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Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87 Sr 86 Sr "> 87Sr86Sr ratios by less than 0.00001 at 1.95θ of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87 Sr 86 Sr "> 87Sr86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material.

Chemical Geology: Isotope Geoscience Section

Late-Wisconsin paleohydrology of the West-Central Amargosa Desert, Nevada, U.S.A.

Studies of isotopes in groundwater using 14 C, 2 H (deuterium) and 18 O have provided significant insight into the paleoclimate of middle and late Wisconsin age in a typical arid environment of southern Nevada, the west-central Amargosa Desert. Evidence indicates that recharge probably was through infiltration of runoff in paleostream channels and that this runoff was important only from ∼ 17,000 to ∼ 10,000 yr. B.P. Mean annual temperature at 17,000 yr. B.P. was ∼ 8°C less than present mean annual temperature; some summer moisture was effective in recharge. Winter (October–May) temperature at ∼ 10,000 yr. B.P. was ∼ 1°C less than present; summer moisture did not contribute to recharge.

Chemical Geology: Isotope Geoscience Section

Isotopic composition of pyrite: Relationship to organic matter type and iron availability in some North American cretaceous shales

The S isotope composition of pyrite in Cretaceous shales from the Western Interior of North America is related to organic C abundance, kerogen type and Fe availability. Both calcareous and noncalcareous rocks show a correlation between S and C, but noncalcareous rocks are relatively enriched in S with a higher S/C ratio. This higher ratio probably shows that pyrite formation was Fe limited in the calcareous rocks. Organic-carbon-rich noncalcareous shales accumulated slowly beneath anoxic bottom waters. The anoxic bottom waters allowed hydrogen-rich organic matter to be preserved. Such shales have a narrow range of 34 S-depleted sulfide and have Fe/S ratios like stoichiometric pyrite, suggesting that pyrite formation in organic-rich shales was also limited by Fe availability. Conversely, organic-poor shales commonly accumulated at comparatively high rates, contain hydrogen-poor and refractory organic matter, and have a wide range of pyrite-S isotopic compositions. These organic-poor shales contain post-sulfidic authigenic minerals such as siderite and have excess reactive Fe rather than pyrite stoichiometry. Evidently Fe played a large role in early diagenesis and determined the course of post-sulfidic diagenesis. Fe availability was, however, mainly controlled by provenance, by the rates of sediment accumulation, and by the oxygen content of the depositional environment.

Chemical Geology: Isotope Geoscience Section

Normalization of oxygen and hydrogen isotope data

To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the δ 18 O of SLAP is −55.5% relative to VSMOW. H 3 + contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content.

Chemical Geology: Isotope Geoscience Section

Paleozoic age of the Capo Spartivento Orthogneiss, Sardinia, Italy

Zircon U Pb "> UPb isotope dating of the Capo Spartivento Orthogneiss, proposed as a possible Precambrian basement of southern Sardinia, shows that this rock is Caledonian in age. Conventional multi-grain analyses yield an imprecise age of roughly 480 Ma, and ion-microprobe analyses of cores of single grains yield a consistent age of 449 Ma. Though some inherited grains of Proterozoic age are present in the zircon population, they are neither abundant nor consistent with Caledonian growth of new zircons within an older protolith.

Chemical Geology: Isotope Geoscience Section

Contrasting zircon morphology and UPb systematics in peralkaline and metaluminous post-orogenic granite complexes of the Arabian Shield, Kingdom of Saudi Arabia

Uzircon ages are reported for seven metaluminous-to-peralkaline post-orogenic granites from the Late Proterozoic Arabian Shield of Saudi Arabia. Zircons from the metaluminous rocks are prismatic, with length-to-width ratios of ∼ 2–4: 1 and small pyramidal terminations. In contrast, zircons from three of the four peralkaline complexes either lack well-developed prismatic faces (are pseudo-octahedral) or are anhedral. Some zircons from the peralkaline granites contain inherited radiogenic Pb and have very high common Pb contents ( 206 Pb/ 204 Pb < 150), making the UPb method poorly suited for determining the age of these rocks. Zircons in the metaluminous granites do not contain inheritance and yield well-defined concordia intercepts. The span of ages of the seven complexes (670-470 Ma) indicates that post-orogenic granitic magmatism was not a singular event in the Arabian Shield but rather occurred as multiple intrusive episodes from the Late Proterozoic to the Middle Ordovician.

Chemical Geology: Isotope Geoscience Section

UPb ages of zircon rims: A new analytical method using the air-abrasion technique

We present a new technique for directly dating, by conventional techniques, the rims of zircons. Several circumstances, such as a xenocrystic or inherited component in igneous zircon and metamorphic overgrowths on igneous cores, can result in grains with physically distinct age components. Pneumatic abrasion has been previously shown by Krogh to remove overgrowths and damaged areas of zircon, leaving more resistant and isotopically less disturbed parts available for analysis. A new abrader design, which is capable of very gently grinding only tips and interfacial edges of even needle-like grains, permits easy collection of abraded material for dating. Five examples demonstrate the utility of the “dust-collecting” technique, including two studies that compare conventional, ion microprobe and abrader data. Common Pb may be strongly concentrated in the outermost zones of many zircons and this Pb is not easily removed by leaching (even in weak HF). Thus, the benefit of removing only the outermost zones (and avoiding mixing of age components) is somewhat compromised by the much higher common Pb contents which result in less precise age determinations. A very brief abrasion to remove the high common Pb zones prior to collection of material for dating is selected.

Chemical Geology: Isotope Geoscience Section

Resetting of RbSr ages of volcanic rocks by low-grade burial metamorphism

We report a nine-point RbSr whole-rock isochron age of 70±3 Ma (MSWD 3.97) for Mid-Jurassic volcanic rocks. The same rocks have also been dated by the UThPb method on zircon, giving a crystallization age of 166 ± 11 Ma, over twice as old as the RbSr age. The data demonstrate that whole-rock RbSr ages of volcanic rocks, even lava flows with SiO 2 content as low as 57 wt.%, are susceptible to complete resetting. The rocks range in composition from rhyodacite tuffs to andesite lavas. The complete breakdown of all major minerals that contain Rb and Sr resulted in an alteration mineral assemblage consisting of phengite, albite, secondary quartz, and minor amounts of chlorite and epidote. Phengite is the K-bearing product of the breakdown of biotite and K-feldspar. Pressure during low-grade metamorphism of the volcanic rocks, estimated from phengite composition to have been in the range of 4 to 6 kbar, points to thrust-related burial as the main cause of resetting. Consequently, such reset isochrons may date large-scale events such as regional thrusting and metamorphism. The coherent resetting of the RbSr isochron suggests large-scale pervasive fluid movement during thrust-related burial metamorphism.

Chemical Geology: Isotope Geoscience Section

Caution on the use of Viton® or FETFE® O-rings in carbon dioxide sample containers for δ 18 0 analysis

After 10 days, 3-&mu;mol CO 2 samples in containers having glass stopcocks with Viton &reg; or FETFE O-rings were enriched in 18 O by 1.5% as a result of absorption by the elastomer; this amount of enrichment is &sim;20 times greater than the precision of &delta; 18 O measurements of most laboratories. No change in 13 C content was observed. Increasing the sample size to 100 &mu;mol resulted in an 18 O enrichment of 0.2% and did not affect the 13 C content. Caution needs to be exercised in selecting sample containers for CO 2 isotope-ratio samples of < 200 &mu;mol. If stopcocks are used in construction of containers for such samples, the use of all-glass stopcocks with Apiezon N &reg; hydrocarbon-based grease will eliminate the fractionation of oxygen isotopes.

Chemical Geology: Isotope Geoscience Section