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.     

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.     

Organic carbon 13C12C variations in estuarine sediments

The δC¹³ value for sedimentary organic carbon in four estuaries of the Gulf of Mexico increases with radial distance from the river mouth. Mass balance calculations indicate that terrestrial organic carbon is limited to sediments within a relatively short distance from the river mouth. This distance is a function of the discharge rate of the river. For the Mississippi River, terrestrial organic carbon is limited to sediments within 69 km of the mouth of Pass à Loutre and 61 km of South Pass. These data indicate that the low δC¹³ (< ?22%.) values reported for Pleistocene sediments in the Gulf of Mexico may be the result of factors in addition to the postulated large influx of terrestrial organic carbon.     

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.     

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     

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.     

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.     

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.     

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.     

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.     

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.     

Quaternary sea level fluctuations on a tectonic coast: New 230Th234U dates from the Huon Peninsula,New Guinea

Emerged coral reef terraces on the Huon Peninsula in New Guinea were reported in a reconnaissance dating study by Veeh and Chappell 1970. Age definition achieved was not good for several important terraces, and we report here a series of new ${}^{230}\text{Th}{}^{234}\text{U}$ dates, which further clarify the history of late Quaternary eustatic sea level fluctuations. More than 20 reef complexes are present, ranging well beyond 250,000 yr old: we are concerned with the seven lowest complexes. Major reef-building episodes dated by ${}^{30}\text{Th}{}^{234}\text{U}$ are reef complex I at 5–9 ka (kilo anno = 1000 yr), r.c. IIIb at 41 ka (four dates), r.c. IV at 61 ka (four dates), r.c. V at 85 ka (two dates), r.c. VI at 107 ka (two dates), and r.c. VII at 118–142 ka. Complex II was previously dated by ¹⁴C at 29 ka: this age has not yet been confirmed, and may be only a lower limit. The reef crests were built during or immediately before intervals of sea level maxima, when rates of rising sea level and tectonic uplift briefly coincided. The culmination of each reef-building episode was only a few thousand years in duration, and multiple dates from the same reef complex generally group within the statistical errors of the individual dates.Several methods can be used to estimate the altitude of each sea level maximum relative to present sea level. The least complicated is to calculate mean tectonic uplift rate for each profile of the terraces, and use the mean rate to calculate the tectonic displacement of each dated reef complex on that profile. The difference between the present altitude of a reef complex and its calculated tectonic uplift gives the paleosea level at the time the reef grew. We estimate uplift rates for six surveyed sections by calibrating against published paleosea level estimates from Barbados and elsewhere, viz 125 ka, paleosea at +6 m; 103 ka, ?15 m; 82 ka, ?13 m. For each section the individual uplift rates for reefs V, VI, and VIIb are within 5% of their section means. Using the mean rates. paleosea level estimates for reef crests II, IIIB, and IV are made for each section. Consistency of estimates between sections is good, giving ?28 m for the 60 ka paleosea level, around ?38 m for the 42 ka level and ?41 m for the 28 ka level (if the age is older the paleosea level would be lower. Using the mean uplift rates, the 82 ka and 103 ka paleosea levels are also estimated for each section: all individual estimates are plotted graphically, and a sea level curve drawn. The reef stratigraphy indicates sea level lowerings between each dated reef crest: the crests probably represent the interstadials of the Wisconsin (Würm, Weichsel) Glaciation, and intervening lower levels correspond to stadials. Since the last time of eustatic sea level higher than the present (about 125 ka), five sea level maxima occurred at roughly 20-ka intervals, none being as high as the present.     

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.     

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.     

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.     

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.