(Ca + Mg)}$ (gt, cpx).Consideration of a number of different models that have been proposed for the genesis of kimberlites, their xenoliths and diamonds shows that they are all consistent with the conclusion that in the mantle, regions exist that are characterized by different mean carbon isotopic compositions.     

Geochemistry and petrology of the Main Limestone Series (Lower Carboniferous), South Wales,U.K.

Dolomitized Main Limestone rocks of the Lower Carboniferous crop out in a narrow band of about three fourths of a mile along the south, east and northeast rims of the South Wales Coalfield Basin which encompasses the general regions of Miskin, Taffs Well and the Clydach, respectively. The thickness of these rocks varies from a maximum of 2,750 feet to nothing.The Ca/Mg ratio in the Main Limestone in general ranged from 1.7 : 1 to over 100 : 1 with less than 2 : 1 to 3.5 : 1 being the commonest. Magnesium content ranged from less than 5% to over 60% (mole percent MgCO₃), with 40–50 mole percent p.f. MgCO₃ being the commoner.Petrographic study of the Main Limestone led to recognition of six major microfacies. They are: (1) biosparite; (2) dolobiomicrite; (3) quartz-dolomicrite; (4) dolomicrite; (5) oosparite; and (6) dolorudite. In terms of their geographic distribution, dolobiomicrite predominates in the Taffs Well region, while quartz-dolobiomicrite is common in the Clydach region. In terms of their distribution in time, biosparite is common in the basal part (Lower ZC₁ zone), dolobiomicrites (including the quartz-bearing variety) in the middle part (ZC₁ and C₂S₁ zone) of the Taffs Well region and its corresponding Calcite-Mudstone Group in the Clydach region.The bulk of dolomitization in these rocks occurred in the Caninia-Seminula zone or the Calcite-Mudstone Group. In this study, it marks geochemical stage B: the sea-connected lagoonal phase similar to one observed today in South Australia. It is suggested that such a sea-connected Lagoon in the Main Limestone Sea formed largely in response to a reef barrier (or a ridge) - a remnant of which is found today between Miskin and the Taffs Well region where the transition from lime to dolomite facies occurs. The Miskin area represented the deeper-water reef flank towards the open sea whereas the Taffs Well region marked the shallow-water reef flank landward.It is concluded that the Main Limestone Series contains predominantly diagenetic dolostones whilst the syngenetic and epigenetic dolostones are restricted in time and space. The diagenetic dolostone dominates in the Taffs Well and Clydach regions.     

CaAl ratio and composition of the Earth's upper mantle

Undifferentiated meteorites (chondrites) have the same relative abundances of refractory lithophile elements (Ca, Al, Ti, Sc, REE, etc.), despite variable absolute concentrations. The reasonable assumption of chondritic ratios among refractory elements in the bulk Earth is used to constrain the chemical composition of the upper mantle in the following way: Correlations of the compatible refractory elements Ca, Al, Ti, Sc and Yb with MgO are worldwide very similar in suites of spinel-lherzolite xenoliths from basaltic rocks. Such suites represent upper mantle material depleted to differing degrees by extraction of partial melts. From these refractory elements vs. MgO correlations, ratios of pairs of refractory elements were calculated at various MgO contents. Chondritic $\text{Al}\text{Ti}$ and $\text{Sc}\text{Ti}$ ratios were only obtained for MgO contents below 36%. A chrondritic $\text{Sc}\text{Yb}$ ratio requires an MgO content above 35%. We therefore accept 35.5% as the most reasonable MgO content of undepleted upper mantle. This MgO content is slightly below the spinel-lherzolite with the lowest measured MgO content (36.22%). The corresponding Al₂O₃ content of 4.75% is higher than in previous estimates of upper mantle composition. The concentrations of other elements were obtained from similar correlations at a MgO content of 35.5%. The resulting present upper mantle composition is enriched in refractory elements by a factor of 1.49 relative to Si and Cl and by a factor of 1.12 for Mg relative to Si and Cl. These enrichments are in the same range as those for the Vigarano type carbonaceous chondrites. The Mg/Mg + Fe ratio of 89 is slightly lower than previous estimates.The $\text{Ca}\text{Al}$ ratio in spinel lherzolite suites is, however, uniformly higher worldwide than the chondritic ratio by about 15%. Orogenic peridotites as well as komatiites appear to have similar non-chondritic $\text{Ca}\text{Al}$ ratios. It is therefore suggested that this non-chondritic $\text{Ca}\text{Al}$ ratio is a characteristic of the upper mantle, possibly since the Archean. A minor fractionation of about 4% of garnet in an early, global melting event (deep magma ocean?) is presented as the most likely cause for the high $\text{Ca}\text{Al}\text{-}\text{ratio}$. In this case the addition of 4% of such a garnet component to the undepleted present upper mantle would be required to obtain the composition of the primordial upper mantle. The $\text{Ca}\text{Al}\text{-}\text{ratio}$ of this primordial mantle would be 15% higher than that of the undepleted present upper mantle, resulting in an enrichment of refractory elements of 1.70 ($\text{Al}\text{Si}$ relative to Cl) for the primordial upper mantle.     

A kinetic model for distribution coefficients and application to Mg-calcites

A review of experimental and natural Mg-calcite occurrences indicates that no simple relation exists between $\text{mMg}\text{mCa}$ in solution and $\text{X}{}^{\mathrm{Mg}}\text{X}{}^{\mathrm{ca}}$ in growing calcite crystals. The great variability of the data suggests a strong influence of precipitation kinetics on the distribution of Mg⁺² between solution and crystal. We have derived a kinetic formulation for the distribution coefficient (λ^Mg = X^Mg/X_Ca/ mMg/mCa) based upon the existence, at steady state conditions, of a constant mass surface phase. The resulting formulation is consistent with both experimental and natural Mg-calcite compositions. The primary factors which influence the value of λ^Mg are temperature and the ratio of K_sp^MCO3 to the activity product ([M⁺²][CO₃^?2]/[MCO₃]) for magnesite and calcite. The results suggest that Mg-calcite composition (X^Mg/X^Ca) is at best a crude measure of the mMg/mCa ratio in paleosolutions.     

Subsolidus and melting relations for the join CaCO3-MgCO3 at 10 kbar

Mixtures of pure dry CaCO₃ and MgCO₃ were reacted at 10 kbar in a piston-cylinder apparatus. Solidus and liquidus boundaries were delineated by interpretation of quenched textures. X-ray determined compositions of quenched carbonates are not a reliable guide to the phase relations. The binary melting loop for CaCO₃-MgCO₃ extends from CaCO₃ at 1460°C through a liquidus minimum near 30 wt% MgCO₃ and 1075°C, and it is terminated at the incongruent melting reaction for dolomite solid solution at 1125° C (liquid with 32 wt% MgCO₃) Magnesite solid solution dissociates at 1090°C to produce dolomite + periclase + CO₂, truncating the dolomite-magnesite solvus. The 10 kb liquidus minimum at 1075°C and 30 wt% MgCO₃ occurs at lower temperature and higher $\text{Ca}\text{Mg}$ ratio than the 27 kbar liquidus minimum at 1290°C and 38 wt% MgCO₃. This relationship suggests that the first liquid produced by melting of a carbonate-bearing peridotite has increasing $\text{Mg}\text{Ca}$ ratio with increasing pressure. These phase relations provide part of the framework required to trace paths of crystallization of kimberlite and carbonatite magmas.     

Cation-exchange characteristics of Amazon River suspended sediment and its reaction with seawater

The cation-exchange characteristics of Amazon River suspended sediment have been studied in order to determine the contribution of exchangeable cations to the geochemical fluxes from the river. Sediment samples were obtained throughout most of the Amazon Basin. The range of exchangeable cation compositions is very narrow in the river and in seawater as well. In river water, the exchangeable cation complement (equivalent basis, exclusive of H⁺) is 80% Ca²⁺, 17% Mg²⁺, 3% Na⁺ plus K⁺. In seawater Na⁺ and Mg²⁺ are about equal (38%) while Ca²⁺ ~ 15% and K⁺ ~ 9%.On reaction with seawater, river suspended sediment took up an amount of Na⁺ equal to nearly one-third of the dissolved river load, as well as amounts corresponding to 15–20% of the dissolved fluvial K⁺ and Mg²⁺. These estimates reflect an unusually high suspended-sediment:dissolved-solids ratio of 6.4 at the time of sampling. At a more representative world average ratio of four, the uptake of Na⁺ would be 20% of the dissolved fluvial load, and that for K⁺ and Mg²⁺ about 10%. Over the annual cycle of the Amazon, it is estimated that ion exchange has a still smaller effect, as a consequence of the low average suspended-solids:dissolved-solids ratio of 1.7.Variations in the ratio $\text{X}{}_{\mathrm{Ca}}\text{X}{}_{\mathrm{Mg}}$, the equivalent fraction of exchangeable Ca²⁺ and Mg²⁺, throughout the river, can be described by a single isotherm. This same isotherm accurately describes the distribution of exchangeable Ca²⁺ and Mg²⁺ on sediment equilibrated with seawater, despite that a high proportion of exchange sites is occupied by Na⁺ and K⁺.     

鄂尔多斯盆地中南部马五1-2亚段岩相古地理特征及其对储层的影响

为探讨岩相古地理环境对储层的影响,以鄂尔多斯盆地中南部马五_1-2亚段为例,综合利用岩芯观察及薄片鉴定、多矿物测井解释模型以及单因素分析多因素综合作图法等多种方法,对研究区岩相、岩相古地理特征进行了研究,并结合测井解释储层厚度的分布特征及实际天然气产量数据分析了岩相古地理环境对储层分布的影响。分析结果表明,研究区马五_1-2亚段岩石类型主要包括白云岩（泥晶白云岩、膏盐溶蚀角砾白云岩、溶蚀角砾泥晶白云岩、溶蚀角砾含灰粉晶白云岩、灰云岩、含膏云岩、含泥含灰云岩、泥云岩）、石灰岩（云灰岩、含泥云灰岩）以及部分蒸发岩（石膏岩、盐岩）。岩相古地理环境以蒸发台地和局限台地亚相为主,蒸发台地亚相包括云坪和含膏云坪微相,局限台地亚相包括膏盐湖、膏湖和含膏湖微相。岩相古地理环境在一定程度上影响储层分布,蒸发台地亚相中的云坪微相、含膏云坪微相以及局限台地亚相中的部分含膏湖微相、膏湖微相均是储层发育的有利区域。     

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.     

Precise age determinations and petrogenetic studies using the KCa method

High precision mass spectrometric determination of calcium isotope ratios allows the ⁴⁰K → ⁴⁰Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ is used to monitor enrichments in ⁴⁰Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low $\text{K}\text{Ca}$ (～0.01) that it has retained “primordial” ${}^{40}\text{Ca}{}^{42}\text{Ca}\text{= 151.016}$ ± 0.011 (normalized to ${}^{42}\text{Ca}{}^{44}\text{Ca}\text{= 0.31221}$), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ ratios can be conveniently expressed relative to this value as ?_Ca in units of 10^?4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λ_K = 0.5543 b.y.^?1, $\text{λ}{}_{\mathrm{\beta ?}}\text{λ}{}_{\mathrm{<mtext>K</mtext>}}\text{= 0.8952}$, ⁴⁰K = 0.01167%). The initial ${}^{40}\text{Ca}{}^{42}\text{Ca}$ of 151.024 ± 0.016 (?_Ca = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of ⁴⁰K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.     

Enthalpy of formation of forsterite,enstatite, akermanite,monticellite and merwinite at 1073 K determined by alkali borate solution calorimetry

Enthalpies of solution of synthetic enstatite (Mg₂Si₂O₆), forsterite (Mg₂SiO₄), akermanite (Ca₂MgSi₂O₇), monticellite (CaMgSiO₄), and merwinite (Ca₃MgSi₂O₈) and their component oxides were determined in eutectic (Li, Na)BO₂ at 1073 K. Resulting enthalpies of formation at 1073 are enstatite: $\text{?8.10 ± 0.42}\text{kcal}$; forsterite: $\text{?14.23 ± 0.45}\text{kcal}$; akermanite: $\text{?42.60 ± 0.39}\text{kcal}$; monticellite: $\text{?25.05 ± 0.41}\text{kcal}$; and merwinite: $\text{?51.10 ± 0.49}\text{kcal}$. The value for the synthetic monticellite of composition Mo_.965Fo_.035 was corrected slightly for non-stoichiometry based on experimental monticellite-forsterite phase equilibrium relations.The enthalpies of formation of enstatite and forsterite are somewhat less negative than yielded by several other solution calorimetric studies but are in good agreement with the recent Pb₂B₂O₅ solution calorimetry of Kiselevaet al. (1979), and are in good agreement with values to be derived from reliable phase equilibrium data in the system MgO-Al₂O₃-SiO₂. The enthalpies of formation of akermanite, monticellite and merwinite are all much less negative than values tabulated by robieet al. (1978) and helgesonet al. (1978) but are shown to be compatible with reliable phase equilibrium data for the system CaO-MgO-SiO₂, whereas the tabulated values are not. Several methods of analysis yield an entropy of monticellite at 1000 K of $\text{69.9 ± 0.2 cal/K}$.     

On the age of the Onverwacht Group,Swaziland Sequence,South Africa

Some rocks of the Onverwacht Group, South Africa, have been analyzed for Rb and Sr concentrations and Sr isotopie composition. These rocks include volcanic rocks, layered ultramafic differentiates and cherty sediments. Whole rock data indicate that the Rb-Sr isotopie systems in many samples were open and yield no reasonable isochron relationships. However, the data of mineral separates from a basaltic komatiite define a good isochron of $\text{t = 3.50 ± 0.20}$ (2δ) b.y. with an initial Sr⁸⁷/Sr⁸⁶ ratio of $\text{0.70048 ± 5}$(2δ). The orthodox interpretation of this age is the time of the low grade metamorphism. Since the basaltic komatiite is stratigraphically lower than the Middle Marker Horizon (dated as $\text{3.36 ± 0.07}$ b.y. Hurley et al., 1972), and since it is commonly found that volcanism, sedimentary deposition, metamorphism and igneous intrusion in many Archean greenstone-granite terrain all took place in a relatively short time interval (less than 100 m.y.), it is reasonable to assume that the age of 3.50 b.y. might also represent the time of initial Onverwacht volcanism and deposition. The initial Sr⁸⁷/Sr⁸⁶ ratio obtained above is important to an understanding of the Sr isotopic composition of the Archean upper mantle. If the komatiite represents a large degree of partial melt (40–80 per cent) of the Archean upper mantle material, then the initial ratio obtained from the metamorphic komatiite should define an upper limit for the Sr isotopic composition of the upper mantle under the African crustal segment.     

Carbon content and carbonate 13C abundances in the Early Precambrian Swaziland sediments of South Africa

Carbon content (0.02–0.68% organic), carbonate content (0–69.7%) and carbonate ¹³C abundances (${}^{\mathrm{?}}\text{7.5?+2.3‰}$) were obtained on samples from the Swaziland sediments of South Africa, which are among the oldest known sedimentary rocks on earth (> 3·10⁹ years old). The carbon chemistry of these sediments may serve as evidence for early life and/or for products of chemical evolution. The variation of organic and carbonate carbon concentrations in different sedimentary horizons seems to be controlled by differences in depositional and diagenetic histories. The carbonate δ ¹³C values did not vary significantly from the ordinary range of Phanerozoic limestone values.     

Uranium-series dating of lacustrine limestones from pan deposits with final Acheulian assemblage at Rooidam,Kimberley district,South Africa

Lacustrine limestone samples from sedimentary pan deposits at Rooidam, near Kimberley, South Africa, that contain late Acheulian (Fauresmith) artifacts have been dated by ${}^{230}\text{Th}{}^{234}\text{U}$ and ${}^{231}\text{Pa}{}^{235}\text{U}$ methods. Results indicate a minimum age of about 200,000 yr B.P. for the terminal Acheulian in the interior of South Africa.