Geochemistry of Archean metasedimentary rocks from West Greenland

Archean metasedimentary rocks occur as components of the Isua supracrustals, Akilia association and Malene supracrustals of southern West Greenland. Primary structures in these rocks have been destroyed by metamorphism and deformation. Their chemistry and mineralogy is consistent with a sedimentary origin, but other possible parents (e.g. acid volcanics, altered pyroclastic rocks) cannot be excluded for some of them. There is little difference in the composition of metasedimentary rocks from the early Archean Isua supracrustals and probable correlative Akilia association. Both have a wide range in rare earth element (REE) patterns with $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ ranging from 0.61?5.8. The REE pattern of one Akilia sample, with low $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$, compares favourably with that of associated tholeiites and it is likely that such samples were derived almost exclusively from basaltic sources. Other samples with very steep REE patterns are similar to felsic volcanic boulders found in a conglomeratic unit in the Isua supracrustals. Samples with intermediate REE patterns are best explained by mixing of basaltic and felsic end members. Metasedimentary rocks from the Malene supracrustals can be divided into low silica (≤55% SiO₂) and high silica (>77% SiO₂) varieties. These rocks also show much variation in $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ (0.46?14.0) and their origin is explained by derivation from a mixture of mafic volcanics and felsic igneous rocks. The wide range in trace element characteristics of these metasedimentary rocks argues for inefficient mixing of the various source lithologies during sedimentation. Accordingly, these data do not rigorously test models of early Archean crustal composition and evolution. The systematic variability in trace element geochemistry provides evidence for the bimodal nature of the early Archean crust.     

Geochemistry of the Archean Yellowknife Supergroup

The Archean Yellowknife Supergroup (Slave Structural Province. Canada) is composed of a thick sequence of supracrustal rocks, which differs from most Archean greenstone belts in that it contains a large proportion ( ~ 80%) of sedimentary rocks. Felsic volcanics of the Banting Formation are characterized by HREE depletion without Eu-anomalies, indicating an origin by small degrees of partial melting of a mafic source, with minor garnet in the residua. Granitic rocks include synkinematic granites [HREE-depleted; low (${}^{87}\text{Sr}{}^{86}\text{Sr}$)_I], post-kinematic granites [negative Eu-anomalies, high (${}^{87}\text{Sr}{}^{86}\text{Sr}$)_I] and granitic gneisses with REE patterns similar to the post-kinematic granites. Sedimentary rocks (turbidites) of the Burwash and Walsh Formations have similar chemical compositions and were derived from 20% mafic-intermediate volcanics, 55% felsic volcanics and 25% granitic rocks. Jackson Lake Formation lithic wackes can be divided into two groups with Group A derived from 50% mafic-intermediate volcanics and 50% felsic volcanics and Group B, characterized by HREE depletion, derived almost exclusively from felsic volcanics.REE patterns of Yellowknife sedimentary rocks are similar to other Archean sedimentary REE patterns, although they have higher $\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}$. These patterns differ significantly from typical post-Archean sedimentary REE patterns, supporting the idea that Archean exposed crust had a different composition than the present day exposed crust.     

Geochemical modelling of basalts from DSDP Leg 65, East Pacific Rise,Gulf of California

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO₂ content (0.88%), $\text{FeO}{}^1\text{MgO}$ ratio (0.95 with total Fe as FeO), and Mg# (100 $\text{Mg}\text{Mg + Fe}\text{″ = 70}$), sample 483-17-2-(78–83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (chondrite-normalized) = 0.36, and $\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ = 1.05. Because other samples analyzed have higher SiO₂, lower Mg#, and a negative Eu anomaly ($\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An₈₈), 6.7% olivine (Fo₈₆), and 4.7% clinopyroxene (Wo₄₁En₄₉Fs₁₀) from 483-17-2-(78–83) to form the least differentiated sample with Mg# = 63. The $\text{La}\text{Sm}{}_{\mathrm{cn}}$ of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO₂ and P₂O₅ are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower $\text{La}\text{Sm}{}_{\mathrm{cn}}$ and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78–83) is required.     

An unusual basalt fragment in Luna 20 sample L2010

A Luna 20 basaltic fragment contains 70 per cent pyroxene, 25 per cent plagioclase (An₈₀) and 5 per cent ilmenite. There are two varieties of augite which differ markedly in their alumina content. The composition of this fragment, calculated from the analyses of the minerals, shows that the $\text{Al}{}_2\text{O}{}_3\text{FeO}$ ratio is different from that of other lunar basalts.     

Geochemistry of Archean shales from the Pilbara Supergroup,Western Australia

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group (ca. 3.4 Ae) and shales from the Whim Creek Group (ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition.Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ($\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}\text{≥ 7.5}$) and no or very slight Eu depletion ($\text{Eu}\text{Eu}{}^1\text{= 0.82 – 0.99}$). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.     

Geochemistry of loess,continental crustal composition and crustal model ages

Isotopic, major and trace element studies of loess deposits from America, China, Europe and New Zealand show general uniformity of composition. Silica, Zr and Hf are enriched relative to estimates of bulk composition of the upper continental crust. The REE data are indistinguishable from those of average shales, confirming the concept that these REE patterns ($\text{La}{}_{\mathrm{N}}\text{/}\text{Yb}{}_{\mathrm{N}}\text{= 9.5}\text{Eu}\text{/}\text{Eu}{}^1\text{= 0.66}$) represent the upper crustal average. Sm-Nd model ages are variable but <1700 m.y. They reflect derivation from younger elevated erogenic areas subject to Pleistocene glaciation. Although Sm-Nd model ages vary by a factor of two, the REE patterns remain constant. This indicates that processes responsible for formation of the upper crust have produced no secular change in composition since the mid-Proterozoic.     

Transfer and exchange equilibria in a portion of the pyroxene quadrilateral as deduced from natural and experimental data

Differences in the chemical composition of metamorphic and igneous pyroxene minerals may be attributed to a transfer reaction, which determines the Ca content of the minerals, and an exchange reaction, which determines the relative Mg:Fe²⁺ ratios. Natural data for associated Ca pyroxene (Cpx) and orthopyroxene (Opx) or pigeonite are combined with experimental data for Fe-free pyroxenes, to produce the following equations for the Cpx slope of the solvus surface: $\text{> 1080°C: T =}\text{1000}\text{(0.468 + 0.246X}{}^{\mathrm{Cpx}}\text{? 0.123 ln (1–2 [Ca]))}$$\text{< 1080°C: T =}\text{1000}\text{(0.054 + 0.608X}{}^{\mathrm{Cpx}}\text{? 0.304 ln (1–2 [Ca]))}$, and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: $\text{T =}\text{1130}\text{(}\text{ln}\text{K}{}_{\mathrm{p}}\text{+ 0.505)}$, where T is absolute temperature, X is $\text{Fe}{}^{\mathrm{2+}}\text{(Mg + Fe}{}^{\mathrm{2+}}\text{))}$, [Ca] is $\text{Ca}\text{(Ca + Mg + Fe}{}^{\mathrm{2+}}\text{)}$ in Cpx, and K_D is the distribution coefficient, defined as $\text{X}{}^{\mathrm{Opx}}\text{/(1 ? X}{}^{\mathrm{Opx}}\text{) ÷ X}{}_{\mathrm{Cpx}}\text{/(1 ?}{}^{\mathrm{Cpx}}\text{)}$.The transfer and exchange equations form useful temperature indicators, and when applied to 9 sets of well-studied rocks, yield pairs of temperatures that are in good agreement. For example, temperatures obtained for the Bushveld Complex are 1020°C (solvus equation) and 980°C (exchange equation), based on 7 specimens. The uncertainty in these numbers, due to precision and accuracy errors, is estimated to be ±60°.     

Trace element partitioning and melt structure: An experimental study at 1 atm pressure

Diopside-melt and forsterite-melt rare earth (REE) and Ni partition coefficients have been determined as a function of bulk compositions of the melt. Available Raman spectroscopic data have been used to determine the structures of the melts coexisting with diopside and forsterite. The compositional dependence of the partition coefficients is then related to the structural changes of the melt.The melts in all experiments have a ratio of nonbridging oxygens to tetrahedral cations ($\text{NBO}\text{T}$) between 1 and 0. The quenched melts consist of structural units that have, on the average, 2 (chain), 1 (sheet) and 0 (three-dimensional network) nonbridging oxygens per tetrahedral cation. The proportions of these structural units in the melts, as well as the overall $\text{NBO}\text{T}$, change as a function of the bulk composition of the melt.It has been found that Ce, Sm, Tm and Ni crystal-liquid partition coefficients ($\text{K}{}^{\mathrm{crystal?liq}}{}_{\mathrm{i}}\text{=}\text{C}{}^{\mathrm{crystal}}{}_{\mathrm{i}}\text{C}{}^{\mathrm{liq}}{}_{\mathrm{i}}$) decrease linearly with increasing $\text{NBO}\text{T}$. The values of the individual REE crystal-liquid trace element partition coefficients have different functional relations to $\text{NBO}\text{T}$, so that the degree of light REE enrichment of the melts would depend on their $\text{NBO}\text{T}$.The solution mechanisms of minor oxides such as CO₂, H₂O, TiO₂, P₂O₅ and Fe₂O₃ in silicate melts are known. These data have been recast as changes of $\text{NBO}\text{T}$ of the melts with regard to the type of oxide and its concentration in the melt. From such data the dependence of crystal-liquid partition coefficients on concentration and type of minor oxide in melt solution has been calculated.     

Correction of ground-water chemistry and carbon isotopic composition for effects of CO2 outgassing

Direct measurements on water samples from several CO₂-charged warm springs are significantly higher than values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO₂ outgassing during pH measurement. Because samples for direct measurement can be taken with minimal disturbance to the water chemistry, we have used the measured to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of $\text{δ}{}^{13}\text{C}$, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.     

Luna 20: mineral chemistry of spinel,pleonaste, chromite,ulvöspinel,ilmenite and rutile

Electron microprobe analyses of the spinel mineral group, ilmenite and rutile have been carried out on part of the Luna 20 soil sample. The spinel group shows an almost continuous trend from MgAl₈O₄ to FeCr₂O₄ and a discontinuous trend from FeCr₂O₄ to Fe₂TiO₄. Well defined non-linear relationships exist within the spinel group for Fe-Mg substitution, for divalent ($\text{FeO}\text{FeO + MgO}$) versus trivalent ($\text{Cr}{}_2\text{O}{}_3\text{Cr}{}_2\text{O}{}_3\text{+ A1}{}_2\text{O}{}_3$), and for divalent versus $\text{TiO}{}_2\text{TiO}{}_2\text{+ A1}{}_2\text{O}{}_3\text{+ Cr}{}_2\text{O}{}_3$. For Cr-Al substitution the relationship is linear and is negative for Mg-rich spinel and positive for Fe-Ti rich spinel. In general a combination of aluminous-rich chromite and ulvöspinel in the Luna 16 samples, combined with the chromian-pleonaste in Apollo 14 define comparable major compositional trends to those observed in Luna 20. Ilmenite is present in trace amounts. It is exsolved from pleonaste and pyroxene, is present in subsolidusreduced ulvöspinel and has undergone reequilibration to produce oriented intergrowths of chromite + rutile. Primary ilmenite is among the most magnesian-rieh (6 wt.% MgO) yet found in the lunar samples. The high MgO, inferred high Cr₂O₃ concentrations and the iron content of rutile (2.5 wt.% FeO) suggest crystallization at high temperatures and pressures for some components of the Luna 20 soil.     

Rare-earth and other trace element contents and the origin of minettes (mica-lamprophyres)

Instrumental neutron activation and X-ray fluorescence analyses of minettes from New Brunswick, Canada, indicate that these rocks are strongly enriched in REE, especially the LREE, and other incompatible elements as well as Cr and Co. The geochemistry of minettes precludes their formation by anatexis or assimilation of crustal rocks, contamination of mantle-derived basalts by non-crystalline residua of granite crystallization, or any process involving fractional crystallization of feldspar. Their peculiar geochemical characteristics must be a direct function of their origin in the mantle.Ultrapotassic rocks, kimberlites, and, to a lesser extent, carbonatites are strikingly similar to minettes in their rare earth and other trace element contents, suggesting genetic links among these rock types. It is difficult to explain the temporal and spatial constancy of this similarity by post-anatectic late enrichment of diversely produced magmas by volatile transport. We tentatively propose that the process best able to account for their unique geochemistry is limited partial melting of the subcontinental mantle following and dependent on the metasomatic introduction of K, Ti, Fe, REE, halogens, P, and other elements as well as H₂O and/or CO₂. If the enriched mantle is H₂O-rich, minette magma is produced; if it is CO₂-rich or has an intermediate $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, carbonatitic-kimberlitic and/or ultrapotassic magmas result.     

FUN with PANURGE: High mass resolution ion microprobe measurements of Mg in Allende inclusions

The performance characteristics of PANURGE, a modified CAMECA IMS3F ion microprobe, have been studied at a mass resolving power of 5000 for the purpose of determining isotopic ratios at a precision level approaching that of counting statistics using beam switching. The techniques used for this type of measurement are described. Using this approach, the isotopic composition of Mg and Si and the atomic ratio of $\text{Al}\text{Mg}$ in minerals from the Allende inclusion WA and the Allende FUN inclusion Cl have been measured with the ion microprobe at high mass resolving power. Enrichments in ²⁶Mg of up to 260%. have been found. Mg and $\text{Al}\text{Mg}$ measurements on cogenetic spinel inclusions and host plagioclase crystals yield Mg-Al isochrons in excellent agreement with precise mineral isochrons determined by thermal emission mass spectrometry. The measurements confirm the presence of substantial excess ²⁶Mg in WA (${}^{26}\text{Mg}{}^1{}^{27}\text{Al = 5 × 10}{}^{\mathrm{?5}}$) and its near absence in Cl (${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{< 4 × 10}{}^{\mathrm{?6}}$). In WA plagioclase, data for which ${}^{27}\text{Al}{}^{24}\text{Mg}\text{= 300 to 1000}$ define a linear array with ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{= 3 × 10}{}^5$ and with initial ${}^{26}\text{Mg}{}^{24}\text{Mg}$ composition 30%. greater than in high Mg phases. This suggests a metamorphic reequilibration of Mg in Allende plagioclase at least 0.6 my after WA formation. There were no variations in detected ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}$ in WA plagioclase associated with concentration of ²⁶Mg¹ into isolated clusters. We have confirmed by ion probe measurements that the Mg composition in Allende Cl is highly fractionated and is uniform among pyroxene, melilite, plagioclase, spinel crystals and spinel included in melilite and plagioclase crystals. Likewise, the Si composition is mass fractionated and is the same in pyroxene, melilite and plagioclase.     

The role of apatite in mantle enrichment processes and in the petrogenesis of some alkali basalt suites

Analyses of Sr and REE in apatites from a variety of mantle-derived parageneses are used in conjunction with trace element data from the literature to investigate relationships between alkali basalts and apatite-rich materials in upper-mantle source regions. Despite difficulties in interpretation, positive P-anomalies in the hygromagmatophile element abundance patterns of some continental primary alkali basalts suggest either P-enrichment of their source or assimilation of P-rich material, or both. Amphibole- and apatite-rich xenoliths occur in several alkali-basalt provinces, and by virtue of the P and LREE enrichment represent a probable source of the P anomalies and part of the other trace element enrichments of these magmas. Incorporation of such apatite-rich materials by later primary magmas would be enhanced by the high P₂O₅ concentrations required to achieve apatite saturation in basaltic liquids.In the early stages of mantle diapirism an undersaturated magma, produced by slight partial melting of garnet peridotite, might fractionate as it rises to the range of amphibole stability. Hygromagmatophile element patterns of clinopyroxenite xenoliths indicate that clinopyroxene fractionation could produce P-enriched liquids which might subsequently crystallize amphibole- and apatite-rich materials now represented by xenoliths. During generation of later primary magma, apatite-rich materials might preferentially contaminate the liquids, to yield positive P-anomalies. This model requires that magmas undergo prolonged fractionation at considerable depth (~ 100 km), a process which is apparently most probable in subcontinental environments.An apatite- and zircon-bearing mica-clinopyroxenite xenolith from Matsoku provides a link between the S. African MARID suite and amphibole and apatite-rich xenoliths from various alkali basalt provinces. Unusual REE patterns ($\text{La}{}_{\mathrm{N}}\text{<}\text{Ce}{}_{\mathrm{N}}\text{<}\text{Nd}{}_{\mathrm{N}}\text{,}\text{Ce}{}_{\mathrm{N}}\text{/Y}{}_{\mathrm{N}}\text{?10}$) of apatites in this xenolith suggest a link between the MARID suite xenoliths and postulated pre-Karroo mantle metasomatism.     

Experimental hydrogen isotope studies—I. Systematics of hydrogen isotope fractionation in the systems epidote-H2O,zoisite-H2O and AlO(OH)-H2O

$\text{H}\text{D}$ Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules.$\text{H}\text{D}$ Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the $\text{H}\text{D}$ equilibrium fractionation factor (α^e) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In α_epidote-H2O^e = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals.     

The role of CO2 in the chemical modification of deep continental crust

Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO₂-rich fluid inclusions in granulites, have led to the suggestion that CO₂ must play a role in modifying the composition of deep continental crust. How CO₂ effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios, with ion solubilities being Na⁺ >K⁺ ? Ca⁺⁺. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO₂-rich regions contain rocks which consistently have low ratios, while H₂O-rich regions consistently have high ratios. Magnetite rims on sulfide grains are ubiquitous in high regions and are absent in high regions, and they provide evidence that CO₂ was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.     

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.     

A systematic deviation from Na-K-Ca geothermometer below 75°C and above 10−4 atm Pco2

If the temperature of ground water is below 75°C and the partial pressure of CO₂ in the aquifer is above 10^?4 atm, a chemical steady-state between water and felsic rocks (rather than chemical equilibrium) may be maintained. The temperature of water in the aquifer may be estimated using a modified form of the Na-K-Ca geothermometer from, . where the departure of the steady-state from equilibrium, $\text{I}$, is a function of : .     

Genesis of cordierite-gedrite-cummingtonite rocks of the northern portion of the khetri Copper Belt,Rajasthan, India

The cordierite-gedrite-cummingtonite rocks occur in the zone of sulphide mineralization. Field and petrographic evidences suggest formation of these rocks from the $\text{chlorite}\text{±}\text{garnet}$ schists which are associated with them. Time relations between crystallization and deformation, as evident by textural relations, suggest that this transformation constitutes a progressive sequence in time during prograde metamorphism in the area. Bulk chemical compositions of the cordierite-gedrite-cummingtonite rocks plot in the compositional range of the chlorite schists in the AKF, ACF and AFM diagrams. The AFM diagram shows a discontinuity in the topology as revealed by the intersection of the coexisting garnet-chlorite join with the three-phase field of cordierite-gedrite-garnet, suggesting the reaction: $\text{Al-chlorite}\text{+}\text{quartz}\text{(±}\text{garnet}\text{) ?}\text{gedrite}\text{+}\text{cordierite}\text{+}\text{H}{}_2\text{O}$. The reaction took place under conditions of , brought about by dilution of pore fluid by B, Cl, F, S, etc., which reduce the activity of water.     

Selective flotation of inherently hydrophobic minerals by controlling the air/solution interfacial tension

Selective wettability and floatability of several inherently hydrophobic minerals have been investigated using aqueous methanol solutions of various surface tensions. The relationship between the critical surface tension of wetting, $\text{γ}{}_{\mathrm{<mtext>c</mtext>}}$, and of floatability, $\text{γ}{}_{\mathrm{<mtext>cf</mtext>}}$, of the samples is examined. Experimental evidence is provided to show that a flotation feed cannot be represented by an uniquely defined $\text{γ}{}_{\mathrm{<mtext>cf</mtext>}}$ value. It is appropriate to specify for an inherently hydrophobic solid a critical surface tension range of floatability with upper and lower limits, $\text{γ}{}_{\mathrm{<mtext>cmf</mtext>}}$ and $\text{γ}{}_{\mathrm{<mtext>clf</mtext>}}$ respectively. The particles which are predominated by cleavage or crystal faces determine the lower limit, while those with some threshold degree of ionic character determine the upper limit. Examples of separation tests presented demonstrate that in the case of equality between $\text{γ}{}_{\mathrm{<mtext>c</mtext>}}$ values of two inherently floatable solids (or their $\text{γ}{}_{\mathrm{<mtext>clf</mtext>}}$ values), a difference in $\text{γ}{}_{\mathrm{<mtext>cmf</mtext>}}$ values determines the efficiency of their separation. It is also shown that the interfacial tension of maximum separation efficiency may be predicted from the individual surface tension of floatability curves which may be represented by second-order functions.     

Distribution of ammonium in minerals of metamorphic and granitic rocks

Sixty-nine analyses are given for NH₄ in minerals of metamorphic and granitic rocks mostly from the Ryoke belt, Japan. The distribution of NH₄ in coexisting minerals is quite systematic, suggesting that NH₄ is one of the stable geochemical components in high temperature processes.Biotite has the highest content of NH₄, followed by muscovite, K-feldspar and plagioclase. Pure quartz is almost free from NH₄. Calcic plagioclase contains less NH₄ than does sodic plagioclase. The partition coefficients $\text{D}{}^{\mathrm{<mtext>Pl</mtext><mtext>Bi</mtext>}}$, $\text{D}{}^{\mathrm{<mtext>Kf</mtext><mtext>Bi</mtext>}}$ and $\text{D}{}^{\mathrm{<mtext>Kf</mtext><mtext>Bi</mtext>}}$ are, on the average, 0.11, 0.38 and 0.43 respectively. The fractionation of NH₄ in these minerals is quite similar to that of Rb but much smaller than that of Cs.Distribution of NH₄ as well as those of Rb and Cs appears to be explained by its ionic radius and the shortest cation-O distances in alkali positions of minerals.