Chemical studies of L chondrites—III. Mobile trace elements and 40Ar39Ar ages

We report data for trace elements Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Se, Te, Tl and Zn determined by radiochemical neutron activation analysis in L4–6 chondrites with undisturbed ⁴⁰Ar release patterns or with patterns showing some disturbance in the 4.4–4.6 Gyr plateau indicating shock-induced loss. Mean concentrations are lower, many significantly so, in 16 chondrites with disturbed patterns than in 4 with undisturbed ones, consistent with shock-induced mobilization. Similar trends were noted earlier in L4–6 chondrites having mineralogically observable shock indicators: mean concentrations are lower in strongly shocked (i.e. > 22 GPa) than in mildly shocked (<22 GPa) samples. From trace element contents, L4–6 chondrites with undisturbed ⁴⁰Ar release patterns are mildly shocked but chondrites with disturbed patterns are more strongly heated, on average, than those of shock facies d-f (i.e. 22 to > 57 GPa). Pooling these populations, significantly lower mean concentrations of nearly all trace elements in 26 strongly shocked L4–6 chondrites than in 14 mildly shocked ones indicate loss in shock-formed FeS-Fe eutectic and/or by vaporization during cooling of shock-heated collisional debris. Two-element correlations and the pattern of them, i.e. correlation profiles, are also consistent with this picture. Trace elements can act as thermometers for collisional episodes in L4–6 chondrites but not for earlier thermal fractionations, unless compensation can be made for late shock heating.     

Correlation of 13C12C and 34S32S secular variations

Statistical evaluation of 3056 δ¹³C measurements in carbonate rocks and fossils shows that they record a 2‰ ¹³C depletion from the late Proterozoic to the early Paleozoic, a 2.5‰ enrichment to the Permian, and a 1.5‰ depletion to the Cenozoic. These variations, not controlled primarily by facies or alteration phenomena, correlate negatively with the δ³⁴S sulfate secular trend, as confirmed by collation of 1083 δ³⁴S measurements. The correlation suggests that the biologically mediated redox fluxes of the C and S cycles have been approximately balanced through this long span of geological time, generally levelling available oxygen. Such a redox system is consistent with the controlling mechanism proposed by Garrels and Perry (1974). Consequently, the sedimentary reservoirs of C_organic as well as S_{bacteriological'}have varied through geological time.     

SrCa and MgCa ratios in polygenetic carbonate allochems from a Michigan marl lake

Rapid accumulation of CaCO₃ is occurring in Littlefield Lake, a marl lake located in central Michigan. The sediment, which is 95% CaCO₃, primarily consists of eight different genetic groups of carbonate allochems. These include calcite muds, sands, algal oncoids and Chara encrustations, as well as the dominant aragonitic gastropods Valvota tricarinota. Gyraulus deflectus and Amnicola integra. and the dominant aragonitic pelecypod Sphaerium partumeium. Samples of each of these groups were analyzed for Ca, Sr and Mg. Molar $\text{Mg}\text{Ca}$ ratios are primarily controlled by allochem mineralogy, with calcitic forms having $\text{Mg}\text{Ca}$ ratios 5–10 times larger than aragonitic (shelled) forms. The $\text{Sr}\text{Ca}$ ratios are primarily controlled by biochemical fractionation, and are significantly lower than $\text{Sr}\text{Ca}$ ratios of inorganically precipitated aragonite from other settings. Partition coefficients were determined for both Sr and Mg for each carbonate allochem group and, based on comparisons with results reported by other workers, the partition coefficients determined here are generally considered ‘typical’ or representative values for biogeneous freshwater carbonates. An analysis of variance of the data indicates that most genera and species of carbonate-secreting organisms in marl lakes have highly characteristic $\text{Sr}\text{Ca}$ and $\text{Mg}\text{Ca}$ ratios. These ratios can potentially serve as geochemical tracers in future investigations of lacustrine carbonate diagenesis. Both Sr and Mg are influenced by grain size and/or surface area, probably due to the presence of these elements in non-lattice-held (exchangeable) positions.     

Surface study of HF- and HFH2SO4-treated feldspar using Auger electron spectroscopy

Auger electron spectroscopy has been used to study K-feldspar that has been reacted with both aqueous 10% HF and a 50% mixture of a 10% HF/0.1 N H₂SO₄ solution. In the feldspar/HF system, the resulting feldspar surface was shown to have been fluorinated; depth profiling, using argon ion sputtering, showed the fluorination to have occurred substantially into the mineral bulk. In the feldspar/ $\text{HF}\text{H}{}_2\text{SO}{}_4$ system, the resulting surface contained both fluorine and sulfur. The fluorination had again penetrated into the bulk, but the sulfur could be removed with mild argon ion sputtering. The $\text{Al}\text{F}$ signal ratio was much lower on the feldspar surface treated with the 10% HF/0.1 N H₂SO₄ solution than the feldspar surface treated with the weaker 10% HF acid solution.     

Stable hydrogen isotopes in iron oxides—II. DH variations among natural goethites

Goethite samples analyzed for this study have a δD range from ?202 to ?98 per mil with a corresponding δD range of associated waters from about ?110 to +7 per mil. Goethites with the most positive δD values are from marine environments. Goethite-water equilibrium $\text{D}\text{H}$ fractionation factors measured in this laboratory at 100°C and 145°C and estimated for sedimentary temperatures from data on natural samples have values of about 0.900 at all three temperatures. These data suggest that goethite δD values may be a direct, temperature-independent measure of the δD values of the waters with which the goethite last equilibrated. Most of the goethite δD values in this study reflect the δD values of the modern waters in the locales of origin.Substitution of Mn and/or Al for Fe in the goethite structure may affect the mineral-water fractionation factor. Manganese appears to decrease the value of α. The effect of Al substitution on α has not yet been measured, but preliminary arguments suggest that increasing Al content could increase α values.     

18O16O ratios in Luna 16 fines

Partial fluorination experiments developed on a 26 mg sample of Luna 16 fines show a big ¹⁸O enrichment in the first oxygen evolved similar to those observed by Epstein and Taylor on Apollo samples and probably related to the high solar wind content of this sample.     

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.     

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.     

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.     

A high 87Sr86Sr mantle source for low alkali tholeiite,northern Great Basin

Olivine tholeiites, the youngest Tertiary units (about 8–11 m.y. old) at five widely spaced localities in northeastern Nevada, are geologically related to the basalts of the Snake River Plain, Idaho, to the north and are similar in major element and alkali chemistry to mid-ocean ridge basalts (MORB) and island arc tholeiites. The measured K (1250–3350 ppm), Rb (1·9–6·2 ppm) and Sr (140–240 ppm) concentrations overlap the range reported for MORB. Three of the five samples have low, unfractionated rare earth element (REE) patterns, the other two show moderate light-REE enrichment. Barium concentration is high and variable (100–780 ppm) and does not correlate with the other LIL elements. The rocks have ⁸⁷Sr/⁸⁶Sr = 0·7052–0·7076, considerably higher than MORB (~0·702–0·703). These samples are chemically distinct (i.e. less alkalic) from the olivine tholeiites from the adjacent Snake River Plain, but their Sr isotopic compositions are similar. They contain Sr that is distinctly more radiogenic than the basalts from the adjacent Great Basin. About 10 b.y. would be required for the mean measured Rb/Sr (~ 0·02) of these samples to generate, in a closed system, the radiogenic Sr they contain. The low alkali content of these basalts makes crustal contamination an unlikely mechanism. If the magma is uncontaminated, the time-averaged Rb/Sr of the source material must have been ~0·04. A significant decrease in Rb/Sr of the source material (a factor 2?) thus most probably occurred in the relatively recent (1?0⁹ yr) past. Such a decrease of Rb/Sr in the mantle could accompany alkali depletion produced by an episode of partial melting and magma extraction. In contrast, low ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios indicate that the source material of the mid-ocean ridge basalts may have been depleted early in the Earth's history.     

The geochemical coherence of Pu and Nd and the 244Pu238U ratio of the early solar system

Two very different sets of ${}^{244}\text{Pu}{}^{238}\text{U}$ ratios have been reported for early solar system materials. One group of samples yields high (0.015–0.016) ratios (Podosek, 1970a, 1972; Drozd et al., 1977) and calculations based on another group of analyses yield low ratios (~0.004) (Marti et al., 1977). Recently measured partition coefficients for Pu and Sm are used to evaluate the data of Marti et al. and $\text{sol}{}^{244}\text{Pu}{}^{238}\text{U}$ ratios from other sources are also considered. A low $\text{sol}{}^{244}\text{Pu}{}^{238}\text{U}$ ratio (~0.005) is favored, and some implications of this low ratio to galactic nucleosynthesis and meteorite age dating are briefly discussed.     

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.     

Uplift rates of the Loyalty Islands as determined by 230Th234U dating of raised coral terraces

Uplift rates of the Loyalty Islands (S.W. Pacific) have been determined from ${}^{230}\text{Th}{}^{234}\text{U}$ dating of raised coral terraces standing 2 to 7.5 m above sea level. The ages of the terraces on Ouvéa and Lifou correspond closely to previously documented periods of high sea levels at 120,000 and 180,000 yr BP. A +2-m terrace on Beautemps-Beaupré is considered to be beyond the range of the dating technique. The uplift rates of the various islands show a decrease toward the west. This lends support to the hypothesis of a lithospheric bulge of the leading edge of the Australian plate prior to its subduction at the level of the New Hebrides trench.     

The variation of the marine 87Sr86Sr ratio during Phanerozonic time: interpretation using a flux model

The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio in sea water has varied over geologic time due to the addition of strontium to the sea from rocks with a variety of ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios. The measurements by Petermanet al. (Geochim. Cosmochim. Acta34, 105–120, 1970) of the value of the marine ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio have been confirmed by several other workers and by some new measurements on JOIDES samples. They form the basis of a model calculation of the relative proportions of ‘basaltic’ (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.704}$) and ‘granitic’ (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.718}$) strontium being supplied to the sea. For the last 200 million years, the proportions of these two sources appear to reflect the history of global tectonics; ‘basaltic’ during rifting and increasingly ‘granitic’ during the present episodes of uplift and continental collision     

207Pb206Pb ages of individual mineral phases in Luna 20 material by ion microprobe mass analysis

Ion microprobe analyses of returned lunar material have helped to demonstrate that U, Th and radiogenic Pb are concentrated in small accessory mineral phases. It is possible to measure the isotopic composition of this Pb and obtain a radiometric ${}^{207}\text{Pb}{}^{206}\text{Pb}$ age for the mineral. The ages so derived compare favorably with crystallization ages determined by conventional methods. A grain mount ($\text{22003,2}\text{6}$) of Luna 20 material was searched for such accessory mineral phases and two were found. One of these phases gives an age of 4.12 ± 0.04 b.y. and the other an age of 4.42 ± 0.11 b.y. Ages of minerals dated by the ion probe in Apollo samples 14310 and 15555 are given for comparison. Data on the upper limit for Pb concentration in the outermost surface layers of free lunar soil particles are also given.     

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.     

sol18O16O of Archean clastic metasedimentary rocks: a petrogenetic indicator for Archean gneisses?

The oxygen isotopic compositions of over 100 Archean clastic metasedimentary, felsic metavolcanic and gneissic rocks from selected areas within the Superior Province have been determined. δ¹⁸O values of low grade, immature clastic metasediments range from 8.0 to 13.3%. and hence are somewhat depleted in ¹⁸O relative to other clastic metasediments. The lower ¹⁸O content is attributed to the large proportion of unaltered rock fragments in the Archean metasediments. Felsic metavolcanics have a similar range of δ¹⁸O values (7.3 to 13.0%..δ¹⁸O values for the middle amphibolite facies Pakwash paragneiss (8.8–11.7%.) are higher than those determined for the amphibolite to granulite facies Twilight paragneiss (7.3–9.2%.). Archean orthogneisses such as the Clay Lake gneiss (7.0–9.0%.), the Cedar Lake gneiss (7.4–8.7%.) and the Footprint gneiss (5.9-8.8%.) have δ¹⁸O values similar to those of the Twilight paragneiss. Therefore, at least at metamorphic grades higher than middle amphibolite facies, Archean metasedimentary gneisses may have δ¹⁸O values that are indistinguishable from those of Archean orthogneisses, and hence are no longer isotopically recognizable as metasedimentary rocks.     

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.     

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.