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.     

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 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.     

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.     

Columbia River volcanism: the question of mantle heterogeneity or crustal contamination

Basalts from the Columbia River flood basalt province of the northwestern U.S.A. show a large diversity in chemical and Nd and Sr isotopic compositions. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ranges from 0.51303 to 0.51208 and is strongly correlated with variations in ${}^{87}\text{Sr}{}^{86}\text{Sr}$. This correlation suggests mixing between two end member compositions, one characterized by ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{> 0.51303}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{< 0.7035}$, and the other with ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{< 0.5120}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{> 0.715}$. The more radiogenic component could be mantle enriched in incompatible elements during the Precambrian, or Precambrian materials of the continental crust. A quartz-rich xenolith found in the Columbia lavas has Rb-Sr and Sm Nd model ages of ≈ 1.4Æ, implying the existence of old, isotopically evolved crustal basement which could serve as contaminant. Nevertheless, crustal contamination alone cannot explain the chemical variation of the samples studied, and other fractionation processes must have occurred simultaneously. A model involving combined assimilation and crystal fractionation reproduces the chemical and isotopic characteristics of the volumetrically dominant Grande Ronde unit for an assumed crystallizing component of plagioclase, low calcium pyroxene and minor olivine. The data are not consistent with the suggestion that a ‘primordial’ mantle is the source for this continental flood basalt province. Rather they suggest that the main volume of these lavas was originally derived from a mantle similar in isotopic composition to island arc and ocean island basalts of the north Pacific. The primary magma was modified chemically and isotopically by crystal fractionation and assimilation of sialic crustal materials during its transport through, or storage in the continental crust.     

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study

The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10^?8 and 10^?14 atm.The molar distribution coefficients are given by the equations: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 18434/T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu.     

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.     

Chronology and petrogenesis of young achondrites,Shergotty, Zagami,and ALHA77005: late magmatism on a geologically active planet

A study was undertaken to determine the chronology, petrogenesis and relationships among the shergottites, Shergotty and Zagami and the unique achondrite ALHA77005. These meteorites are the product of a variety of complex processes.Petrogenesis: Chondrite-normalized abundance patterns of Shergotty and Zagami are very similar and show pronounced depletions of both the light REE (La-Nd) and heavy REE (Dy-Lu) relative to Sm-Gd. These characteristic depletions are even more pronounced for ALHA77005. The light REE depletion is qualitatively consistent with the presence of cumulus pyroxene and/or olivine in these meteorites, but trace element models show that the parental magmas of all three meteorites were probably also light REE depleted. Both trace element model calculations and combined Rb-Sr and Sm-Nd isotopic systematics show that the meteorites could not have been co-magmatic nor can ALHA77005 be representative of the source material of the shergottites. Light REE depletion of the parental magmas also implies light REE depletion of the source material. The Sm-Nd systematics of the shergottites require a time-averaged sub-chondritic (light REE enriched) Sm-Nd ratio since 4.6 AE ago. The Sm-Nd systematics of ALHA77005 permit a time-averaged super-chondritic (light REE depleted) Sm/Nd ratio if its crystallization age is less than T_ICE = 0.72 AE.Chronology. Rb-Sr internal isochrons for all three meteorites and a Sm-Nd internal isochron for Zagami are concordant at ~ 180 Myr. ³⁹Ar-⁴⁰Ar plateau ages of Shergotty and Zagami maskelynite are ~250–260 Myr. These ages apparently reflect resetting of these isotopic systems by shock metamorphism which converted the feldspar to maskelynite. The concordance of these ages suggests a single shock event during which the meteorites were in close physical proximity. The time of this event is most precisely given by the Rb-Sr age of 180 ± 4 Myr for Zagami.The crystallization ages of the meteorites were not precisely determined. Extreme upper limits are determined by Sm-Nd model ages relative to an eucrite initial ${}^{143}\text{Nd}{}^{144}\text{Nd = 0.505835}$ at 4.6 AE ago. These model ages for Shergotty, Zagami and ALHA77005 are 3600, 3500 and 2850 Myr, respectively. The Sm-Nd whole rock age of 1340 ± 60 Myr for the three meteorites gives the crystallization age if the Sm/Nd ratios of the precursor materials were always the same. We consider this 1340 Myr age as a “best estimate” upper limit. “Best estimate” lower limits for Shergotty and Zagami are taken from the average ³⁹Ar-⁴⁰Ar ages of 1200 and 900 Myr of pyroxene separates. The average ³⁹Ar-⁴⁰Ar age of a whole rock sample of ALHA77005 was 1600 Myr and can be partitioned between a low temperature (feldspar) phase and a high temperature (olivine + pyroxene + inclusions) “phase”. The average apparent ³⁹Ar-⁴⁰Ar age of the low temperature phase is ~1050 Myr, which is chosen as the “best estimate” lower limit to the age. The crystallization ages of Shergotty, Zagami and ALHA77005 probably lie within the ranges of 1200–1300, 900–1300 and 1000–1300 Myr, respectively. The Rb-Sr whole rock age of 4400 ± 400 Myr and single-stage BABI model ages of ~4800–5100 Myr are interpreted as reflecting differentiation of the parent body at ~4600 Myr ago.The complex geochemical and isotopic evolution recorded by these meteorites suggests a geologically active parent body capable of sustaining melting at two or more epochs in its history.     

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.     

Nd and Sr isotopic crustal contamination patterns in an Archaean meta-basic dyke from northern Labrador

Samples from the core to the margin of a 20 cm wide meta-dolerite dyke are sequentially enriched in K, Rb, Sr, and the light REE's. Rb-Sr and Sm-Nd compositional and isotopic profiles in the dyke are interpreted to be the result of selective contamination with components of country rock derivation, rather than the result of simple bulk mixing. ${}^{87}\text{Rb}{}^{86}\text{Sr}$ ratios are higher at the edge of the dyke than at its centre, although they are somewhat irregular, due probably to the effects of subsequent alteration. This profile and one shown by unsupported ⁸⁷Sr are both consistent with contamination of the dyke by a fluid phase derived by the breakdown of biotite. Common Sr shows a parallel, albeit weaker, contamination profile which is interpreted to reflect the contribution of a Sr-bearing phase such as plagioclase. ${}^{147}\text{Sm}{}^{144}$Nd ratios and ¹⁴⁴Nd concentrations increase and decrease respectively from the margin to the core of the dyke. In addition, the margin of the dyke is significantly less radiogenic than the interior. This contrasts with the relatively radiogenic character of an adjacent pegmatite vein. As this sample does not lie on an anticipated contamination profile between the Uivak gneisses and the dyke it is concluded that the REE contamination of the dyke occurred by the addition of a REE-enriched fluid phase which gained access to the dyke by flow along the dyke-pegmatite interface. If it is assumed that both the Rb-Sr and Sm-Nd contamination profiles are the result of diffusion limited processes, then the observations of scale made in this paper suggest that the rate of diffusion of Nd is an order-of-magnitude slower than that for Sr. In view of the scale and nature of these profiles, ages obtained from isotopic data for such mafic dykes must be interpreted with some care. Nevertheless, in spite of these limitations the ?_Nd values for the least contaminated specimens provide a clear indication that the Saglek dykes were derived from a depleted mantle source with ?_Nd? +2.     

Density calculations for silicate liquids. I. Revised method for aluminosilicate compositions

Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature T_r, is given by $\text{V}{}_{\mathrm{r}}\text{= ∑X}{}_{\mathrm{i}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{+ X}{}_{\mathrm{A}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$, where the summation is taken over all oxide components except A1₂O₃, X stands for mole fraction, terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is the composition-dependent apparent partial molar volume of Al₂O₃. The thermal expansion coefficient of aluminosilicate liquids is given by $\text{α = ∑X}{}_{\mathrm{i}}\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}\text{+ X}{}_{\mathrm{A}}\text{}\text{?}\text{ga}{}_{\mathrm{A}}{}^{\mathrm{o}}$, where $\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}$ terms are constants independent of temperature and composition, and $\text{}\text{?}\text{ga}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is a composition-dependent term representing the effect of Al₂O₃ on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = V_rexp[α(T-T_r)], where T_r = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 $\text{cc}\text{mole}$ and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is discussed in terms of several possible interpretations of the structural role of Al³⁺ in aluminosilicate melts.     

Strontium isotope geology of the South Mountain batholith,Nova Scotia

The South Mountain batholith of southwestern Nova Scotia is a large, peraluminous, granodiorite-granite complex which intrudes mainly greenschist facies metasediments of the Cambro-Ordovician Meguma Group. Using Rb-Sr isochrons constructed from whole rocks and mineral separates, the present study shows a variation in age and initial ratios of the intrusive phases of the batholith as follows: biotite granodiorite (371.8 ± 2.2 Ma, (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}$ ranges from 0.7076 ± 0.0003 to 0.7090 ± 0.0003, with the average = 0.7081); adamellite (364.3 ± 1.3 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.70942 ± 35}$); porphyry (361.2 ± 1.4 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.71021 ± 119}$); using λ⁸⁷Rb = 1.42 × 10^?11yr^?1.A suite of Meguma country rock samples showed a variation of ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.7113?0.7177}$ at the time of intrusion of the batholith. A number of xenoliths of this material occurring in the marginal granodiorite had partially equilibrated isotopically with the granodiorite at a higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio than elsewhere in the granodiorites. This evidence demonstrates that isotopic (and probably some accompanying bulk chemical) contamination by the Meguma rocks has been an important factor in determining the ultimate chemical composition and mineralogy of the South Mountain batholith.The $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{372}\text{= 0.7081}$ of the early granodiorites indicates that the parent magma of the South Mountain batholith was derived from a source unlike the Meguma Group. The precise nature of the source region cannot be determined by Rb-Sr work unless the degree of contamination with Megumalike material is known.     

The thermal significance of potassium feldspar K-Ar ages inferred from 40Ar39Ar age spectrum results

${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analyses of three microcline separates from the Separation Point Batholith, northwest Nelson, New Zealand, which cooled slowly (~5°C-Ma^?1) through the temperature zone of partial radiogenic ⁴⁰Ar accumulation are characterized by a linear age increase over the first 65 percent of gas release with the lowest ages (~80 Ma) corresponding to the time that the samples cooled below about 100°C. The last 35 percent of ³⁹Ar released from the microclines yields plateau ages (103,99 and 93 Ma) which reflect the different bulk mineral ages, and correspond to cooling temperatures between about 130 to 160°C. Theoretical calculations confirm the likelihood of diffusion gradients in feldspars cooling at rates ≤5°C-Ma^?1. Diffusion parameters calculated from the ³⁹Ar release yield an activation energy, E = 28.8 ± 1.9 kcal-mol^?1, and a frequency factor/grain size parameter, $\text{D}{}_0\text{l}{}^2\text{= 5.6}{}_{\mathrm{?3.9}}{}^{\mathrm{+14}}\text{sec}{}^{\mathrm{?1}}$. This Arrhenius relationship corresponds to a closure temperature of 132 ± 13°C which is very similar to the independently estimated temperature. From the observed diffusion compensation correlation, this $\text{D}{}_0\text{l}{}^2$ implies an average diffusion half-width of about 3 μm, similar to the half-width of the perthite lamellae in the feldspars. The range in microcline K-Ar ages from the Separation Point Batholith is the result of relatively small temperature differences within the pluton during cooling. Comparison of the diffusion laws determined for microcline with those for anorthoclases and other homogeneous K-feldspars (E = 40 to 52 kcal-mol^?1) reveals that Ar diffusion is more highly temperature dependent in the disordered structural state than in the ordered structural state. Previously published U-shaped age spectra are probably the result of the superimposition of excess ⁴⁰Ar upon diffusion profiles of the kind described here.     

Helium accumulation in groundwater,I: An evaluation of sources and the continental flux of crustal 4He in the Great Artesian Basin,Australia

The rate of accumulation of ⁴He in the groundwaters of the J-aquifer of the Great Artesian Basin, Australia has been determined using ¹⁴C and hydrologic ages. For groundwaters less than 50 Kyr in age, the ⁴He accumulation rate is 4.6 × 10^?12 HeAU (where ) in close agreement with in-situ production rate of ⁴He (3.95 × 10^?12 HeAU) based on U and Th concentrations of 1.7 and 6.1, respectively, of the sandstone. For groundwaters older than 100 Kyr, the rate of ⁴He accumulation is 2.91 × 10^?10 HeAU based on hydrologic ages; or 74 × the rate of in-situ production. The rate of ⁴He “production” due to weathering of the aquifer rock is calculated to be ~10^?16 HeAU, indicating that the weathering input of ⁴He is insignificant. If the groundwater of the GAB can be considered as a trap for the total crustal production of ⁴He, the rate of ⁴He accumulation under a steady-state flux is calculated to be 3.02 × 10^?10 HeAU, in agreement with the measured accumulation rate. It is concluded that over long times the ⁴He accumulation rate in groundwater aquifers may be controlled by the whole crust flux of ⁴He.     

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity,and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

We have calculated the total individual ion activity coefficients of carbonate and calcium, and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of and are $\text{0.038 ± 0.002}$ and $\text{0.173 ± 0.010}$, respectively. These values of and are independent of liquid junction errors and internally consistent with the value . By defining and on a common scale (), the product is independent of the assigned value of and may be determined directly from thermodynamic measurements in seawater. Using the value and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978, Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.     

Solubility product of galena at 298°K: A possible explanation for apparent supersaturation in nature

The synthetic chelating agent ethylenediaminetetraacetic acid (EDTA) has been used to evaluate the stoichiometric solubility product of galena (PbS) at 298°K: $\text{K}{}_{\mathrm{s2}}\text{=}{}^{\mathrm{a}}\text{Pb}{}^{\mathrm{2+}}{}^{\mathrm{a}}\text{HS}{}^{\mathrm{?}}{}^{\mathrm{a}}\text{H}{}^{\mathrm{+}}$ This method circumvents the possible uncertainties in the stoichiometry and stability of lead sulfide complexes. At infinite dilution, $\text{Log K}{}_{\mathrm{s2}}\text{= ?12.25 ±0.17}$, and at an ionic strength corresponding to seawater ($\text{I = 0.7 M}$), $\text{Log K}{}_{\mathrm{s2}}\text{= ?11.73 ± 0.05}$. Using the value of $\text{K}{}_{\mathrm{s2}}$ at infinite dilution, and the free energies of formation of HS^? and Pb²⁺ at 298°K (literature values), the free energy of formation of PbS at 298°K is computed to be $\text{?79.1 ± 0.8 KJ/mol (?18.9 Kcal/mol)}$. Galena is shown to be more than two orders of magnitude more soluble than indicated by calculations based on previous thermodynamic data.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

Settling velocities of particulate systems, 3. Power series expansion for the drag coefficient of a sphere and prediction of the settling velocity

The following equation has been previously developed for the drag coefficient of a sphere.

$\text{C}{}_{\mathrm{D}}\text{= C}{}_0\text{[1 + (σ}{}_0\text{/Re}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)]}{}^2$

In this work the authors propose a power series expansion for C₀ in terms of the Reynolds number:

$\text{C}{}_0\text{= 0 284153}\text{Σ}\text{α=0}\text{n}\text{B}{}_{\mathrm{\alpha }}\text{Re}{}^{\mathrm{\alpha }}$

A fifth-order polynomial permits obtaining the drag coefficient and the settling velocity of a sphere, up to a Reynolds number of 3 × 10⁵, with an average relative error of about 2%.     

The partial molal volume of silicic acid in 0.725 M NaCl at 1°C determined by the neutralization of Na2SiO3

The partial molal volume of silicic acid ($\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$) in 0.725 M NaCl at 1°C was calculated from the measured volume change (Δ$\text{V}\text{?}{}_{\mathrm{n}}$) due to the neutralization of anhydrous sodium metasilicate with HCl and the $\text{V}\text{?}\text{(HCl)}$ and $\text{V}\text{?}\text{(NaCl)}$ obtained from the literature. $\text{V}\text{?}\text{(Si(OH)}{}_4\text{) = 59.0 cm}{}^3\text{mol}\text{? 1}$, determined under experimental conditions of pH = 2.2, compares favorably with $\text{V}\text{?}\text{(Si(OH)}{}_4\text{) = 58.9 cm}{}^3\text{mol}{}^{\mathrm{?1}}$ calculated from the measured volume change due to the hydrolysis of the meta-silicate salt at pH = 11 and from the partial molal volume due to electrostriction ($\text{V}\text{?}{}_{\mathrm{elect}}$) of water by charged Si species present in the solution at the high pH. This agreement lends support to a semiempirical model for calculating $\text{V}\text{?}{}_{\mathrm{elect}}$ in developed by Millero (1969). $\text{V}\text{?}\text{(NaOH) = ? 5.45 cm}{}^3\text{mol}{}^{\mathrm{?1}}$ in 0.725 M NaCl needed for this calculation was also determined in this work. The rate of polymerization of Si(OH)₄ at 1°C was monitored to insure that the monomer Si(OH)₄ was the main Si species present during the determination of $\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$ by neutralization of the alkali silicate. $\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$ determined in this study compares favorably with the value calculated from high pressure solubility measurements.     

Sr and Nd isotope geochronology,geologic history,and origin of the Adirondack Anorthosite

We have analyzed samples from the Adirondack Marcy massif for Rb-Sr and Sm-Nd isotopes in an attempt to determine directly the primary crystallization age of a Proterozoic massif-type anorthosite rock suite. The oldest age obtained (1288 ± 36Ma) is from a 4 point Sm-Nd isochron defined by igneous-textured whole-rock and mineral separate data from a local layered sequence gradational from oxiderich pyroxenite to leuconorite. This age is older than Silver's (1969) 1113 Ma zircon age of associated charnockites, but is within the window of permissible anorthosite ages based on previous geochronology and field relationships. As such, 1288 Ma may represent the time of crystallization of the massif. For the most part, however, both Sm-Nd and Rb-Sr isotopic systems did not survive granulite facies metamorphism. Internal isochrons based on whole rocks and minerals yield ages between 995 and 919 Ma. These isotopic data suggest that the granulite fades metamorphism experienced by the massif was a prograde event that occurred a minimum of 100 Ma and as much as 350 Ma after crystallization of the massif. The relatively large range in Rb abundance, and in calculated initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ (0.7039–0.7050) and ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios among anorthosite suite rocks, particularly those at or near the contacts of the Marcy massif is explicable by variable contamination with “crustal” materials and/or fluids, derived from surrounding acidic metaplutonic rocks, paragneisses, and marbles. Despite uncertainies caused by crustal contamination and metamorphic resetting of primary ages, Marcy samples have epsilon Nd values between +0.44 and +5.08, implying a source for the massif with long-term depletion in light rare earth elements. A probable source material would be depleted mantle.