Investigations of an intrusive contact,northwest Nelson,New Zealand—II. Diffusion of radiogenic and excess 40Ar in hornblende revealed by 40Ar39Ar age spectrum analysis

The Rameka Gabbro, emplaced 367 Ma ago, experienced a well documented reheating on intrusion of the Separation Point Batholith 114 Ma ago. ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analyses of hornblende from the Rameka Gabbro show diffusion gradients which provide information on the ⁴⁰Ar boundary concentration during reheating.Three samples of hornblende exhibit age spectra that conform to a model of ⁴⁰Ar loss by diffusion, implying a zero ⁴⁰Ar boundary concentration during heating. The calculated ⁴⁰Ar loss from these samples, together with a model of heat flow in the aureole, provide estimates of diffusion coefficients of ⁴⁰Ar in Mg-rich hornblende which correspond to an activation energy, E, of ~60 kcal-mol^?1 and a frequency factor. D₀, of ~ 10^?3 cm²-sec^?1. When combined with laboratory diffusion results, these data yield a well defined diffusion law (E = 63.3 ± 1.7 kcal-mol^?1, $\text{D}{}_0\text{= 0.022}{}^{\mathrm{+0.048}}{}_{\mathrm{?0.010}}\text{cm}{}^2\text{-}\text{sec}{}^{\mathrm{?1}}$).The age spectra of the eight other samples record steep gradients of excess ⁴⁰Ar over the first few percent of gas release. Although this effect causes high apparent conventional K-Ar ages, the plateau segments of many sampes still record the crystallization age of 367 ± 5 Ma. These measurements show that the excess ⁴⁰Ar phase developed locally in the intergranular regions of the gabbro, following intrusion of the batholith. on time scales that varied from 10⁴ to 10⁶years. The minimum average ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio of this component was found to be 1300 ± 400. The partial pressure of Ar was at least 10^?2 bars in some places.A single ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of plagioclase reveals a ‘saddle-shaped” release pattern with a minimum at 140 Ma.In conjunction with theoretical diffusion models and a diffusion law, ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of hornblende that has experienced a post-crystallization heating can provide close estimates of the maximum temperature of the thermal event as well as both age of crystallization and reheating.     

40Ar39Ar dating,Ar diffusion properties,and cooling rate determinations of severely shocked chondrites

Determinations of ${}^{40}\text{Ar}{}^{39}\text{Ar}$ ages are reported for seven severely shock-heated chondrites. Shaw gives a plateau age of 4.29 Gyr. Louisville, Farmington, and Wickenburg give well-defined intercept ages of 0.5–0.6 Gyr. Orvinio, Arapahoe, and Lubbock show complex ${}^{40}\text{Ar}{}^{39}\text{Ar}$ release curves, with age minima of 0.7–1.0 Gyr. Degassing times of 0.5–1.0 Gyr are suggested for these meteorites. Most severely shocked chondrites were apparently not totally degassed of ⁴⁰Ar by the event, but retained from ~ 2 to ~45% of their ⁴⁰Ar. When calculated values of the diffusion parameter, $\text{D}\text{a}{}^2$, for Ar are examined in Arrhenius plots, they show two distinct linear relationships, which apparently correspond to the degassing of different mineral phases with distinct $\text{K}\text{Ca}$ ratios and different average temperatures for Ar release. The experimentally determined values of $\text{D}\text{a}{}^2$ for the high temperature phase of several severely shocked chondrites are ~10^?7 to 10^?5sec^?1 for their determined shock-heating temperatures of ~950°C to ~ 1200°C. The inferred reheating temperatures, $\text{D}\text{a}{}^2$ values, and fraction of ⁴⁰Ar loss during the reheating event for these seven chondrites suggest post-shock cooling rates and burial depth of ~ 10^?2 10^?4°C/sec and ~0.5–2m, respectively. For three chondrites these cooling rates agree with those determined from Ni diffusion in metal grains: for five chondrites the cooling rates derived from ⁴⁰Ar and Ni disagree by a factor of ~10⁵. It is suggested that five of these severely shocked chondrites were part of large ejecta blankets containing hot material and cold clasts with a distribution of sizes and that the cooling rate of this ejecta appreciably decreased as a function of time.     

Diffusion of 40Ar in biotite: Temperature,pressure and compositional effects

The measured radiogenic ⁴⁰Ar loss from sized biotite (56% annite) samples following isothermalhydrothermal treatment have provided model diffusion coefficients in the temperature interval 600°C to 750°C, calculated on the assumption that Ar transport proceeds parallel to cleavage. These data yield an array on an Arrhenius plot with a slope corresponding to an activation energy 47.0 ± 2 kcal-mol^?1 and a frequency factor of 0.077^+0.21_?0.06 cm²-sec^?1. Together with previous diffusion data for micas in the annitephlogopite series, our results indicate a strong compositional effect, with increasing $\text{Fe}\text{Mg}$ ratio corresponding to an increase in diffusivity. An effective diffusion radius of about 150 μm for biotite is inferred from the experimental data which compares favorably with that estimated from geological studies. A pressure effect on activation energy corresponding to an activation volume of about 14 cm³-mol^?1 is observed. These data yield closure temperature estimates for this biotite composition cooling at rates of 100°C-Ma^?1, 10°C-Ma^?1 and 1°C-Ma^?1 of 345°C, 310°C and 280°C, respectively. ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age-spectrum analysis of a hydrothermally treated biotite yields a complex release pattern casting doubt on the general usefulness of such measurements for geochronological purposes.     

Recognition of extraneous argon components through incremental-release 40Ar39Ar analysis of biotite and hornblende across the Grenvillian metamorphic gradient in southwestern Labrador

${}^{40}\text{Ar}{}^{39}\text{Ar}$ incremental-release ages have been determined for 15 hornblende and 20 biotite concentrates separated from rocks collected across the garnet and kyanite zones of Grenvillian metamorphism in southwestern Labrador. Most hornblende spectra from the kyanite zone are slightly discordant, with low-temperature increments yielding ages older than the ca 1000 Ma date suggested for culmination of Grenvillian metamorphism in the area. However, all the hornblende concentrates record well-defined plateau ages. These range from 968 to 905 Ma across the kyanite zone and date times of diachronous post-metamorphic cooling. The discordant spectra are interpreted to result from low-temperature liberation of excess ⁴⁰Ar components from grain margins. Two hornblende concentrates from the garnet zone display very discordant spectra (total-gas ages of 2100 and 3017 Ma) in which incremental dates systematically decrease during analysis. This pattern of discordance suggests that excess argon components are inhomogeneously distributed throughout these hornblende grains.Most biotites from the garnet and kyanite zones record total-gas or plateau ages in excess of 1000 Ma (2066-857 Ma), reflecting the widespread presence of excess argon components. Because most of the ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectra are internally concordant, the ratios of excess ⁴⁰Ar relative to radiogenic ⁴⁰Ar must have been uniform in the various gas fractions liberated from each sample. This is also reflected in the inability of isotope correlation diagrams to differentiate between excess, radiogenic, and atmospheric argon components. The biotite total-gas or plateau dates show marked local variation. This is interpreted to indicate that the biotite grains were in contact with a post-metamorphic intergranular vapor phase that was characterized by large and variable ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratios. Such ratios most likely resulted from widespread diffusion of the argon liberated from adjacent Archean basement gneisses during the Grenvillian metamorphic overprint.     

40Ar39Ar and KAr dating of altered glassy volcanic rocks: the Dabi Volcanics,P.N.G.

KAr and ${}^{40}\text{Ar}{}^{39}\text{Ar}$ ages have been determined for altered submarine tholeiitic and boninite (high-Mg andesite) lavas from the Dabi Volcanics, Cape Vogel Peninsula, Papua New Guinea. ${}^{40}\text{Ar}{}^{39}\text{Ar}$ whole rock total fusion and plateau ages identify a Late Paleocene age for the tholeiitic lavas (58.9 ± 1.1 Ma) and also for the boninitic lavas (58.8 ± 0.8 Ma). Apparent KAr ages for the same samples range from 27.2 ± 0.7 to 63.9 ± 4.5 Ma, and young KAr ages for glassy boninites are probably due to variable radiogenic ⁴⁰Ar (⁴⁰Ar¹) loss. These new ages effectively reconcile previously ambiguous age data for the Dabi Volcanics and indicate contemporaneous tholeiitic and boninitic volcanism occurring in southeast PNG during the Late Paleocene.Smectites, developed as alteration products after glass in oceanic lavas commonly do not retain ³⁹Ar during or subsequent to irradiation, but in some cases may contain ⁴⁰Ar1. In the absence of other factors modifying K and Ar contents, samples which have not lost ⁴⁰Ar¹ from smectite and suffer ³⁹Ar loss only, are interpreted to have been altered immediately subsequent to the crystallization of the lava; whereas samples which have lost ⁴⁰Ar¹ as well as ³⁹Ar may be the result of either recent alteration, or of continuous ⁴⁰Ar¹ loss since the time of crystallization.     

3He4He ratio,noble gas abundance and K-Ar dating of diamonds—An attempt to search for the records of early terrestrial history

The ${}^3\text{He}{}^4\text{He}$ ratios measured in 27 Southern Africa diamond stones, four from Premier Mine and the rest of unidentified origin, range from 4.2 × 10^?8 to 3.2 × 10^?4, with three stones above 1 × 10^?4. We conclude that the initial helium isotopic ratio (${}^3\text{He}{}^4\text{He)}{}_0$ in the earth was significantly higher than that of the planetary helium-A (${}^3\text{He}{}^4\text{He = 1.42 × 10}{}^{\mathrm{?4}}$), but close to the solar helium (${}^3\text{He}{}^4\text{He ? 4 × 10}{}^{\mathrm{?4}}$).The apparent K-Ar ages for the twelve diamonds of unidentified origin show enormously old age, indicating excess argon-40. ${}^3\text{He}{}^4\text{He}$ evolution in diamonds suggests that the diamonds with the high ${}^3\text{He}{}^4\text{He}$ ratio (>2 × 10^?4) may be as old as the earth.Noble gas elemental abundance in the diamonds relative to the air noble gas abundance shows monotonie decrease with a decreasing mass number.This paper discusses the implications of these observations on the early solar system and the origin of diamonds.     

Further 40Ar39Ar evidence for the multi-collisional heating of the Kirin chondrite

Results of an ${}^{40}\text{Ar}{}^{39}\text{Ar}$Ar age spectrum obtained on a sample of the Kirin chondrite (K-5-13) show a similar character to previous published analyses of Kirin samples K-1 and K-2. The K-5-13 age spectrum shows clear evidence of having been substantially outgassed during a presumed collisional event about 0.5 Ga, ago, in good agreement with the estimate obtained from K-2, The differing amounts of ⁴⁰Ar loss registered by K-2 and K-5-13 during the 0.5 Ga event of about 60 and 50%, respectively, allows calculation of their vertical separation in the parent body at about 10cm.     

Application of the 227Th230Th method to dating Pleistocene carbonates and comparison with other dating methods

The ${}^{227}\text{Th}{}^{230}\text{Th}$ dating method is described in detail and its usefulness investigated by comparing ages of sixteen Pleistocene carbonates (mainly cave deposits) with those determined by the ${}^{231}\text{Pa}{}^{235}\text{U}$ and ${}^{230}\text{Th}{}^{234}\text{U}$ methods. The ${}^{227}\text{Th}{}^{230}\text{Th}$ ages are found to be critically dependent on corrections for decay of ²²⁷Th prior to alpha counting and ingrowth of daughter isotopes of ²³²Th derived from clastic detritus. Of nineteen sets of ages determined for the sixteen samples, good agreement is found for only seven sets. Differences are attributed to low U content of some samples and the possibility of excess ²²⁷Th in the calcite of samples younger than ~50 ky, possibly due to the coprecipitation of ²³¹Pa during formation. Calculated “negative” ${}^{227}\text{Th}{}^{230}\text{Th}$ ages may be a direct result of this process and the fact that, unlike the other methods, the activity ratio is non-zero at zero age. Nevertheless, the ${}^{227}\text{Th}{}^{230}\text{Th}$ is found to be a useful alternative dating technique for carbonates which are between ~50 and 300 ky, because no spiking is required. It also serves as a check for partial concordancy with ages dated by the other methods.     

40Ar39Ar ages of biotite and hornblende from a progressively remetamorphosed basement terrane: their bearing on interpretation of release spectra

Biotite and hornblende from a portion of the Blue Ridge Precambrian basement terrane that was progressively retrograded during Paleozoic metamorphism have been analyzed by the ${}^{40}\text{Ar}{}^{39}\text{Ar}$ dating technique to determine if incremental release spectra can distinguish thermally altered samples. Where not severely overprinted by Paleozoic metamorphism, both minerals show generally undisturbed age spectra with plateau ages similar to those of hornblende and biotite from non-retrograded portions of the Grenville terrane elsewhere in the Appalachians (hornblende ~1000 m.y.; biotite ~ 790 m.y.). The age spectra show a progressive disturbance which is correlated with increasing intensity of Paleozoic metamorphism. Modification of the hornblende spectra is that expected of diffusive argon loss during geologic reheating (incremental ages become older from low to high release temperatures). Disturbed biotite spectra do not show this type of modification, but develop increasingly broader low-age ‘saddles’ with increasing retrograde intensity. Eventually, Paleozoic metamorphism effected total retrograde alteration of the Grenville minerals and new generations of chemically distinct biotite and hornblende occur. Release spectra of these phases generally define plateaus although they are of different ages (biotite ~310–340 m.y.; hornblende ~355–460 m.y.). This discordancy is similar to that reported for other recrystallized portions of the Appalachian Grenville terrane and suggests that the ages represent times of argon retention following a 480 m.y. Paleozoic metamorphism.The data suggest that ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectra can distinguish thermally altered samples.     

26Al and rare gases in Allende,Bereba and Juvinas: implications for production rates

The ²⁶Al, light rare gas and major and minor element contents of Al-rich and poor samples separated from Allende. Bereba and Junivas have been measured. The production rate of ²¹Ne from Al (²¹P_Al) is $\text{(1.9 ± 0.6) ×}{}^{21}\text{P}{}_{\mathrm{Si}}$ and ${}^{\mathrm{<mtext>22</mtext><mtext>21</mtext>}}\text{P}{}_{\mathrm{Al}}\text{= 1.4 ± 0.4.}$ The ³He, ²¹Ne and ³⁸Ar exposure ages of the eucritic pyroxenes agree suggesting complete cosmogenic gas retention. The eucritic feldspars have lost virtually all ³He and most radiogenic ⁴He. The equation ²⁶Al = 0.42 ± 0.41 Mg + 2.74 ± 0.21 Si + 4.92 ± 0.51 Al + 1.33 S + 0.24 Ca + 0.03 Fe reproduces within 15% our ²⁶Al measurements and the average values measured in ordinary chondrites without recourse to unusual cosmic-ray effects.     

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.     

Radium content and the 226Ra228Ra activity ratio in groundwater from bedrock

The relative abundance of ²²⁶Ra and ²²⁸Ra were determined in the groundwater from 125 drilled wells containing from < 0.1 to 51.3 pCi/l of ²²⁶Ra. The determination of ²²⁸Ra was carried out with a liquid scintillation counter by measuring only the weakly energetic β particles emitted from ²²⁸Ra. Thus the interference from the daughter nuclides of ²²⁶Ra was avoided, without specific separation of ²²⁸Ac. The direct measurement of ²²⁸Ra made the method decisively simpler and faster in terms of the chemistry involved.The concentration of ²²⁸Ra was found to be independent of the amount of ²²⁶Ra present in the samples. The concentrations of ²²⁸Ra were nearly the same over the whole range of ²²⁶Ra concentrations and the average $\text{sol}{}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio sharply increased as the ²²⁶Ra content of water increased. The ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio in the drilled wells varied from 0.3 to 26. Abnormally high ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratios were found in areas with known uranium deposits as well as in several drilled wells at other locations. The abnormally high ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratios present in groundwater suggest that the radioactivity anomaly is caused by uranium deposits and not by common rocks. In samples with a low radioactivity level the average ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio was slightly below unity, corresponding to the typical U/Th ratio of granite, the most common kind of rock in the study area. The samples from the rapakivi area proved to be exceptional in that they had a low ${}^{226}\text{Ra}{}^{228}\text{Ra}$ ratio independent of the concentration of ²²⁶Ra.     

40Ar-39Ar dating of inclusions from IAB iron meteorites

Silicate and troilite from IAB iron meteorites were dated by the ⁴⁰Ar-³⁹Ar technique. Silicate from four IAB meteorites gave well-defined apparent-age plateaus which accounted for 71–99% of the released ³⁹Ar. At low temperatures, only Copiapo showed appreciable loss of ⁴⁰Ar, while Mundrabilla and Woodbine released excess ⁴⁰Ar. The plateau ages are: 4.50 Byr for Copiapo, 4.57 Byr for Mundrabilla, 4.57 Byr for Woodbine, 4.54 Byr for unetched Pitts, and 4.57 Byr for etched Pitts; the 1σ error in each case is ± 0.03 Byr. A poorly-defined age plateau for Landes gives an age of 4.48 Byr, while the total K-Ar age (4.55 Byr) is significantly higher. The average $\text{(}{}^{40}\text{Ar/}{}^{36}\text{Ar)}$_trapped ratio for all silicate samples is 0.4 ± 0.4.Simple and undisturbed K-Ar systems are rare for meteorites, yet it appears to be a common feature for IAB silicates. In addition, plateau ages of IAB silicates are as old or older than the mean age of unshocked chondrites (4.47 Byr).Troilite samples yielded complex patterns which were evaluated via ⁴⁰Ar/³⁶Ar vs ³⁹Ar/³⁶Ar plots. Data for Pitts troilite are consistent with silicate and troilite retaining Ar at about the same time initially, but then 4.25 Byr ago nearly all the Ar in troilite was redistributed. The 700–1000°C points for Mundrabilla troilite define a line which gives an age of 6.2 Byr and $\text{(}{}^{40}\text{Ar/}{}^{36}\text{Ar)}{}_{\mathrm{trapped}}\text{= 42}$. This line may be an artifact, perhaps produced by homogenization of Ar and K.Approximate estimates of cosmic-ray exposure ages are 240 Myr for Landes, 130 Myr for Copiapo, 190 Myr for Woodbine, 170 Myr for Mundrabilla troilite, and 60 Myr for Pitts troilite.The I-Xe study of these same samples revealed a good correlation between well-defined I-Xe ages of silicates and Ni contents of metal (Niemeyer, 1979). The poorer resolution of the ⁴⁰Ar-³⁹Ar technique hampers a similar evaluation; nevertheless, plateau ages of the silicates suggest a systematic trend with Ni contents.     

Rare gases and 36Cl in stony-iron meteorites: cosmogenic elemental production rates,exposure ages,diffusion losses and thermal histories

Metal and silicate portions from 13 mesosiderites, one pallasite, Bencubbin (“unique”) and Udei Station (‘iron with silicate inclusions’) have been analysed for their content of He, Ne and Ar; in most cases ³⁶Cl could be determined as well. ³⁶Cl-³⁶Ar cosmic ray exposure ages fall between 10 and 160 Myr. Half of the metal samples show a deficit of spallogenic ³He (up to 30%) which we ascribe to a loss of tritium. The observed depletion of ³He in the silicates is correlated with their mineralogical composition: feldspar has lost its ³He in all cases, pyroxene definitely in one and possibly in five others, while olivine has been affected in only two meteorites. The thermal histories during their exposure to the cosmic radiation have been different for different meteoroids. Nevertheless, with the exception of Veramin, the data are compatible with the assumption of a continuous diffusion loss during a considerable fraction of the exposure era. For Veramin, however, an episodic event late in the exposure history is required. The exceptionally high ${}^{39}\text{Ar}{}^{36}\text{Cl}$ ratio in the metal, which is due to a high ³⁹Ar activity, indicates that the event occurred during the last 500,000 years or so and resulted in an extremely excentric orbit (large aphelion).Production rates of ^38,39Ar from Ca and ^21,22Ne from Mg are given. The ratio $\text{P}{}^{38}{}_{\mathrm{Ca}}\text{P}{}^{21}{}_{\mathrm{Mg}}$ is close to unity. The ratios $\text{P}{}^{38}{}_{\mathrm{Ca}}\text{P}{}^{38}{}_{\mathrm{Fe}}$ vary between 20 and 50, and are not correlated with the absolute production rate of ³⁸Ar from metal. The ${}^{22}\text{Ne}{}^{21}\text{Ne}$ production ratio from Mg is found to be close to but below unity.Of the mesosiderites only Veramin shows unambiguous evidence for primordial rare gases with larger amounts and a higher ${}^{20}\text{Ne}{}^{36}\text{Ar}$ ratio in the olivine, suggesting in situ fractionation to have at least been partly responsible for the abundance pattern found. Bencubbin contains large amounts of strongly fractionated primordial gases, but again part of the fractionation may have occurred in situ. Udei Station shows an excess of (3.5 ± 0.6) × 10^?10 cm³ STP ¹²⁹Xe/g in the non-magnetic portion.     

U234U238 Ratios in limestone cave seepage waters and speleothem from West Virginia

Speleothem from West Virginia, ranging in age from 2000 to 200,000 yr B.P. contains uranium with $\text{U}{}^{234}\text{U}{}^{238}$ ratios significantly greater than unity. This ratio varies from one speleothem to another, as does average U content. Initial ratios, corrected for age, are remarkably constant for a given speleothem. By contrast, $\text{U}{}^{234}\text{U}{}^{238}$ ratios in seepage waters vary significantly from month to month at a given drip site, and their average values differ from that of the speleothem which they are depositing. This discrepancy is attributed either to long-term averaging-out of fluctuations, or fractional precipitation on the speleothem of a chemical species of uranium with a more constant ratio. Constancy of initial $\text{U}{}^{234}\text{U}{}^{238}$ ratios from $\text{Th}{}^{230}\text{U}{}^{234}$. datable portions of speleothems should permit $\text{U}{}^{234}\text{U}{}^{238}$-dating of older portions of the same speleothem, back to about 10⁶ yr B.P., with estimated precision of ±5 per cent.     

Complex formation in the ternary system Mg(II)-CO2-H2O

The carbonato and hydrogencarbonato complexes of Mg²⁺ were investigated at 25 and 50° in solutions of the constant ClO₄^? molality (3 M) consisting preponderantly of NaClO₄. The experimental data could be explained assuming the following equilibria: Mg²⁺ + CO_2B + H₂O ag MgHCO⁺₃ + H⁺, $\text{log}{}^1\text{β}{}_1\text{= ?7.64}{}_4\text{± 0.01}{}_7\text{(25°), ?7.46}{}_2\text{± 0.01}{}_1\text{(50°)}$, Mg²⁺ + 2 CO_2g + 2 H₂Oag Mg(HCO₃)⁰₂ ± 2 H⁺, $\text{log}{}^1\text{β}{}_2\text{= ?15.00 ± 0.14 (25°)}$, ?15.37 ± 0.39 (50°), Mg²⁺ + CO_2g + H₂Oag MgCO⁰₃ + 2 H⁺, $\text{log}{}^1\text{k}{}_1\text{= ?15.64 ± 0.06 (25°)}$,?15.23 ± 0.02 (50°), with the assumption γ_MgCO3⁰ = γ_Mg(HCO3)⁰2, ΔG⁰(I = 0) for the reaction MgCO⁰₃ + CO_2g + H₂O = Mg(HCO₃)⁰₂ was estimated to be ?3.9₁ ± 0.8₆ and 0.6 ± 2.4 kJ/mol at 25 and 50°C, respectively. The abundance of carbonate linked Mg(II) species in fresh water systems is discussed.     

An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

Mineral-solution equilibria—III. The system Na2OAl2O3SiO2H2OHCl

Chemical equilibrium between sodium-aluminum silicate minerals and chloride bearing fluid has been experimentally determined in the range 500–700°C at 1 kbar, using rapid-quench hydrothermal methods and two modifications of the Ag + AgCl acid buffer technique. The temperature dependence of the thermodynamic equilibrium constant (K) for the reaction $\text{NaAlSi}{}_3\text{O}{}_8\text{+ HCl}{}^{\mathrm{o}}\text{= NaCl}{}^{\mathrm{o}}\text{+}\text{1}\text{2Al}{}_2\text{SiO}{}_5\text{, +}\text{5}\text{2SiO}{}_2\text{+}\text{1}\text{2H}{}_2\text{O}$ Albite Andalusite Qtz. can be described by the following equation: log k = ?4.437 + 5205.6/T(K) The data from this study are consistent with experimental results reported by Montoya and Hemley (1975) for lower temperature equilibria defined by the assemblages albite + paragonite + quartz + fluid and paragonite + andalusite + quartz + fluid. Values of the equilibrium constants for the above reactions were used to estimate the difference in Gibbs free energy of formation between NaCl^o and HCl^o in the range 400–700°C and 1–2 kbar. Similar calculations using data from phase equilibrium studies reported in the literature were made to determine the difference in Gibbs free energy of formation between KCl^o and HCl^o. These data permit modelling of the chemical interaction between muscovite + kspar + paragonite + albite + quartz assemblages and chloride-bearing hydrothermal fluids.     

Complexing of silica by iron(III) in natural waters

Determination of amorphous silica solubility in acidified ferric nitrate solutions confirms the presence of ferric silicate complexing. A dissociation constant for the reaction:

$\text{FeH}{}_3\text{SiO}{}_4{}^{\mathrm{2+}}\text{→}\text{Fe}{}^{\mathrm{3+}}\text{+}\text{H}{}_3\text{SiO}{}_4{}^{\mathrm{?}}$

of 10^?9.8 ± 0.3 pK units at room temperature (22 ± 3°C) is obtained, in close agreement with reported values at 25°C corrected to zero ionic strength of 10^?9.9 by Weber and Stumm and 10^?9.5 by Olson and O'Melia. Iron-silicate complexing may be of significance to the mobilization of silica in acid waters associated with oxidizing sulphide deposits and coal strip mining and the precipitation of secondary silicate mineral phases.