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Iridium has been determined in a drill core from the Great Lake (Tasmania) dolerite sheet. Iridium decreases systematically from the mafic dolerites (0.25 ppb) to the granophyres (0.006 ppb). The trend with differentiation closely parallels that of chromium.
New analyses of high-alumina basalts reveal an average nickel content higher than previously indicated. Ni in high-alumina basalts correlates with magnesium in the same way as it does in other basalt types. There is therefore no reason, based on Ni contents, to hypothesize a special origin for high-alumina basalts and it is permissible (based on Ni contents) to form andesites by fractional crystallization from high-alumina basalts.
All carbonates associated with the ultramafic rocks and serpentinites of the western United States are shown by their stable isotope ratios to be of near-surface, low-temperature origin. These include vein materials that have been previously classified as hydrothermal. New laboratory and natural data were obtained on the equilibrium isotope relations between hydromagnesite and water. The origins of travertines in the ultramafic area are easily distinguished on the basis of their stable isotope ratios. The extremely heavy isotope ratios of nesquehonites suggest an intricate evaporating-film mechanism of formation.
Two calcium-magnesium carbonate solid solutions form Holocene travertines and conglomerate cements in fresh water stream channels of the Coast Range of California. Calcite does not yield the {015} diffraction maximum. The {006} diffraction maximum is lacking over most of the range of composition of calcite. Calcite has compositions from CaCO 3 to Ca 0.5 Mg 0.5 CO 3 . Dolomite yields both the {006} and {015} diffraction maxima over its entire composition range, Ca 0.6 Mg 0.4 CO 3 to Ca 0.5 Mg 0.5 CO 3 . The Ca-Mg carbonates form in isotopic equilibrium and thermodynamic disequilibrium from dispersion of Ca 2+ -rich water into CO 3 2− -rich water within the alluvium. The stable isotope data suggest that all the Mg-rich carbonates are primary precipitates and not a result of Mg-substitution in precursor CaCO 3 . There is a correlation between δC 13 and Mg content of the carbonates which predicts a 5%. fractionation of C 13 between dolomite and calcite at sedimentary temperatures. C 14 is incorporated in Ca-Mg carbonates forming from C 13 -poor meteoric waters and C 13 -rich waters from Cretaceous sediments. C 14 ages of the Ca-Mg carbonates are apparent, and cannot be corrected to absolute values. Solution rates of calcite decrease with increasing MgCO 3 content; dolomite dissolves slower than any calcite.
A large tektite from Cuba is classified with other North American tektites on the basis of its age. The major-element chemistry, oxygen isotopic composition, refractive index and density of the Cuban tektite are within the ranges exhibited by bediasites.
Quartz crystals from calcite veins of unknown age in Precambrian metasedimentary rocks at Geiaus No. 6 and Aukam farms in South-West Africa contain both primary and secondary inclusions filled with one or a variable combination of: organic liquid, moderately saline aqueous liquid, dark-colored solid, and vapor. Analysis of these materials by microscopy and by gas chromatography and mass spectrometry shows the presence of constituents of both low and high molecular weights. The former include CH 4 , C 2 H 6 , C 3 H 8 and possibly C 4 H 10 as well as CO, CO 2 , H 2 O, N 2 and H 2 . High molecular weight components are dominantly n-alkanes and isoprenoid hydrocarbons. The n-alkanes range from at least n-C 10 to n-C 33 . Concentrations of n-alkanes larger than n-C 17 decrease regularly with increasing carbon number. An homologous series of isoprenoid hydrocarbons ranging from at least C 14 to C 20 is present in unusually high concentrations. Pristane (C 19 ) is most abundant, and C 17 isoprenoid is least abundant. The molecular composition and distribution of hydrocarbons suggest biological precursors for these components. Consideration of data provided by freezing, crushing and heating experiments suggests that the pressures at the time these in part supercritical fluids were trapped probably exceeded 30–40 atm, and the minimum trapping temperature was about 120–160°C. Both primary and secondary inclusions apparently containing only organic materials were trapped by the growth of the host quartz from aqueous solution. The data obtained neither prove nor preclude Precambrian, Paleozoic or younger sources for the organic materials.
Borax, gaylussite, nahcolite and trona were synthesized in aqueous solution at temperatures ranging from 8° to 35°C. Except for borax, deuterium was always depleted in these hydrated minerals relative to the solutions from which they were crystallized. In borax, no significant fractionation was found. The fractionation factor of D H "> DH for the trona-water system exhibited a marked temperature dependence. By combining the deuterium contents of trona and the solution from which trona was crystallized, the following thermometer scale was obtained: In ( D H ) trona ( D H )water = 1.420 × 10 4 T 2 + 23.56 T "> (DH) trona(DH)water =1.420 × 104T2+23.56T (1) An attempt to establish a geothermometer based on C 13 C 12 "> C13C12 fractionation between carbonate minerals and carbonate ions in aqueous solution was not successful.
Fourteen Ivory Coast tektites exhibit a range of bulk indices of refraction of 1.5156 to 1.5217 ± 0.0004 and of bulk specific gravities of 2.428 to 2.502 ±0.005. Seven of these Ivory Coast (IVC) tektites were analyzed for major and minor element content. Compared to tektites from other strewn fields, their SiO 2 content is low (67.2–69.1 %), A1 2 O 3 relatively high (15.8–16.8 %), and total iron relatively high but with a more restricted range (6.3–6.8 % as FeO). Their lime content is low (0.71–1.35%) compared to Australasian tektites but their MgO CaO "> MgOCaO ratio (about 3.1) is unusually high. All other tektite groups have Na 2 O K 2 O "> Na2OK2O ratios less than unity, but the Na 2 O K 2 O "> Na2OK2O ratio of the IVC tektites is slightly greater than unity. Their K Rb "> KRb ratios range from 200 to 256 and average 227, which is higher than those determined for Australasian tektites, but similar to some obtained for moldavites. The Li content (41–48 ppm) is about the same as that of the Australasian tektites, but the Cs and Rb are lower, being 1.9 to 2.9 and 57 to 86 ppm, respectively. The IVC tektites are high in Cr (260–375 ppm), Co (19–25 ppm) and Ni (101–167 ppm), and particularly in Pb (<10–18 ppm ), Cu (13–21 ppm) and Ga (14–23 ppm). The high Cr Ni "> CrNi ratios of the IVC tektites (range 2–3.6) are similar to those found for australites, philippinites and thailandites, but not the javanites and indochinites. Evaluation of these and other reported data show that compositional similarities between the IVC tektites and green or black Bosumtwi Crater glasses strongly support the hypothesis of a common impact origin—i.e. the Bosumtwi Crater site. Comparison of the IVC tektite composition with those of returned lunar materials (gabbros, basalts, breccia and soils) do not support a lunar origin for the Ivory Coast tektites.
An empirical method of estimating the last temperature of water-rock interaction has been devised. It is based upon molar Na, K and Ca concentrations in natural waters from temperature environments ranging from 4 to 340°C. The data for most geothermal waters cluster near a straight line when plotted as the function log ( Na K ) + β log [ √ (Ca) Na ] "> log (NaK) + β log [ √(Ca)Na] vs reciprocal of absolute temperature, where β is either 1 3 "> 13 or 4 3 "> 43 depending upon whether the water equilibrated above or below 100°C. For most waters tested, the method gives better results than the Na K "> NaK methods suggested by other workers. The ratio Na K "> NaK should not be used to estimate temperature if √ ( M Ca ) M Na "> √ (MCa)MNa is greater than 1. The Na K "> NaK values of such waters generally yield calculated temperatures much higher than the actual temperature at which water interacted with the rock. A comparison of the composition of boiling hot-spring water with that obtained from a nearby well (170°C) in Yellowstone Park shows that continued water-rock reactions may occur during ascent of water even though that ascent is so rapid that little or no heat is lost to the country rock, i.e. the water cools adiabatically. As a result of such continued reaction, waters which dissolve additional Ca as they ascend from the aquifer to the surface will yield estimated aquifer temperatures that are too low. On the other hand, waters initially having enough Ca to deposit calcium carbonate during ascent may yield estimated aquifer temperatures that are too high if aqueous Na and K are prevented from further reaction with country rock owing to armoring by calcite or silica minerals. The Na-K-Ca geothermometer is of particular interest to those prospecting for geothermal energy. The method also may be of use in interpreting compositions of fluid inclusions.
Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O 18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins.
Several recent laboratory studies and field investigations have indicated that shales and compacted clay minerals behave as semipermeable membranes. One of the properties of semipermeable membranes is to retard or prevent the passage of charged ionic species through the membrane pores while allowing relatively free movement of uncharged species. This phenomenon is termed salt filtering, reverse osmosis, or ultrafiltration. This paper shows how one can proceed from the ion exchange capacity of clay minerals and, by means of Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane. Reasonable agreement between theory and laboratory results were found. The concentration of the ultrafiltrate was always greater than predicted because of uncertainty in values of some parameters in the equations. Ultrafiltration phenomena may be responsible for the formation of some subsurface brines and mineral deposits. The effect should also be taken into consideration in any proposal for subsurface waste emplacement in an environment containing large quantities of clay minerals.
Bismuth has been determined in 74 rocks from a differentiated tholeiitic dolerite, two calc-alkaline batholith suites and in 66 mineral separates from one of the batholiths. Average bismuth contents, weighted for rock type, of the Great Lake (Tasmania) dolerite, the Southern California batholith and the Idaho batholith are, 32, 50 and 70 ppb respectively. All three bodies demonstrate an enrichment of bismuth in residual magmas with magmatic differentiation. Bismuth is greatly enriched (relative to the host rock) in the calcium-rich accessory minerals, apatite and sphene, but other mineral analyses show that a Bi-Ca association is of little significance to the magmatic geochemistry of bismuth. Most of the bismuth, in the Southern California batholith at least, occurs in a trace mineral phase (possibly sulfides) present as inclusions in the rock-forming minerals.
Microscopic and electron microprobe studies were made of polished thin sections of part of a 30-mg sample of 250–500 μm lunar soil returned by Luna 20 from a point between Mare Fecunditatis and Mare Crisium. Very fine-grained lithic (crystalline) rock fragments, composing about one fifth of the total sample, have mineralogical compositions equivalent to various types of gabbro, anorthositic gabbro, gabbroic anorthosite and troctolite, with minor basalt. The textures now observed in these fragments are in large part metamorphic. Twentyseven electron microprobe analyses of minerals from these fragments are presented, including olivine, plagioclase, pyroxene, spinel, nickel-iron and a Zr-Ti-REE mineral possibly similar to ‘phase B’ of Lovering and Wark (1971). Analyses of seven melt inclusions and twenty-eight defocused beam analyses of lithic fragments are also given. Some of the fragments contain ‘gas’ inclusions which, along with the fine grain size, are believed to indicate final crystallization under low pressure near surface conditions. The almost complete absence of granophyric material in this sample raises the question of whether or not there are at least two distinct magmas for the plagioclase-rich terrae rocks from which this soil sample was derived in part.
Magnetic susceptibility measurements have been made on four glass spherules and fragments from the Luna 20 fines; two at 300°K and two from 300°K to 4°K. From these data the magnetic susceptibility extrapolated to infinite field, the magnetization at low fields and also the saturation magnetization at high fields, the Curie constant, the Weiss temperature, and the temperature-independent susceptibility were determined. Using a model previously proposed for the Apollo specimens, the Curie constant of the antiferromagnetic inclusions and a zero field splitting parameter were calculated for the same specimens. The data show the relatively low concentration of iron in all forms in these specimens. In addition, the Weiss temperature is lower than that measured for the Apollo specimens, and can be attributed almost entirely to the ligand field distortion about the Fe 2+ ions in the glassy phase. The data further suggest that the Luna 20 specimens cooled more slowly than those of the Apollo missions, and that some of the antiferromagnetic inclusions in the glass may have crystallized from the glass during cooling.
Water and gas samples from research wells in hydrothermal areas of Yellowstone National Park, U.S.A., have been mass spectrometrically analyzed for their rare gas contents and isotopic composition. In agreement with previous findings, the rare gases have been found to originate from infiltrating run-off water, saturated with air at 10 to 20°C. The atmospheric rare gas retention values found for the water varied between 3 and 87 per cent. The fine structure of the Ar, Kr and Xe abundance pattern in the water reveals fraotionational enrichment of the heavier gases due to partial outgassing of the waters. Radiogenic He and Ar have been detected. No positive evidence for magmatic water contribution has been found. Nevertheless, additions of magmatic waters free of rare gas can not be excluded, but if present the proportion is significantly less than 13 to 36 per cent.
The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO 2 . All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO x at pH 7) while the γ-MnO 2 showed the least (0.3 moles silver/ mole MnO x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.
The relative retardation by geological membranes of cations and anions generally present in subsurface waters was investigated using a high pressure and high temperature ‘filtration cell’. The solutions were forced through different clays and a disaggregated shale subjected to compaction pressures up to 9500 psi and to temperatures from 20 to 70°C. The overall efficiences measured increased with increase of exchange capacity of the material used and with decrease in concentration of the input solution. The efficiency of a given membrane increased with increasing compaction pressure but decreased slightly at higher temperatures for solutions of the same ionic concentration. The results further show that geological membranes are specific for different dissolved species. The retardation sequences varied depending on the material used and on experimental conditions. The sequences for monovalent and divalent cations at laboratory temperatures were generally as follows: Li < Na < NH 3 < K < Rb < Cs Mg < Ca < Sr < Ba. The sequences for anions at room temperature were variable, but at 70°C, the sequence was: HCO 3 < I < B < SO 4 < Cl < Br. Monovalent cations contrary to some field data were generally retarded with respect to divalent cations. The differences in the filtration ratios among the divalent cations were smaller than those between the monovalent cations. The passage rate of B, HCO 3 , I and NH 3 was greatly increased at 70°C.
Regolith samples from the Apollo 15 landing site are described in terms of two major fractions, a homogeneous glass fraction and a non-homogeneous glass fraction. The proportions of different components in the homogeneous glass fraction were determined directly by chemical analyses of individual particles. They are mainly green glass, a mare-like glass, and different types of Fra Mauro and Highland type glasses. The proportions of various components in the remainder of each of the soils were determined indirectly by finding the mix of components that best fits their bulk compositions. The mixing model suggests that the Apennine Front consists mainly of rocks of low-K Fra Mauro basalt composition. These may overlie rocks with the composition of anorthositic gabbro. Green glass, which occurs widely throughout the site is believed to be derived from a green glass layer which darkens upland surfaces and lies beneath the local mare surface.