The role of carbon and oxygen in cosmic gases: some applications to the chemistry and mineralogy of enstatite chondrites

A new condensation sequence appears if the $\text{C}\text{O}$ ratio in a gas of otherwise solar composition is increased by less than a factor of two. As the ratio increases from the solar value of 0.6 to ? 1 the gas becomes extremely reduced, the condensation temperatures of silicates and oxides are depressed markedly ～ 400 K and a new suite of refractory minerals appears: AIN, CaS, MgS, SiC, TiN, graphite, Si₂N₂O and probably metastable (Fe,Ni)³C. Many of these minerals are unique to enstatite chondrites and may be analogues of the refractory silicates and oxides found in more oxidized meteorites such as Allende.The change in chemistry is related to the stability of CO, the most stable C or O compound at high T. Since the elements occur in a 1:1 ratio in CO, only the element which is in excess is free to form other compounds. But as T decreases CO reacts with H₂ to form graphite, CH₄ or other hydrocarbons thereby freeing O to form H₂O. If equilibrium is maintained oxides and silicates form at about 1000 K ($\text{C}\text{O}\text{> 1}$, P_τ = 10^?4atm) as products of reactions among the carbides, nitrides, sulfides and the gas. The possibility that equilibrium was not maintained among the C-bearing species was also investigated. If either graphite or CH₄ does not form as predicted the stability fields of the reduced minerals expands to lower temperatures. If neither graphite nor CH₄ form as predicted, CO remains stable and the nebular gas is highly reduced at all temperatures.Enstatite chondrites appear to have originated in a region of the nebula where the $\text{C}\text{O}$ ratio was somewhat higher than the solar value. Various fractionation mechanisms are considered. An interesting possibility is that graphite, which is quite refractory under a wide range of conditions, survived the collapse of the solar nebula.     

Hydrogen,oxygen and carbon isotopic evidence for the origin of rodingites in serpentinized ultramafic rocks

$\text{D}\text{H}$, ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ analyses were made of 14 whole rock and 28 mineral samples of rodingites associated dominantly with lizardite-chrysotile serpentinites from the West Coast of the U.S.A., New Zealand, and the Northern Appalachian Mtns. The δD values of the rodingite minerals are in three groupings: 5 monomineralic veins of pectolite, ?281 to ?429; 8 monomineralic veins of xonotlite, ?112 to ?135; all other minerals, including hydrogarnet, idocrase, prehnite, actinolite, nephrite, and chlorite, ?34 to ?80. Most calcites in rodingites have δ¹⁸O (+9.3 to +14.4) and (δ¹³C (?6.7 to +0.9) values similar to calcites in other Franciscan rocks, but distinct from the very low temperature calcite veins in serpentinites. The $\text{D}\text{H}$ data, combined with δ¹⁸O values of xonotlite (+5.7 to +10.9) and pectolite (+8.9 to +12.4) suggest formation from meteoric-type waters at low temperatures; the $\text{D}\text{H}$ depletion of pectolite, however, is anomalous. Rodingite whole rock values range from δ¹⁸O = +4.1 to +11.5 and δD = ?50 to ?86; one sample containing minor amounts of lizardite-chrysotile serpentinite has δD = ?92, outside this range. However, most rodingites of basaltic or gabbroic parentage are more restricted in δ¹⁸O (+4.1 to +8.6). Such a wide range in δ¹⁸O is consistent with the idea that most rodingites form over a relatively broad range of hydrothermal temperatures. Hydrogen isotopic data for most rodingite minerals (except xonotlite and pectolite) and for whole rocks are suggestive of non-meteoric waters. These $\text{D}\text{H}$ data overlap those observed for veins of hydrous minerals found in Franciscan igneous rocks studied by Margaritz and Taylor (1976, Geochim. Cosmochim. Acta40, 215–234), possibly suggesting evolved D-enriched, connate type metamorphic waters generated during high P, low T Franciscan-type metamorphism at temperatures (250–500°C) comparable to estimates based on mineral stabilities. Such an interpretation is supported by the ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ data for calcite in rodingites.The isotope data appear to contradict some of the conclusions derived from geologic and petrologic studies that indicate concomitant metasomatism and serpentinization of their presently observed host rock. These data appear most consistent with the interpretation that most rodingite minerals, with the exception of late-stage veins of xonotlite and possibly pectolite, may involve metasomatism in association with antigorite serpentinization of ultramafic rock. Subsequent upward tectonic transport in many instances may result in incorporation of the rodingites into their presently observed lizarditechrysotile host rock during or subsequent to pervasive shallow level serpentinization by meteoric waters.     

Experimental investigation of the partitioning of phosphorus between metal and silicate phases: implications for the Earth,Moon and Eucrite Parent Body

The solid metal/silicate melt partition coefficient for P, D(P), has been determined experimentally at 1190°C and 1300°C. The dependence of the partition coefficient on oxygen fugacity has been investigated, and is consistent with a valence state of 5 for P in the silicate melt. The experimental partition coefficients are given by: $\text{log D(P) = ?1.21 log ?O}{}_2\text{? 15.95 at 1190°C}$$\text{log D(P) = ?1.53 log ?O}{}_2\text{? 17.73 at 1300°C}$The experimentally determined partition coefficients may be used to interpret the low $\text{P}\text{La}$ ratios of the Earth, Moon and eucrites relative to C1 chondrites. The low $\text{P}\text{La}$ ratios in the eucrites may be explained by partitioning of P into 5% to 25% of a sulfur-bearing metallic liquid assuming equilibration and separation of the liquid metal from the silicates at low degrees of partial melting of the silicates. The low $\text{W}\text{La}$ ratios in the eucrites compared to C1 chondrites require the separation of an additional 2% to 10% solid metal.The lowering of both $\text{P}\text{La}$ and $\text{W}\text{La}$ ratios in the Moon may be explained by partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. The $\text{W}\text{La}$ ratios in the Earth and Moon are virtually indistinguishable, while $\text{P}\text{La}$ ratios differ by a factor of two. The concentrations of FeO also appear to be different. These observations are difficult to reconcile with the hypothesis of a terrestrial origin of the Moon following formation of the Earth's core, but are consistent with independent formation of the Earth and Moon.     

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.     

An ion microprobe study of the partitioning of trace elements between clinopyroxene and liquid in the system diopside-albite-anorthite

The partitioning of trace elements (Sc, Ti, Sr and Sm) between diopsidic clinopyroxene and liquid was studied experimentally in the system diopside-albite-anorthite at 1250°C, 1300°C and 1345°C at 1 atm. Twelve different bulk compositions were selected to study the effects of temperature and chemical composition. A Cameca ion microprobe was used to determine trace element concentrations in both clinopyroxene and liquid. Experiments of different run duration $\text{1}\text{4}\text{8}\text{?}$ days) showed that equilibrium was approached in less than 4 days at 1275°C. Equilibrium was also evaluated by a reversal run. A series of runs of constant bulk composition but with variable trace element contents showed that Henry's Law was obeyed over concentration ranges of the trace elements similar to those encountered in natural systems. The partition coefficients show significant ranges: Sc, 0.345~2.61; Ti, 0.084~0.214; Sr, 0.075~0.136; Sm, 0.054~0.328; the values are comparable with those obtained experimentally by other investigators. The partition coefficients vary as a function of both temperature and chemical composition. The experimental results are discussed in terms of exchange equilibria using the Bottinga-Weill silicate melt model. It is demonstrated that analytical uncertainties of both major and trace elements play an important role in understanding trace element exchange equilibria; propagation of analytical errors in the thermodynamic treatment is equally important.     

Isotopic anomalies of noble gases in meteorites and their origins—III. LL-chondrites

Nine LL-chondrites were studied by a selective etching technique, to characterize the noblegas components in three mineral fractions: HF-HCl-solubles (silicates, metal, troilite, etc.; comprising ～ 99% of the meteorite), chromite and carbon (～ 0.3–0.7%) and Q (a poorly characterized mineral defined by its solubility in HNO₃, comprising ～ 0.05% of the meteorite but containing most of the Ar, Kr, Xe and a neon component of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 10.9 ± 0.8}$). The ${}^{20}\text{Ne}{}^{36}\text{Ar}$ ratio in Q falls wi petrologic type and rising ³⁶Ar content, as expected for condensation from a cooling solar nebula, but contrary to the trend expected for metamorphic losses. Chondrites of different petrologic types therefore cannot all be derived from the same volatile-rich ancestor, but must have formed over a range of temperatures, with correspondingly different intrinsic volatile contents.The CCFXe (carbonaceous chondrite fission) component varies systematically with petrologic type. The most primitive LL3s (Krymka, Bishunpur, Chainpur) contain substantial amounts of CCFXe in chromite-carbon, enriched relative to primordial Xe as shown by high ${}^{136}\text{Xe}{}^{132}\text{Xe}$ (0.359–0.459, vs 0.310 for primordial Xe). These are accompanied by He and by Ne with ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{≈ 8.0}$ and by variable amounts of a xenon component enriched in the light isotopes. The chromite in these meteorites is compositionally peculiar, containing substantial amounts of Fe(III). These meteorites, as well as Parnallee (LL3) and Hamlet (LL4) also contain CCFXe in phase Q, heavily diluted by primordial $\text{Xe}\text{(}{}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.317–0.329)}$. On the other hand, LL5s and 6s (Olivenza, St. Séverin, Manbhoom and Dhurmsala) contain no CCFXe in either mineral. This deficiency must be intrinsic rather than caused by metamorphic loss, because Q in these meteorites still contains substantial amounts of primordial Ne.If CCFXe comes from a supernova, then its distribution in LL-chondrites requires three presolar carrier minerals of the right solubility properties, containing three different xenon components in certain combinations. These minerals must be appropriately distributed over the petrologic types, together with locally produced Q containing primordial gases, and they must be isotopically normal, in contrast to the gases they contain. On the other hand, if CCFXe comes from fission of a volatile superheavy element, then its decrease from LL3 to LL6 can be attributed to progressively less complete condensation from the solar nebula. Ad hoc assumptions must of the host phase Q, its association with ferrichromite and the origin of the associated xenon component enriched in the light isotopes.Soluble minerals in LL3s and LL4s contain a previously unobserved, solar xenon component, which, however, is not derived from the solar wind. Three types of ‘primordial’ xenon thus occur side-by-side in different minerals of the same meteorite: strongly fractionated Xe in ferrichromite and carbon, lightly fractionated Xe in phase Q, and ‘solar’ Xe in solubles. Because the first two can apparently be derived from the third by mass fractionation, it seems likely that all were trapped from the same solar nebula reservoir, but with different degrees of mass fractionation.     

Al-Sm-Eu-Sr systematics of eucrites and Moon rocks: Implications for planetary bulk compositions

Analysis of the Eu and Sr “anomalies” of eucrites and lunar rocks allows constraints to be placed on the bulk compositions of the eucrite parent body (EPB) and the Moon. The elements Al, REE, and Sr, all are essentially incompatible with the major minerals of these small, low-?(O₂) bodies, except for plagioclase, into which Al, Sr, and Eu tend to concentrate. Therefore, the hypothesis that Al, REE, and Sr in the EPB and the Moon are all in proportions close to those in the bulk solar system (i.e., chondrites) leads to certain predictions about the concentrations of these elements in samples affected by plagioclase fractionation. The predictions are almost ideally fulfilled by eucrites and lunar samples. For the EPB, the ratios $\text{REE}\text{Al}$, $\text{Sr}\text{Al}$, and $\text{Sr}\text{REE}$ are constrained to be probably within 10%, almost certainly within 20%, of the chondritic ratios. For the more complicated Moon, the constraints are less precise: $\text{REE}\text{Al}$ is very probably within 25% of chondritic; $\text{Sr}\text{Al}$ and $\text{Sr}\text{REE}$ are probably within 35% of chondritic. These findings are proof that there is a strong similarity between the bulk compositions of the planets and the compositions of chondritic meteorites.The eucrites' Sm-Eu-Sr systematics are also valuable sources of constraints on the distribution coefficients for Eu and Sr into plagioclase, at low ?(O₂). From the slope of data for noncumulate eucrites on a Eu-Sm plot, D(Eu,pl/liq) can be inferred to be 1.1_?0.1^0.2. From the slope on a Sr-Sm plot, D(Sr,pl/liq)) can be inferred to be 1.5 ± 0.3. In the case of D(Eu), this is in excellent agreement with experimental data. In the case of D(Sr), the empirical result is probably more appropriate for eucritic systems than most experimental data, which, due to compositional effects, scatter widely.     

The rare alkalies in hydrothermal alteration at Wairakei and Broadlands,geothermal fields,N.Z.

Drillcores and waters from Wairakei and Broadlands geothermal areas New Zealand have been analyzed for Li, Rb, Cs, Na, K, Mg, Ca, Al, Ti, Mn, and Be. The drillcores were altered to various degrees at temperatures below 300°C in slightly alkaline chloride water, probably derived from rock-water interaction in untapped horizons at higher temperature. It changes its composition as it leaches Ca and Na from the rock and adds K, Rb, Cs and Li. Evaluation of these changes in relation to the dimensions of the altered zone under observation suggests that a high mass ratio of water to rock (e.g., 100) and a period of up to 1 million years are responsible for the present stage of alteration.Increase of K and Rb in the altered rocks is a result of the formation of abundant adularia in addition to illite. The $\text{K}\text{Rb}$ ratio of the rock decreases during alteration but remains higher than that of the fluid. Only clay materials and zeolites that preferentially absorb Rb give slightly lower $\text{K}\text{Rb}$ ratios than the fluid.The mineral phases responsible for the uptake of lithium during alteration are chlorite (300 ppm Li) and quartz (up to 430 ppm Li). Li uptake in quartz is considered to be the mechanism by which Al-rich quartz crystallises from alumino-silicates. $\text{Li}\text{Al}$ atomic ratios of 0.3–0.57 and Al concentrations up to 3000 ppm have been observed.Relatively small concentrations of Cs are found in potassic minerals (e.g. 10 ppm Cs in adularia, 44 ppm Cs in illite). However, 240 ppm Cs are found in wairakite from Wairakei equilibrated at 235°C. Lower equilibration temperatures may lead to higher cesium concentrations. This effect, in conjunction with a more concentrated hydrothermal fluid, could explain a content of 4500 ppm Cs in wairakite extracted from a drillcore taken in the El-Tatio geothermal field in Chile.     

The geochemistry of the stable isotopes of silicon

One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of ^δ30Si found is 6.2%., centered on the mean of terrestrial mafic and ultramafic igneous rocks, δ³⁰Si = ?0.4%.. Igneous rocks show limited (1.1%.) variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly $\text{1}\text{3}$ the magnitude of concomitant oxygen isotopic fractionations at 1150°C. In both igneous minerals and rocks, δ³⁰Si shows a positive correlation with silicon content, as does δ¹⁸O. Opal from both sponge spicules and sinters is light, with $\text{}\text{?}\text{gd}{}^{30}\text{Si}\text{= ?2.3}$ and ?1.4%., respectively. Large ^δ30Si values of both positive and negative sign are reported for the first time from clay minerals (?2.3 to +1.8%.), opaline phytoliths (?1.4 to +2.8%.), and authigenic quartz (+ 1.4%.). All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of ≈3.5%. is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in ²⁸Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic δ³⁰Si variations. Chert ^δ30Si values are largely inherited, but the primary opal ^δ30Si values can be modified by isotopic equilibration of silicate silicon and dissolved silicon during the transformation of opal into quartz.     

Rare-earth elements in the rock-forming minerals of melilitic rocks in alkaline-ultrabasic complexes

The rare-earth distributions in melilites and other coexisting minerals of melilite-containing rocks from five alkaline-ultrabasic complexes were analysed by partition paper chromatography and neutron activation. Relatively late differentiates are characterized by elevated relative alkalinity and reduced absolute basicity. The characteristics of melilitic sövites markedly differ from established trends. The minerals studied are richer in LREE than chondrites and REE concentrations in these minerals increase in the late differentiates of the melilitic series. A proportionality between logarithms of La and Sm concentrations in pyroxene and melilite imply that melilite-containing rocks (except melilitic sövite) belong to a similar comagmatic series. The degree of LREE-enrichment in rock-forming minerals directly depends on the alkalinity of the rock. The distribution of REE between coexisting melilite and pyroxene may be used as an additional genetic criterion: p.e. magmatic $\text{La}{}_{\mathrm{Pyx}}\text{La}{}_{\mathrm{Mel}}$ ratio is 0.91, while in metasomatic rocks this ratio is between 1.80 and 1.97.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

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.     

Chronology and petrogenesis of a 1.8 g lunar granitic clast:14321,1062

A study was undertaken to determine the chronology of a pristine granite clast (1062) from Apollo 14 breccia 14321 using Rb-Sr, Sm-Nd and ³⁹Ar-⁴⁰Ar methods. The genesis of the granite as constrained by the isotopic results and trace element characteristics is discussed.Chronology: The Rb-Sr internal isochron is slightly disturbed and yields an age of 4.09 ± 0.11 AE ($\text{λ(}{}^{87}\text{Rb) = 0.0139}\text{AE}{}^{\mathrm{?1}}$) and an imprecise initial I(Sr) = 0.702 ? .008. If two data are excluded, the age becomes 4.13 ± 0.03 AE and I(Sr) = 0.698 ? .003. The whole rock and mineral separates are extremely radiogenic; they yield model ages which are relatively well-defined. The average model age is 4.12 ± 0.03 AE (relative to BABI = 0.69898). The Sm-Nd internal isochron is also slightly disturbed and gives an age of 4.11 ± 0.20 AE ($\text{λ(}{}^{147}\text{Sm) = 0.00654}\text{AE}$^?1). The ³⁹Ar-⁴⁰Ar average age of the non-magnetic fraction of the sample yields a slightly younger age of 3.88 ± 0.03 AE (K-Ar constants from Steiger and $\text{>a}\text{?}$, 1977). The concordancy of Rb-Sr and Sm-Nd internal isochrons with the Rb-Sr model age strongly suggests that the granitic clast formed at 4.1 AE ago in the shallow crust and was later excavated and brecciated about 3.88 AE ago.Petrogenesis: Isotopic and trace element data of the lunar granite show large K/La and Rb/Sr fractionations, small Sm/Nd fractionation and the distinct V-shaped REE distribution pattern at the time of crystallization. A two-stage model involving crystal fractionation followed by silicate liquid immiscibility (SLI) is proposed for lunar granite genesis. We propose that the granite can be the immiscible acidic liquid produced by SLI from a residual liquid which underwent fractionation of ca, 3% of phases with REE distribution coefficients similar to those of phosphate minerals from a highly evolved parental magma with REE contents about twice those of the 15405,85 quartz monzodiorite (QMD).The extreme scarcity of lunar granitic samples and their young formation ages suggest that they are probably not directly crystallized from the differentiation of the primordial magma ocean. Our isotopic results and trace elements data from other workers suggest that granites, QMD and probably Mggabbronorites may be genetically related and may have formed in a plutonic environment similar to gabbro-granophyre associations in terrestrial layered intrusions such as the Skaergaard Intrusions.     

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al₂(SO₄)₃ · 17H₂O, alunite, KAl₃(SO₄)₂(OH)₆, jurbanite, Al(SO₄)(OH) · 5H₂O, and basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O. An examination of literature values shows that the log $\text{K}{}_{\mathrm{sp}}\text{= ?85.4}$ for alunite and log $\text{K}{}_{\mathrm{sp}}\text{= ?117.7}$ for basaluminite. In this report the log $\text{K}{}_{\mathrm{sp}}\text{= ?7.0}$ is estimated for alunogen and log $\text{K}{}_{\mathrm{sp}}\text{= ?17.8}$ is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from $\text{pH < 0}$ up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals.Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.     

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°.     

Effet de la température sur les distributions de Na,Rb et Cs entre la sanidine,la muscovite,la phlogopite et une solution hydrothermale sous une pression de 1 kbar

The distribution of trace amounts of Na, Rb and Cs, between muscovite, phlogopite, sanidine and hydrothermal solution have been studied by ion exchange in a temperature range from 400 to 800°C.These distributions have been expressed with a partition ratio P^aq?m_x = $\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{aq}}\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{m}}$ (where X is Na, Rb or Cs).In the case of Na and Cs in muscovite, even for the dilute solutions, the ratio P^aq?m_x is not the equilibrium constant k_x of exchange reactions. In other cases, P^aq?m_x does not depend on the trace alkali ion concentration in silicates (X) and is equal to k_x. Variations of P_x or k_x with T are greater for Na and Cs than for Rb. Generally, k_x decreases with increase in T. The function log $\text{P}{}_{\mathrm{x}}\text{= f(}\text{1}\text{T}\text{)}$ is not linear for Na or Cs, but in the case of Rb, $\text{f(}\text{1}\text{T}\text{)}$ is linear and the standard enthalpy and entropy of exchange reactions have been estimated by applying the Arrhenius relation.The distribution relations obtained between silicate and vapour phase permit the determination of distributions of Na, Rb and Cs between two minerals mI and mII, relative to K. These have been expressed with the partition ratio Q_x =$\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{mI}}\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{mII}}$. Variations of Q_x with T are not remarkable, and even for Rb between phlogopite and feldspar are negligible. Nevertheless, one may use the distributions of Rb and Cs between muscovite and feldspar for geothermometry. Experimental results have been applied to some rocks by effecting corrections from the major element composition of the natural minerals. Estimated temperatures are near to 400°C in the granites and pegmatite studied here.     

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

The partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid has been investigated experimentally to evaluate the geochemical coherence of Pu and the light REEs. ${}^{\mathrm{Pu}}\text{D}{}^{\mathrm{Sm}}\text{D}$ is 2̃ for both diopsidic pyroxene and whitlockite. This small amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Our experimental results thus validate the suggestion that Pu behaves as a LREE during igneous processes in reducing environments.Our data and the data of Ray et al. (1983) indicate that temperature rather than melt composition is the most important control on elemental partitioning. This is true even though we demonstrate that additions of only 1–2 wt.% of P₂O₅ to the diopside-anorthite-albite system change ^PuD_cpx by a factor of two. Our data suggest that P₂O₅ in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.     

Strontium isotopic composition of some brines from the Precambrian Shield of Canada

Twenty-four groundwater samples from seven operating mines at Sudbury, Yellow-knife and Thompson (Ontario, North West Territories and Manitoba, resp.), all from depths greater than 1 km and ranging in total dissolved solids (TDS) from 1900 to 250,000 mg l^?1, were measured for their ${}^{87}\text{Sr}{}^{86}\text{Ar}$ values. Each geographic location gives a limited range in values and each location is distinct from the others. This is interpreted as the result of extensive water-rock interaction on a local scale. For most of the time, these brines were isolated and only recently have been exposed to surface water as a result of the mining operations. The extent of the isolation is shown by the contrasting isotopic values of two “pockets” of water (0.711 vs. 0.716) located on opposite sides of the same fault system on the North Range at Sudbury. The exchange at all sites probably has continued until the present, as indicated by the close agreement between water and present-day${}^{87}\text{Sr}{}^{86}\text{Sr}$ whole-rock values. If so, it suggests that there is no single age for such brines, but it may be possible to date stages in the water's evolution by determining the age of secondary minerals that equilibrated with the water.