Changes in the HOAr isotope composition of clays during retrograde alteration

K-Ar ages of illite alteration associated with Middle Proterozoic Athabasca unconformity-type U deposits in Saskatchewan range from 414 to 1493 Ma. The K-Ar ages correlate with water contents and δD values such that illites with young K-Ar ages have δD values as low as −169 and water contents as high as 7.7 wt.% whereas illites with older ages have δD values near −70 and water contents near 4 wt.%. Water extracted at 400°C from illites with low δD values and high water contents has low δD and δ¹⁸O values similar to those of modern meteoric water suggesting that some of the illites associated with the original deposition of the ore underwent varying degrees of retrograde alteration. The alteration is initiated by hydration of sites in the interlayer region of the illite which results in the partial resetting of the K-Ar ages and introduction of excess structural water in the form of interlamellar water. The interlamellar water is enriched in ¹⁸O by about 7 per mil relative to the water that physically surrounded the clay particle. Further alteration decreases the δD value and increases the δ¹⁸O value of the illite by isotopic exchange between the mineral and the interlamellar water. Although the chemical compositions and XRD patterns of the altered illites indicate that no detectable smectite component is present in the samples, the isotopic results suggest that the altered illites may be an early precursor in the formation of mixed-layer illite/smectite by retrograde alteration of pure illite. The wide variation of δD values of chlorite and kaolinite from these U deposits is analogous to that of the illite suggesting that retrograde alteration of clays by meteoric water can be substantial. The general association of altered clays with areas containing the highest concentrations of U is probably related to localized permeability within the ore zone.     

Geothermometry, geochronology, and mass transfer associated with hydrothermal alteration of a rhyolitic hyaloclastite from Ponza Island, Italy

A rhyolitic hyaloclastite from Ponza Island, Italy, was hydrothermally altered, producing four distinct alteration zones based on X-ray diffraction mineralogy and field textures: (1) nonpervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the nonpervasive argillic zone, characterized by smectite and disordered opal-CT. The other three zones exhibit more complete alteration of the hyaloclastite. The propylitic zone is characterized by mixed-layer illite-smectite (I-S) with 10 to 85% I, mordenite, opal-C, and authigenic K-feldspar (akspar). The silicic zone is characterized by I-S with ≥90% I, pure illite, quartz, akspar, and occasional albite. The sericitic zone consists primarily of I-S with ≥66% I, pure illite, quartz, and minor akspar and pyrite. K/Ar dates of I-S indicate hydrothermal alteration occurred at 3.38 ± 0.08 Ma.Oxygen isotope compositions of I-S systematically decrease from zones 1 to 4. In the argillic zone, smectite has δ¹⁸O values of 21.7 to 22.0‰ and I-S from the propylitic, silicic, and sericitic zones ranges from 14.5 to 16.3‰, 12.5 to 14.0‰, and 8.6 to 11.9‰, respectively. δ¹⁸O values for quartz from the silicic and sericitic zones range from 12.6 to 15.9‰. By use of isotope fractionation equations and data from authigenic quartz-hosted primary fluid inclusions, alteration temperatures ranged from 50 to 65°C for the argillic zone, 85 to 125°C for the propylitic zone, 110 to 210°C for the silicic zone, and 145 to 225°C for the sericitic zone. Fluid inclusion data and calculated δ¹⁸O_water values indicate that hydrothermal fluids were seawater dominated.Mass-transfer calculations indicate that hydrothermal alteration proceeded in a relatively open chemical system and alteration in the sericitic zone involved the most extensive loss of chemical species, especially Si. Systematic gains in Mg occur in all alteration zones as a result of I-S clay mineral formation, and systematic losses of Na, Ca, and K occur in most zones. With the exception of Ca, calculations of mass transfer associated with hydrothermal alteration on Ponza agree with chemical fluxes observed in laboratory experiments involving hydrothermal reactions of rhyolite and seawater. The anomalous Ca loss at Ponza may be due to hydrothermal formation of anhydrite and later low-temperature dissolution. On the basis of Mg enrichments derived from circulating seawater, we estimate the following minimum water/rock ratios: 9, 3, 6, and 9 for the argillic, propylitic, silicic, and sericitic zones, respectively. Hydrothermal fluid pH for the propylitic and silicic zones was neutral to slightly basic and relatively acidic for the sericitic zone as a result of condensation of carbonic and perhaps other acids.     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.     

Influence de la diagenèse d''enfouissement sur l''homogénéisation isotopique K-Ar des illites: exemple du Jurassique-Crétacé du bassin d''Agadir, Maroc

The clay assemblages of the Late Jurassic-Early Cretaceous sediments of the Agadir Basin are affected by burial diagenesis. Apparent ages of these formations, from the K-Ar dating of fine grain size fractions (< 2 μm), decrease downward. This indicates an opening of the K-Ar isotopic system of detrital Hercynian minerals during burial. The extent of the isotopic rehomogenisation is more important in sandstones than in clayey marl facies. During burial diagenesis, a temperature of 165°C in clayey marl and 110°C in sandstone can be enough for isotopic rehomogenisation of fine-grained Hercynian illite. The migration of pore water seems to favour the diffusion of radiogenic ⁴⁰Ar in sandstones.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

Metamorphic growth and recrystallization of zircons in extremely O-depleted rocks during eclogite-facies metamorphism: Evidence from U-Pb ages, trace elements, and O-Hf isotopes

A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ¹⁸O values of 0.1-10.1‰, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ¹⁸O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ¹⁸O values of −10.0‰ to −2.2‰, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ¹⁸O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ¹⁸O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ¹⁸O magmatic core and the negative δ¹⁸O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ¹⁸O fluids. The zircons recrystallized in solid-state maintained positive δ¹⁸O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ¹⁸O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ¹⁸O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.     

Relationship between compositions of basaltoids in geosynclinal and orogenic volcanic associations

During the early stages of North Atlantic rifting, in the Late Triassic and Early Liassic, intracontinental basins with the eruption of tholeiitic lavas developed along the Atlantic margin of Morocco and in the Atlas domain. K-Ar dating of different grain-size fractions of Cambrian schists from the Hercynian basement and of sediments from the Triassic cover yield apparent ages which decrease with grain size, from 330-300 Ma for the coarse fractions to about 220-200 Ma for the clay-size fractions. These apparent ages indicate either K-Ar resetting of Hercynian minerals, or the development of new minerals during one or more Upper Triassic to Lower Liassic thermal or hydrothermal events. Theoretical calculations indicate that a temperature of 185-210 ° C maintained for 15 ± 10 m.y. can account for the isotopic rehomogenization of the fine-grained Hercynian micas of the High Atlas. The probable cause was a rise of the upper mantle in a thin continental crust during the first stages of Atlantic rifting.     

Sedimentary K-Ar signatures in clay fractions from Mesozoic marine shelf environments in Israel

The K-Ar system in clay fractions from shallow marine carbonate shelf environments was investigated on silicate fractions (clay minerals, feldspar) separated from 20 Lower Jurassic to Upper Cretaceous sedimentary rocks, deposited in the southern Tethys ocean. The range of lithologies investigated included dolomite and chalk [IR (insoluble residue)<10%], marl, shale (IR= 70–85%) and sandstone (IR>90%). The results show that K-bearing clay fractions often have K-Ar ages similar to the suggested age of deposition, which means either supply of land-derived authigenic K-bearing clays or synsedimentary diagenetic authigenesis, or both. This K-Ar synsedimentary signal is recorded in clay fractions from the whole range of studied lithologies and stratigraphic units. Among the clay minerals, the synsedimentary K-Ar signature was recorded and retained in illite/smectite of the <2-um and <0.2-um fractions. A prominent synsedimentary signature is found in K-feldspars, from shaly and especially from calcareous rocks, which is substantiated by their authigenic origin based on idiomorphic crystal morphology and their limited size distribution (4–10 um). Post-depositional closure of the K-Ar system is indicated by ages up to 15 Ma younger than the stratigraphic age in different lithologies from dispersed localities. A distinct late diagenetic (20–25 Ma younger) event is recorded in the formation of authigenic K-feldspar within Upper Cretaceous chalk and shale. In the IR and >10-um fractions the K-Ar ages reflect the contribution of detrital mica and feldspar which accompanies the kaolinite-dominated samples. The overall results differ considerably from K-Ar age patterns observed in deep-sea sediments, a difference which may be connected with the occurrence of brines in these shelf deposits. The findings indicate the potential in the K-Ar dating of fine IR fractions of marine shelf sediments in terms of geochronological-stratigraphic and palaeogeographical aspects as well as in the petrology of clay minerals themselves.     

Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Ion microprobe measurements of O/O ratios of phosphate minerals in the Martian meteorites ALH84001 and Los Angeles

Oxygen isotope ratios of merrillite and chlorapatite in the Martian meteorites ALH84001 and Los Angeles have been measured by ion microprobe in multicollector mode. δ¹⁸O values of phosphate minerals measured in situ range from ∼3 to 6‰, and are similar to Martian meteorite whole-rock values, as well as the δ¹⁸O of igneous phosphate on Earth. These results suggest that the primary, abiotic, igneous phosphate reservoir on Mars is similar in oxygen isotopic composition to the basaltic phosphate reservoir on Earth. This is an important first step in the characterization of Martian phosphate reservoirs for the use of δ¹⁸O of phosphate minerals as a biomarker for life on Mars. Cumulative textural, major-element, and isotopic evidence presented here suggest a primary, igneous origin for the phosphates in Los Angeles and ALH84001; textural and chemical evidence suggests that phosphates in ALH84001 were subsequently shock-melted in a later event.     

Natural fractionation of U/U

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the ²³⁸U/²³⁵U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed ²³⁶U-²³³U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ²³⁸U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ²³⁸U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ²³⁸U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ²³⁸U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ²³⁸U (−0.41‰ to −0.16‰) compared to seawater, which has δ²³⁸U of −0.41 ± 0.03‰. Granites define a range of δ²³⁸U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ²³⁸U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble U^VI to insoluble U^IV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that ²³⁸U/²³⁵U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in ²⁰⁷Pb/²⁰⁶Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.     

Low δO zircons, U-Pb dating, and the age of the Qinglongshan oxygen and hydrogen isotope anomaly near Donghai in Jiangsu Province, China

Zircons from metamorphosed granites exposed near Qinglongshan have δ¹⁸O_VSMOW values of −7 to 0‰ in both grain rims and cores. The concordant ²³⁸U/²⁰⁶Pb ages of zircon cores are 684 to 754 Ma with rims at 221 Ma. Discordant ²³⁸U/²⁰⁶Pb ages range from 242 to 632 Ma. Results demonstrate a Neoproterozoic age for the origin of the Qinglongshan oxygen and hydrogen isotope anomaly. The low δ¹⁸O values were imprinted on the rocks by a hydrothermal system charged with meteoric water from a cold climate. Groundwater circulation was driven by heat from cooling granitic magma. The geologic age of the hydrothermal system correlates with that of the Nantuo tillite in the Sinian strata of the South China block, suggesting that Qinglongshan’s cold climate may be a manifestation of Neoproterozoic “snowball Earth.”     

Zircon U-Pb and oxygen isotope evidence for a large-scale O depletion event in igneous rocks during the Neoproterozoic

Oxygen isotope analysis and U-Pb dating were carried out on zircons from granite, granitic gneiss and eclogite in the Dabie-Sulu orogenic belt of east-central China. The results show a wide variation in zircon δ¹⁸O values from −10.9 to 8.5‰. Most of the values are lower than normal mantle zircon and almost half have prominently negative values. The low δ¹⁸O zircons have protolith ages of 700 to 800 Ma and metamorphic ages of 205 to 250 Ma, respectively. Fluid availability within the metaigneous rocks dictates the extent of metamorphic recrystallization and overgrowth. The igneous zircons have preserved their magmatic zoning and middle Neoproterozoic U-Pb age during the Triassic metamorphism, indicating low fluid availability. Widespread low δ¹⁸O values are identified in the magmatic zircons of middle Neoproterozoic age, within an outcrop area of over 20,000 km² along the northern edge of the South China Block. The low δ¹⁸O zircons record the presence of large volumes of low δ¹⁸O igneous rocks that were derived from remelting of meteoric-hydrothermally altered rocks at some time between 700 and 800 Ma.The U-Pb ages for metaigneous protoliths and granites are correlated not only with the timing of rifting accompanying the breakup of Rodinia, but also with contemporary glacial deposits in the South China Block at paleolatitudes of 30 to 40°N. Melting of glacial ice and snow is suggested, instead of the direct involvement of meteoric water, to produce the low δ¹⁸O fluid with oxygen isotopic signatures like the cold-climate meteoric water. The rifting created conditions favorable to anatexis of meteoric-hydrothermally altered rocks. Glaciated regions supplied copious water for the water-rock interaction during magma emplacement along rifting zones. Both rifting and glaciation favored the generation of the low δ¹⁸O magmas in the region. The low δ¹⁸O zircons are thus interpreted to have crystallized from the low δ¹⁸O magmas of middle Neoproterozoic age, and onset of the generation of low δ¹⁸O magmas in the northern margin of the South China Block is estimated to occur at about 758 ± 15 Ma. The large-scale remelting of hydrothermally altered crust not only results from repetitive emplacement of mafic magmas along the rifting zones with protracted episodes of water-rock interaction, but also involves rift systems that rapidly introduce large volumes of fluid through confined pathways and traps in a short space of time in response to tectonic triggers. Occurrence of the large-scale ¹⁸O depletion during the middle Neoproterozoic may be a manifestation of the cold paleoclimate related to the snowball Earth event.     

Environmental significance of C/C and O/O ratios of modern land-snail shells from the southern great plains of North America

¹³C/¹²C and ¹⁸O/¹⁶O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ¹⁸O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ¹³C values ranged from −13.2‰ to 0.0‰. δ¹⁸O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ¹⁸O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ¹⁸O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ¹³C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ¹³C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C₃, C₄) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.     

Assessment of grain-scale homogeneity and equilibration of carbon and oxygen isotope compositions of minerals in carbonate-bearing metamorphic rocks by ion microprobe

Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ¹⁸O and ±0.71‰ for δ¹³C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ¹⁸O and 0.10-0.29‰ for δ¹³C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ¹³C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ¹³C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ¹⁸O (up to 9.4‰), intercrystalline inhomogeneity in δ¹⁸O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ¹⁸O and δ¹³C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ¹⁸O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ¹⁸O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.     

O/O and D/H in goethite from a North American Oxisol of the Early Eocene climatic optimum

An Early Eocene Oxisol in the Ione Formation of California formed in a coastal continental weathering environment at a paleolatitude of ∼38°N. The dominant minerals in the Oxisol are goethite, quartz, and kaolinite. Material balance calculations were applied to new measurements of chemical composition, D/H, and ¹⁸O/¹⁶O ratios of Oxisol samples to determine the δD (−150 ± 3‰) and δ¹⁸O (−2.4 ± 0.3‰) values of the goethite (α-FeOOH). These data, in combination with the global meteoric water line (MWL), yielded an isotopic temperature of 21(±4) °C. The nominal value of 21 °C contrasts with the modern mean annual temperature (MAT) of 16 °C in that area. The warmer temperature is consistent with formation of the goethite during the Early Eocene climatic optimum. The isotopic composition of the goethite and a temperature of 21 °C imply ancient water with a δD value of −61(±4)‰ and a δ¹⁸O value of −8.9(±0.5)‰. This Early Eocene δ¹⁸O (or δD) value is more negative than values in the range of isotopic scatter observed for modern global precipitation at sites with a MAT of 21 °C.At times of warm global climates, the location of a near-surface atmospheric isotherm would generally shift relative to its location under modern climatic conditions. A simple Rayleigh-type condensation model indicates that, if one “follows the isotherm”, the associated scatter in δD and δ¹⁸O of precipitation in very warm global climates should shift (for a given isotherm) to more negative values that may be detectable in proxy records. The isotopic results from the goethite of the Early Eocene Oxisol appear to add to evidence in support of this idea.     

High precision SIMS oxygen three isotope study of chondrules in LL3 chondrites: Role of ambient gas during chondrule formation

We report high precision SIMS oxygen three isotope analyses of 36 chondrules from some of the least equilibrated LL3 chondrites, and find systematic variations in oxygen isotope ratios with chondrule types. FeO-poor (type I) chondrules generally plot along a mass dependent fractionation line (Δ¹⁷O ∼ 0.7‰), with δ¹⁸O values lower in olivine-rich (IA) than pyroxene-rich (IB) chondrules. Data from FeO-rich (type II) chondrules show a limited range of δ¹⁸O and δ¹⁷O values at δ¹⁸O = 4.5‰, δ¹⁷O = 2.9‰, and Δ¹⁷O = 0.5‰, which is slightly ¹⁶O-enriched relative to bulk LL chondrites (Δ¹⁷O ∼ 1.3‰). Data from four chondrules show ¹⁶O-rich oxygen isotope ratios that plot near the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line. Glass analyses in selected chondrules are systematically higher than co-existing minerals in both δ¹⁸O and Δ¹⁷O values, whereas high-Ca pyroxene data in the same chondrule are similar to those in olivine and pyroxene phenocrysts.Our results suggest that the LL chondrite chondrule-forming region contained two kinds of solid precursors, (1) ¹⁶O-poor precursors with Δ¹⁷O > 1.6‰ and (2) ¹⁶O-rich solid precursors derived from the same oxygen isotope reservoir as carbonaceous chondrites. Oxygen isotopes exhibited open system behavior during chondrule formation, and the interaction between the solid and ambient gas might occur as described in the following model. Significant evaporation and recondensation of solid precursors caused a large mass-dependent fractionation due to either kinetic or equilibrium isotope exchange between gas and solid to form type IA chondrules with higher bulk Mg/Si ratios. Type II chondrules formed under elevated dust/gas ratios and with water ice in the precursors, in which the ambient H₂O gas homogenized chondrule melts by isotope exchange. Low temperature oxygen isotope exchange may have occurred between chondrule glasses and aqueous fluids with high Δ¹⁷O (∼5‰) in LL the parent body. According to our model, oxygen isotope ratios of chondrules were strongly influenced by the local solid precursors in the proto-planetary disk and the ambient gas during chondrule melting events.     

沧参1井石炭,二叠纪地层粘土矿物年代学研究

笔者对沧参1井石炭、二叠纪地层中的粘土矿物特征进行研究,并对不同深度的粘土矿物进行了K－Ar、40Ar－39Ar及Rb－Sr法同位素地质年龄测定,得出至少存在三期伊利石的结论;碎屑伊利石,年龄为400Ma左右,在235—243Ma时受到热扰动;海西期末一印支早期形成的高温伊利石,其年龄为214—234Ma,在145Ma时经受一次热扰动;早侏罗世时期形成的伊利石,年龄为180Ma左右,分布比较普遍。这一研究结果无疑将有助于深入探讨区域地热场的演化,以及进一步研究有关地层的生、储油气能力。     

Volcanic arc of Kamchatka: a province with high-δO magma sources and large-scale O/O depletion of the upper crust

We present the results of a regional study of oxygen and Sr-Nd-Pb isotopes of Pleistocene to Recent arc volcanism in the Kamchatka Peninsula and the Kuriles, with emphasis on the largest caldera-forming centers. The δ¹⁸O values of phenocrysts, in combination with numerical crystallization modeling (MELTS) and experimental fractionation factors, are used to derive best estimates of primary values for δ¹⁸O(magma). Magmatic δ¹⁸O values span 3.5‰ and are correlated with whole-rock Sr-Nd-Pb isotopes and major elements. Our data show that Kamchatka is a region of isotopic diversity with high-δ¹⁸O basaltic magmas (sampling mantle to lower crustal high-δ¹⁸O sources), and low-δ¹⁸O silicic volcanism (sampling low-δ¹⁸O upper crust). Among one hundred Holocene and Late Pleistocene eruptive units from 23 volcanic centers, one half represents low-δ¹⁸O magmas (+4 to 5‰). Most low-δ¹⁸O magmas are voluminous silicic ignimbrites related to large >10 km³ caldera-forming eruptions and subsequent intracaldera lavas and domes: Holocene multi-caldera Ksudach volcano, Karymsky and Kurile Lake-Iliinsky calderas, and Late Pleistocene Maly Semyachik, Akademy Nauk, and Uzon calderas. Low-δ¹⁸O magmas are not found among the less voluminous products of stratovolcano eruptions and these volcanoes do not show drastic changes in δ¹⁸O during their evolution. Additionally, high-δ¹⁸O(magma) of +6.0 to 7.5‰ are found among basalts and basaltic andesites of Bezymianny, Shiveluch, Avachinsky, and Koryaksky volcanoes, and dacites and rhyolites of Opala and Khangar volcanoes (7.1-8.0‰). Phenocrysts in volcanic rocks from the adjacent Kurile Islands (ignimbrites and lavas) define normal-δ¹⁸O magmas. The widespread and volumetric abundance of low-δ¹⁸O magmas in the large landmass of Kamchatka is possibly related to a combination of near-surface volcanic processes, the effects of the last glaciation on high-latitude meteoric waters, and extensive geyser and hydrothermal systems that are matched only by Iceland. Sr and Pb isotopic compositions of normal and low-δ¹⁸O, predominantly silicic, volcanic rocks show negative correlation with δ¹⁸O, similar to the trend in Iceland. This indicates that low-δ¹⁸O volcanic rocks are largely produced by remelting of older, more radiogenic, hydrothermally altered crust that suffered δ¹⁸O-depletion during >2 My-long Pleistocene glaciation. The regionally-distributed high-δ¹⁸O values for basic volcanism (ca. + 6 to +7.5‰) in Kamchatka cannot be solely explained by high-δ¹⁸O slab fluid or melt (± sediment) addition in the mantle, or local subduction of hydrated OIB-type crust of the Hawaii-Emperor chain. Overall, Nd-Pb isotope systematics are MORB-like. Voluminous basic volcanism (in the Central Kamchatka Depression in particular) requires regional, though perhaps patchy, remobilization of thick (30-45 km) Mesozoic-Miocene arc roots, possibly resulting from interaction with hot (ca. 1300°C), wedge-derived normal-δ¹⁸O, low-⁸⁷Sr/⁸⁶Sr basalts and from dehydration melting of lower crustal metabasalts, variably high in δ¹⁸O and ⁸⁷Sr/⁸⁶Sr.