Ar/Ar ages and paleomagnetism of São Miguel lavas, Azores

We present new ⁴⁰Ar/³⁹Ar ages and paleomagnetic data for São Miguel island, Azores. Paleomagnetic samples were obtained for 34 flows and one dike; successful mean paleomagnetic directions were obtained for 28 of these 35 sites. ⁴⁰Ar/³⁹Ar age determinations on 12 flows from the Nordeste complex were attempted successfully: ages obtained are between 0.78 Ma and 0.88 Ma, in contrast to published K–Ar ages of 1 Ma to 4 Ma. Our radiometric ages are consistent with the reverse polarity paleomagnetic field directions, and indicate that the entire exposed part of the Nordeste complex is of a late Matuyama age. The duration of volcanism across São Miguel is significantly less than previously believed, which has important implications for regional melt generation processes, and temporal sampling of the geomagnetic field. Observed stable isotope and trace element trends across the island can be explained, at least in part, by communication between different magma source regions at depth. The ⁴⁰Ar/³⁹Ar ages indicate that our normal polarity paleomagnetic data sample at least 0.1 Myr (0–0.1 Ma) and up to 0.78 Myr (0–0.78 Ma) of paleosecular variation and our reverse polarity data sample approximately 0.1 Myr (0.78–0.88 Ma) of paleosecular variation. Our results demonstrate that precise radiometric dating of numerous flows sampled is essential to accurate inferences of long-term geomagnetic field behavior. Negative inclination anomalies are observed for both the normal and reverse polarity time-averaged field. Within the data uncertainties, normal and reverse polarity field directions are antipodal, but the reverse polarity field shows a significant deviation from a geocentric axial dipole direction.     

Temporal–compositional trends over short and long time-scales in basalts of the Big Pine Volcanic Field, California

Primitive basaltic single eruptions in the Big Pine Volcanic Field (BPVF) of Owens Valley, California show systematic temporal–compositional variation that cannot be described by simple models of fractional crystallization, partial melting of a single source, or crustal contamination. We targeted five monogenetic eruption sequences in the BPVF for detailed chemical and isotopic measurements and ⁴⁰Ar/³⁹Ar dating, focusing primarily on the Papoose Canyon sequence. The vent of the primitive (Mg# = 69) Papoose Canyon sequence (760.8 ± 22.8 ka) produced magmas with systematically decreasing (up to a factor of two) incompatible element concentrations, at roughly constant MgO (9.8 ± 0.3 (1σ) wt.%) and Na₂O. SiO₂ and compatible elements (Cr and Ni) show systematic increases, while ⁸⁷Sr/⁸⁶Sr systematically decreases (0.7063–0.7055) and ε_Nd increases (− 3.4 to − 1.1). ¹⁸⁷Os/¹⁸⁸Os is highly radiogenic (0.20–0.31), but variations among four samples do not correlate with other chemical or isotopic indices, are not systematic with respect to eruption order, and thus the Os system appears to be decoupled from the dominant trends. The single eruption trends likely result from coupled melting and mixing of two isotopically distinct sources, either through melt-rock interaction or melting of a lithologically heterogeneous source. The other four sequences, Jalopy Cone (469.4 ± 9.2 ka), Quarry Cone (90.5 ±17.6 ka), Volcanic Bomb Cone (61.6 ± 23.4 ka), and Goodale Bee Cone (31.8 ± 12.1 ka) show similar systematic temporal decreases in incompatible elements. Monogenetic volcanic fields are often used to decipher tectonic changes on the order of 10⁵–10⁶ yr through long-term changes in lava chemistry. However, the systematic variation found in Papoose Canyon (10⁰–10² yr) nearly spans that of the entire volcanic field, and straddles cutoffs for models of changing tectonic regime over much longer time-scales. Moreover, ten new ⁴⁰Ar/³⁹Ar ages combined with chemistry from all BPVF single eruption sequences show the long-term trend of BPVF evolution comprises the overlapping, temporal–compositional trends of the monogenetic vents. This suggests that the single eruption sequences contain the bulk of the systematic chemical variation, whereas their aggregate compositions define the long-term trend of volcanic field evolution.     

Ar/Ar illite dating of Late Caledonian (Acadian) metamorphism and cooling of K-bentonites and slates from the Welsh Basin, U.K.

The vacuum-encapsulation laser ⁴⁰Ar³⁹Ar technique allows extremely small (10⁻⁶ g) samples of fine-grained materials such as diagenetic clays to be dated. Here we show that the method can be extended to higher-grade clay minerals. The integration of transmission electron microscopic (TEM) characterization with ⁴⁰Ar³⁹Ar dating of vacuum encapsulated samples permits the resolution of the timing of metamorphic growth/cooling from the time of diagenesis. We have applied this technique to well characterized Lower Paleozoic slates and K-bentonites from the Welsh Basin, which span the transition from anchizonal to epizonal grade, which had been previously studied using RbSr and SmNd dating.

TEM observations of epizonal K-bentonites and slate showed that illite in these samples is of 2M₁ polytype, of muscovite-like composition, and oriented parallel to cleavage, suggesting that they are of metamorphic origin. Total gas ages (equivalent to conventional KAr ages) for encapsulated epizonal K-bentonites and slate (340–408 Ma) are considerably variable. The Ar retention ages (calculated from ³⁹Ar and ⁴⁰Ar atoms retained in the sample after irradiation) are more consistent (383–411 Ma). The ³⁹Ar recoil losses are minor for illites from whole rock samples of epizonal K-bentonites but very significant for clay separates of epizonal slate. Plateaus in age spectra were observed in epizonal K-bentonites and slate. The plateau ages (414–421 Ma) and retention ages (383–411 Ma) can be correlated with the onset of Acadian metamorphism and culmination of uplift and inversion of the Welsh Basin, respectively. These ages are significantly younger than the 450 Ma ages previously reported for diagenetic clays using the same method, suggesting that diagenetic history has been lost in these epizonal K-bentonites and slate.

TEM observations of anchizonal slates showed that there are two modes of illite. The first mode is similar to that observed in epizonal samples, suggesting a metamorphic origin. The second mode consists of the 1M_d polytype, has typical diagenetic illite composition, and is oriented parallel to bedding, suggesting a diagenetic origin. Total gas ages for encapsulated anchizonal slates vary considerably (361–422 Ma). The retention ages are more consistent (413–432 Ma) than the total gas ages. The ³⁹Ar recoil losses are more significant than those for epizonal K-bentonites and slate. Plateaus in age spectra are generally not observed. However, the consistent retention ages for the anchizonal slates correspond to the plateau ages for the epizonal samples, and are inferred to represent the onset of Acadian metamorphism.

These data, when combined with our previously published results for diagenetic shales, suggest that thermal conditions near the boundary of anchizonal and epizonal grades are necessary to completely reset Ar systems in shales and slates.     

Refining the noble gas record of the Réunion mantle plume source: Implications on mantle geochemistry

We report isotope analyses of helium, neon, argon, and xenon using different extraction techniques such as stepwise dynamic and static crushing, and high-resolution stepwise heating of three mantle xenoliths from Réunion Island. He and Ne isotopic compositions were similar to previously reported Réunion data, yielding a more radiogenic composition when compared to the Hawaiian or Icelandic mantle plume sources. We furthermore observed correlated ¹²⁹Xe/¹³⁰Xe and ¹³⁶Xe/¹³⁰Xe ratios following the mantle trend with maximum values of 6.93 ± 0.14 and 2.36 ± 0.06, respectively. High-resolution argon analyses resulted in maximum ⁴⁰Ar/³⁶Ar ratios of 9000–11,000, in agreement with maximum values obtained in previous studies. We observed a well-defined hyperbolic mixing curve between an atmospheric and a mantle component in a diagram of ⁴⁰Ar/³⁶Ar vs. ²⁰Ne/²²Ne. Using a mantle ²⁰Ne/²²Ne of 12.5 (Ne–B) a consistent ⁴⁰Ar/³⁶Ar value of 11,053 ± 220 in sample ILR 84-4 was obtained, whereas extrapolations to a higher mantle ²⁰Ne/²²Ne ratio of 13.8 (solar wind) would lead to a much higher ⁴⁰Ar/³⁶Ar ratio of 75,000, far above observed maximum values. This favours a mantle ²⁰Ne/²²Ne of about 12.5 considered to be equivalent to Ne–B. Extrapolated and estimated ⁴⁰Ar/³⁶Ar ratios of the Réunion, Iceland, Loihi, and MORB mantle sources, respectively, tend to be linearly correlated with air corrected ²¹Ne/²²Ne and show the same systematic sequence of increasing relative contributions in radiogenic isotopes (Iceland–Loihi–Réunion–MORB) as observed for ⁴He/³He. In general, He–Ne–Ar isotope systematics of the oceanic mantle can be explained by following processes: (i) different degree of mixing between pure radiogenic and pure primordial isotopes generating the MORB and primitive plume (Loihi-type) endmembers; (ii) relatively recent fractionation of He relative to Ne and Ar, in one or both endmembers; (iii) after the primary fractionation event, different degrees of mixing between melts or fluids of MORB and primitive plume affinity generate the variety of observed OIB data, also on a local scale; (iv) very late-stage secondary fractionation during magma ascent and magma degassing leads to further strong variation in He/Ne and He/Ar ratios.     

Repeated thermal resetting of phengites in the Mulhacen Complex (Betic Zone, southeastern Spain) shown byAr/Ar step heating and single grain laser probe dating

This study reports the results of the first⁴⁰Ar/³⁹Ar combined induction furnace and laser probe dating of phengites from the Mulhacen HP/LT metamorphic complex in the Betic Cordilleras, southern Spain. Laser step heating and spot fusion analyses on different halves of a split single grain were made with a continuous laser probe. Spot fusion analysis resulted in ages of about 30–31 Ma in the core and ages as low as 25–26 Ma in the rim. Laser step heating on the other half of the grain gave a spectrum with apparent ages increasing from about 25 Ma to 29.5 Ma. The age spectrum and the decreasing ages towards the rim of the grain may imply that resetting essentially occurred by volume diffusion of radiogenic⁴⁰Ar due to late stage reheating resulting from extensional tectonics. Ages around 30 Ma in the core of the grain are interpreted as minimum estimates of the cooling age of the main tectono-metamorphic phaseD₂.

Induction furnace step heating on phengite separates from mica schists and one gneiss resulted in two types of age spectra. Type I spectra show monotonously rising apparent ages from14.5 ± 1.9 Ma to20.7 ± 0.2 Ma, and in a second sample from16.9 ± 0.7 to29.7 ± 0.2 Ma. Type II spectra are characterized by plateaus of14.4 ± 0.1 Ma (the gneiss sample),17.3 ± 0.1 Ma and17.6 ± 0.1 Ma. Type II spectra show low temperature apparent ages significantly below the plateau age, implying resetting subsequent to initial cooling. Modelling of the age spectra demonstrated that the plateau ages are possibly the result of strong resetting (75–85% of argon loss) of an older isotope system. Total fusion of a number of phengite single grains from marbles taken close to type II mica schists yielded ages of15.4 ± 1.2 Ma and17.0 ± 0.7 Ma. The observed repeated resetting is coeval with major volcanic activity in basins adjacent to the metamorphic ranges, pointing to a resetting by advective fluid transport related to volcanism.     

Systematics of xenocrystic contamination: preservation of discrete feldspar populations at McCullough Pass Caldera revealed by Ar/Ar dating

Single crystal ⁴⁰Ar/³⁹Ar dating of K-feldspars from silicic volcanic rocks containing xenocrysts often yields a spectrum of ages slightly older than those of juvenile sanidine phenocrysts. In contrast, feldspars from thin, low-volume units of the Tertiary (14 Ma) McCullough Pass Tuff define discrete age populations at 14 Ma, 15 Ma, and 1.3 Ga, reflecting the time of eruption, xenocrysts from an older ignimbrite exposed in the caldera wall, and Proterozoic basement K-feldspars, respectively. Conductive cooling and diffusion modelling suggests preservation of such discrete populations is likely only when xenocrystic material is incorporated into the magma very near or at the surface, or is engulfed in thin, rapidly cooled pyroclastic flows during emplacement. Incorporation of xenocrysts into the subvolcanic magma chamber, into thick rhyolite domes or lava flows, or into large, welded ignimbrite sheets will result in partial or total resetting of the K/Ar isotopic system. Similarly, petrographic evidence such as exsolution lamellae may be homogenized under these conditions but not in thin ignimbrites. Extremely low diffusion rates for disordering of the Al–Si tetrahedral siting of basement feldspars suggests that they will retain their ordered structural state given rhyolitic magma temperatures. Thus, even when petrographic and K/Ar isotopic evidence for xenocrystic contamination is obscured, it may be preserved in the form of Al–Si ordering.     

Link between SSZ ophiolite formation, emplacement and arc inception, Northland, New Zealand: U–Pb SHRIMP constraints; Cenozoic SW Pacific tectonic implications

New U–Pb age-data from zircons separated from a Northland ophiolite gabbro yield a mean ²⁰⁶Pb/²³⁸U age of 31.6 ± 0.2 Ma, providing support for a recently determined 28.3 ± 0.2 Ma SHRIMP age of an associated plagiogranite and  29–26 Ma ⁴⁰Ar/³⁹Ar ages (n = 9) of basalts of the ophiolite. Elsewhere, Miocene arc-related calc-alkaline andesite dikes which intrude the ophiolitic rocks contain zircons which yield mean ²⁰⁶Pb/²³⁸U ages of 20.1 ± 0.2 and 19.8 ± 0.2 Ma. The ophiolite gabbro and the andesites both contain rare inherited zircons ranging from 122–104 Ma. The Early Cretaceous zircons in the arc andesites are interpreted as xenocrysts from the Mt. Camel basement terrane through which magmas of the Northland Miocene arc lavas erupted. The inherited zircons in the ophiolite gabbros suggest that a small fraction of this basement was introduced into the suboceanic mantle by subduction and mixed with mantle melts during ophiolite formation.

We postulate that the tholeiitic suite of the ophiolite represents the crustal segment of SSZ lithosphere (SSZL) generated in the southern South Fiji Basin (SFB) at a northeast-dipping subduction zone that was initiated at about 35 Ma. The subduction zone nucleated along a pre-existing transform boundary separating circa 45–20 Ma oceanic lithosphere to the north and west of the Northland Peninsula from nascent back arc basin lithosphere of the SFB. Construction of the SSZL propagated southward along the transform boundary as the SFB continued to unzip to the southeast. After subduction of a large portion of oceanic lithosphere by about 26 Ma and collision of the SSZL with New Zealand, compression between the Australian Plate and the Pacific Plate was taken up along a new southwest-dipping subduction zone behind the SSZL. Renewed volcanism began in the oceanic forearc at 25 Ma producing boninitic-like, SSZ and within-plate alkalic and calc-alkaline rocks. Rocks of these types temporally overlap ophiolite emplacement and subsequent Miocene continental arc construction.     

Emerald dating through Ar/Ar step-heating and laser spot analysis of syngenetic phlogopite

Emerald, occurring in K-metasomatic rocks developed at the contact of the Carnaíba leucogranite with serpentinite (Bahia State, Brazil), has been dated using an original ⁴⁰Ar/³⁹Ar procedure. It combines step heating and spot fusion experiments on two types of phlogopite crystals: (1) bulk samples and individual grains extracted from the enclosing K-metasomatic host rocks; and (2) syngenetic solid inclusions precipitated along growing zones of the emerald host crystals. The second procedure uses in situ laser probe experiments on rock sections. In spite of the huge amounts of excess ⁴⁰Ar detected in adjacent emerald, we could measure reliable ages of 1951 ± 8 Ma and 1934 ± 8 Ma for the Trecho Velho and Braulia occurrences, respectively. Spot fusion data had higher discrepancy than the step heating data, but minute crystals of phlogopite included in emeralds bearing excess argon do not reveal excess argon. A muscovite belonging to the same granite hydrothermal complex gave a plateau age of 1976 ± 8 Ma, which may correspond to a higher closure temperature of the KAr system during the cooling of the whole pluton and associated hydrothermal halo.

These accurate measurements lead to the following conclusions: (1) direct emerald dating is possible; (2) in spite of a polyphase history during the Transamazonian orogenesis (2 Ga), combined step heating and spot fusion experiments give a better precision for granite-related emerald mineralization than the scattered ages obtained by Rb-Sr and K-Ar methods; (3) the late-Transamazonian tectonothermal retrograde event which probably caused the dispersion of previous Rb-Sr and K-Ar data is not revealed by our procedure; (4) the emerald mineralization and K-metamorphism appear to be linked with the thermal history of the leucogranite; (5) in addition to its use in polyphase crustal domains, accurate ⁴⁰Ar/³⁹Ar dating is of major interest in the field of metallogenic models, even, for instance, for mineralizations characterized by disturbed isotopic systems, which record effects as excess argon.     

Age of Jurassic continental tholeiites of French Guyana, Surinam and Guinea: Implications for the initial opening of the Central Atlantic Ocean

A detailed ⁴⁰Ar/³⁹Ar study, of mineral separates from the Jurassic Atlantic Continental Tholeiites (JACT) of Guyana (French Guyana and Surinam, South America), and Guinea (West Africa) related to the initial opening of the Central Atlantic, has been carried out. In French Guyana, plateau ages of 196.0 ± 5.7 Ma and 196.1 ± 7.5 Ma were obtained on single, small amphibole grains from NNW—SSE trending dykes. In Guinea, single biotite grains from intrusive formations from the Kakoulima and Fouta Djalon areas yielded plateau ages of 200.4 ± 0.2 Ma and 194.8 ± 0.5 Ma, concordant with high temperature apparent ages on other biotites. The bulk plagioclase samples display disturbed age spectra due to alteration and excess argon. However, intermediate temperature, weighted mean plagioclase ages are similar in both regions of Guyana and Guinea, ranging from 200.2 ± 2.4 Ma to 188.7 ± 1.9 Ma, partly in agreement with the amphibole and biotite data.

These data, combined with previous ⁴⁰Ar/³⁹Ar and U/Pb results from the northern part of the Central Atlantic margins, indicate intense magmatic activity distributed over a large area from Iberia to Liberia (ca. 4500 km long) for a short period of time (204-195 Ma, perhaps less for the bulk of the magmatism) during the initial break-up of Pangea continent. These data do not support an initiation of the magmatism from a radial volcano-tectonic system centred in the south of the region, as suggested by May [1], and the initial break-up seems to affect the whole Central Atlantic during a period of 9 Ma.     

Time constraints for Mesoproterozoic upper amphibolite facies metamorphism in NW Namibia: a multi-isotopic approach

This study presents the chronological evolution of the upper amphibolite facies Orue Unit in NW Namibia. Metasedimentary and meta-igneous rocks of the Orue Unit were investigated using the Pb–Pb stepwise leaching technique on garnet and rutile, U–Pb multi-grain analysis on rutile, Sm–Nd–Lu–Hf leaching technique on garnet, SHRIMP analysis on zircon and Ar–Ar dating on amphibole. Each of these techniques pertains to different processes that occurred before, during, or after the metamorphic peak. Our age data can be integrated with petrological constraints to provide a more complete understanding of the metamorphic cycle. Our pre-peak metamorphic zircon ages, peak metamorphic garnet ages and peak to late peak metamorphic amphibole ³⁹Ar–⁴⁰Ar ages bracket the upper amphibolite facies metamorphic event including hydration or dehydration processes into a time span of only ca. 20 Ma. The age data obtained by peak metamorphic mineral analyses cluster around 1340–1320 Ma. Based on age data and field observation, we interpret the upper amphibolite facies metamorphism as a large-scale regional mid-crustal event. Spot analyses of inherited zircon cores obtained by SHRIMP reflect the sedimentary origin of the respective rocks of the Orue Unit and derivation from Palaeoproterozoic protoliths. The metamorphic rocks south of the anorthositic Kunene Intrusive Complex (KIC) have previously been ascribed to the Palaeoproterozoic Epupa Complex at the SW margin of the Congo craton and were thus thought to be older than the Mesoproterozoic KIC. Our data show that the high-grade metamorphic overprint took place 30–50 Ma after emplacement of the KIC. Rutile growth ages of 1248 Ma in one sample reflect fluid activity which seems to be a local phenomenon since there is no other evidence of geological activity throughout the Orue Unit at that time. The rutile ages predate the emplacement of satellite intrusions in that area by 30 Ma and there is no causal relation between these two events.     

Diffusive fractionation of noble gases and helium isotopes during mantle melting

The large differences in He and Ar diffusivities in silicate minerals could result in fractionation of the He/Ar ratio during melting of the mantle, producing He/Ar ratios in the primary mantle melts that are higher than those of the bulk mantle. Modeling noble gas diffusion out of the bulk mantle into fast diffusion pathways (such as fractures or melt channels) suggests that significant (order of magnitude) He/Ar fractionation will occur if the fast diffusion channels are spaced several meters apart and the noble gas residence in these diffusion channels is of the order days to weeks. In addition, the 15% difference in ³He and ⁴He diffusivities could also produce isotopic fractionation between the melt and its solid source. Modeling the behavior of He and Ar during melting shows that small increases (few %) in ³He/⁴He should be correlated with larger variations (factor of 5) in ⁴He/⁴⁰Ar. However, in order to test this hypothesis the effects of subsequent He–Ar fractionation that occur during degassing have to be corrected. I describe a scheme that can separate He/Ar variations in the primary melt from overprinted fractionation during magmatic degassing. Using the degassing-corrected data, there is a correlation between the primary melt’s ⁴He/⁴⁰Ar and ³He/⁴He in mid-ocean ridge basalts (MORBs). The slope of the correlation is consistent with the models of preferential diffusion of ³He relative to ⁴He and of ⁴He relative to ⁴⁰Ar from the solid mantle into the melt. Diffusive fractionation of noble gases during melting of the mantle can also account for low ⁴He/⁴⁰Ar ratios commonly found in residual mantle xenoliths: preferential diffusion of He relative to Ar will produce some regions of the mantle with low ⁴He/⁴⁰Ar, the complement of the high ⁴He/⁴⁰Ar ratios in basalts. Diffusive fractionation cannot, however, account for differences between the He and Ne isotopic compositions of MORBs compared with ocean island basalts (OIBs); not only are the extremely high ³He/⁴He ratios of OIBs (up to 50 Ra) difficult to produce at reasonable mantle time and lengthscales, but also the Ne isotopic compositions of MORBs and OIBs do not lie on a single mass fractionation line, therefore cannot result from diffusive fractionation of a single mantle Ne source. If preferential diffusion of He from the solid mantle into primary melts is a significant process during generation of MORBs, then it is difficult to constrain the He concentration of the mantle: He concentrations in basalts and the He flux to the ocean essentially result from extraction of He from a larger (and unknown) volume of mantle than that that produced the basalts themselves. The He concentration of the mantle cannot be constrained until more accurate estimates of the diffusion contribution are available.     

Noble gas systematics of the Réunion mantle plume source and the origin of primordial noble gases in Earth’s mantle

New noble gas data of ultramafic xenoliths from Réunion Island, Indian Ocean, further constrain the characteristics of primordial and radiogenic noble gases in Earth’s mantle plume reservoirs. The mantle source excess of nucleogenic ²¹Ne is significantly higher than for the Hawaiian and Icelandic plume reservoirs, similar to excess of radiogenic ⁴He. ⁴⁰Ar/³⁶Ar of the Réunion mantle source can be constrained to range between 8000 and 12 000, significant ¹²⁹Xe and fission Xe excess are present. Regarding the relative contribution of primordial and radiogenic rare gas nuclides, the Réunion mantle source is intermediate between Loihi- and MORB-type reservoirs. This confirms the compositional diversity of plume sources recognized in other radioisotope systematics. Another major result of this study is the identification of the same basic primordial component previously found for the Hawaiian and Icelandic mantle plumes and the MORB reservoir. It is a hybrid of solar-type He and Ne, and ‘atmosphere-like’ or ‘planetary’ Ar, Kr, Xe (Science 288 (2000) 1036). ²⁰Ne/²²Ne ratios extend to maximum values close to 12.5 (Ne-B), which is the typical signature of solar neon implanted as solar corpuscular radiation. This suggests that Earth’s solar-type noble gas inventory was acquired by small (less than km-sized) precursor planetesimals that were irradiated by an active early sun in the accretion disk after nebular gas dissipation, or, alternatively, that planetesimals incorporated constituents irradiated in transparent regions of the solar nebula. Previously, such an early irradiation scenario was suggested for carbonaceous chondrites which follow common volatile depletion trends in the sequence CI–CM–CV–Earth. In turn, CV chondrites closely match Earth’s mantle composition in ²⁰Ne/²²Ne, ³⁶Ar/²²Ne and ³⁶Ar/³⁸Ar. This indicates that mantle Ar could well be a planetary component inherited from precursor planetesimals. However, a corresponding conclusion for mantle Kr and Xe is less convincing yet, but this may be just due to the lack of appropriate ‘meteoritic’ building blocks matching terrestrial composition. Alternatively, heavy noble gases in Earth’s mantle could be due to admixing of severely fractionated air, but this effect must have affected all mantle sources to a very similar extent, e.g. by global subduction before the last homogenization of the mantle reservoirs.     

Evidence for a mantle component shown by rare gases, C and N isotopes in polycrystalline diamonds from Orapa (Botswana)

In an attempt to constrain the origin of polycrystalline diamond, combined analyses of rare gases and carbon and nitrogen isotopes were performed on six such diamonds from Orapa (Botswana). Helium shows radiogenic isotopic ratios of R/Ra = 0.14–1.29, while the neon ratios (²¹Ne/²²Ne of up to 0.0534) reflect a component from mantle, nucleogenic and atmospheric sources. ⁴⁰Ar/³⁶Ar ratios of between 477 and 6056 are consistent with this interpretation. The (¹²⁹Xe/¹³⁰Xe) isotopic ratios range between 6.54 and 6.91 and the lower values indicate an atmospheric component. The He, Ne, Ar and Xe isotopic compositions and the Xe isotopic pattern are clear evidence for a mantle component rather than a crustal one in the source of the polycrystalline diamonds from Orapa. The δ¹³C and δ¹⁵N isotopic values of − 1.04 to − 9.79‰ and + 4.5 to + 15.5‰ respectively, lie within the range of values obtained from the monocrystalline diamonds at that mine. Additionally, this work reveals that polycrystalline diamonds may not be the most appropriate samples to study if the aim is to consider the compositional evolution of rare gases through time. Our data shows that after crystallization, the polycrystalline diamonds undergo both gas loss (that is more significant for the lighter rare gases such as He and Ne) and secondary processes (such as radiogenic, nucleogenic and fissiogenic, as well as atmospheric contamination). Finally, if polycrystalline diamonds sampled an old mantle (1–3.2 Ga), the determined Xe isotopic signatures, which are similar to present MORB mantle – no fissiogenic Xe from fission of ²³⁸U being detectable – imply either that Xe isotopic ratios have not evolved within the convective mantle since diamond crystallization, or that these diamonds are actually much younger.     

Geochronology and Nd isotopic data of Grenville-age rocks in the Colombian Andes: new constraints for Late Proterozoic-Early Paleozoic paleocontinental reconstructions of the Americas

New UPb zircon crystallization ages and ⁴⁰Ar/³⁹Ar cooling ages from the Colombian Andes confirm the existence of rocks metamorphosed during the Orinoquian Orogenic Event (ca. 1.0 Ga) of northern South America. ε_Nd (t = 1.1 Ga) for these rocks range from −3.9 to +0.91, which is interpreted as a mixture of Late Archean-Early Proterozoic crust with juvenile material produced during the 1.1 Ga orogenic event. The Colombian Grenville age rocks are part of a much longer metamorphic pericratonal belt, sporadically exposed along the Andes, in western-central Peru, southern Bolivia and northern Argentina. In addition, Nd model (T_DM) ages for the Colombian rocks range from 1.9 to 1.45 Ga, similar to those obtained in the Grenville Province of the eastern U.S. and in the Mexican basement, placing constraints on Late Proterozoic-Early Paleozoic paleocontinental reconstructions.     

Brine history indicated by argon, krypton, chlorine, bromine, and iodine analyses of fluid inclusions from the Mississippi Valley type lead-fluorite-barite deposits at Hansonburg, New Mexico

Argon, krypton, chlorine, bromine, and iodine were measured in a homogeneous population of high-salinity hydrothermal fluid inclusions from the Tertiary-age Mississippi Valley-type (MVT) lead-fluorite-barite deposits at Hansonburg, New Mexico to establish new types of evidence for the history of both the fluid and the major dissolved salts. Noble gases and halogens in fluid inclusions containing 10⁻¹⁰–10⁻⁹ L of brine (Cl= 3 molal) were analyzed by laser microprobe noble-gas mass spectrometry (lmngms) on neutron-irradiated samples.

The concentrations of³⁶Ar (4.7 × 10⁻⁸ molal) and⁸⁴Kr1.8 × 10⁻⁹ molal) in the fluid inclusions are equal to those of fresh surface waters in equilibrium with air at approximately20 ± 5°. The mole ratios ofBr/Cl (1.2 × 10⁻⁴) andI/Cl (1–2 × 10⁻⁶) are among the lowest measured in any natural waters, similar to those of modern brines formed by dissolution of Permian NaCl-bearing evaporites in southeast New Mexico.⁴⁰Ar/³⁶Ar ratios (600) are twice that of air, and indicate that the fluid inclusions had excess radiogenic⁴⁰Ar (1.4 × 10⁻⁵ molal) when trapped. The amount of excess⁴⁰Ar appears to be too large to have been acquired with Cl by congruent dissolution of halite-bearing evaporites, and possibly too small to have been acquired with Pb by congruent dissolution of granitic basement rocks with Proterozoic KAr ages.

From thelmngms data, combined with published Pb and S isotope data, we infer the following sequence of events in the history of the Hansonburg MVT hydrothermal brine: (1) the brine originated as relatively dilute meteoric water, and it did not gain or lose atmospheric Ar or Kr after recharge; (2) the originally dilute fluid acquired the bulk of its Cl and sulfate in the subsurface after recharge by dissolving halite-bearing Permian? marine evaporites; (3) the high salinity brine then acquired most of its Pb and excess radiogenic⁴⁰Ar from interactions with aquifer rocks other than evaporites, possibly clastic sedimentary rocks or basement rocks with Phanerozoic KAr “ages”; and (4) the brine deposited fluorite without having boiled or degassed.     

Excess argon, crustal fluids and apparent isochrons from crushing K-feldspar

Using a combination ofin-vacuo crushing and stepped heating, the⁴⁰Ar³⁹Ar technique has been applied to two K-feldspar-bearing sedimentary rocks from the Proterozoic of North China, with a view to studying ancient fluids trapped in these rocks and their chronology. Correlations between natural Ar isotopes and those produced by neutron irradiation permitted a clear distinction to be made between different components of natural argon. Crushing released Cl-correlated excess⁴⁰Ar (and palaeoatmospheric³⁶Ar) trapped in moderately saline fluid inclusions in quartz and possibly the K-feldspar. The very high⁴⁰Ar/Cl ratios of these fluids (2.7 × 10⁻⁴ and1.7 × 10⁻⁴) is interpreted as indicating a metamorphic source for the⁴⁰Ar. More surprisingly, crushing also released, from the K-feldspar, a K-correlated component with a very well defined⁴⁰Ar/K ratio, which for both samples corresponded formally to an apparent age comparable to or slightly less than the stratigraphic age. In contrast, stepped heating yielded⁴⁰Ar/K ratios corresponding to significantly younger ages which are interpreted as (low-grade) metamorphic ages. The explanation of the K-correlated component released on crushing and the significance (if any) of the distinct⁴⁰Ar/K ratio is obscure, although several effects involving microporosity and a combination of³⁹Ar recoil and diffusion are suggested. There is a contribution of this component to the stepped heating release pattern which may have implications for attempts to use K-feldspar as a⁴⁰Ar³⁹Ar thermochronometer.     

Precise Re–Os mineral isochron and Pb–Nd–Os isotope systematics of a mafic–ultramafic sill in the 2.0 Ga Onega plateau (Baltic Shield)

We present Re–Os, Sm–Nd and Pb–Pb isotope and trace element data for the Konchozero sill, a layered mafic–ultramafic intrusion in the Early Proterozoic Onega plateau, one of the oldest continental flood basalt provinces on Earth. The Sm–Nd and Pb–Pb combined mineral and whole-rock isochron ages of 1988±34 and 1985±57 Ma for the sill coincide with the age of ferropicrites from Pechenga (the Kola Peninsula). The lithostratigraphic, chemical and isotope evidence suggest the derivation of Pechenga lavas and the Onega plateau volcanics from a single mantle plume. Peridotite and gabbro whole-rock samples, and primary ulvospinel and ilmenite mineral separates from the sill yield a Re–Os isochron with a slope corresponding to an age of 1969±18 Ma, γ_Os(T) =−0.61±5.9. This age is consistent with the other isotope data, and indicates the closed-system behavior of Re and Os in the rocks. The peridotites and ulvospinel have high Os concentrations (2.5–14 ppb) and low ¹⁸⁷Re/¹⁸⁸Os ratios (0.35–1.1), thus allowing a more accurate determination of the weighted average initial ¹⁸⁷Os/¹⁸⁸Os of 0.1144±0.0019 (2σ_pop), γ_Os(T) =+0.77±1.7. This value is lower than that determined by Walker et al. (Geochim. Cosmochim. Acta 61 (1997) 3145–3160) for the Pechenga lavas (γ_Os(T) =+6.1±0.7), and implies a substantial Os-isotope heterogeneity in this ancient plume. Compared to the Onega plateau primary basalt magma, Pechenga ferropicrites are relatively enriched in iron and Ni, have lower (Nb/Th)_N ratios (2.1 vs 1.1) and less radiogenic Nd-isotope compositions (_Nd(T) = +3.1 and +1.4, respectively), but share similar low-radiogenic Pb-isotope characteristics (μ₁=8.57 and 8.60). Incorporation of small amounts (1.5%) of outer core material into the hotter central part of the plume and subsequent contamination of the Pechenga ferropicritic magmas with the 2.9 Ga Belomorian gneisses can explain the observed chemical and isotope variations in the two provinces provided that the core had <0.25 ppm of Pb.     

Glacial–interglacial changes in Subantarctic sea surface temperature and δO-water using foraminiferal Mg

Laboratory culturing experiments with living Globigerina bulloides indicate that Mg/Ca is primarily a function of seawater temperature and suggest that Mg/Ca of fossil specimens is an effective paleotemperature proxy. Using culturing results and a core-top Neogloboquadrina pachyderma calibration, we have estimated glacial–interglacial changes in sea surface temperature (SST) using planktonic Mg/Ca records from core RC11-120 in the Subantarctic Indian Ocean (43°S, 80°E) and core E11-2 in the Subantarctic Pacific Ocean (56°S, 115°W). Our results suggest that glacial SST was about 4°C cooler in the Subantarctic Indian Ocean and 2.5°C cooler in the Subantarctic Pacific. Comparison of SST and planktonic δ¹⁸O records indicates that changes in SST lead changes in δ¹⁸O by on average 1–3 kyr. The glacial–interglacial temperature change indicated by the Subantarctic Mg/Ca records suggests that temperature accounts for 40–60% of the foraminiferal δ¹⁸O change. We have used the Mg/Ca-based SST estimates and δ¹⁸O determinations to generate site-specific seawater δ¹⁸O records, which suggest that seawater δ¹⁸O was on average 1‰ more positive during glacial episodes compared with interglacial episodes.     

Granite generation and rapid unroofing related to strike-slip faulting, Aysén, Chile

A stock of biotite-muscovite-garnet leucogranite crops out in the lower course of Río Cisnes as an unusual minor lithology within the predominantly dioritic to tonalitic North Patagonian Batholith. Foliated and unfoliated varieties are present—the former are nearer to the main lineament of the Liquin˜e-Ofqui Fault Zone (LOFZ). Two-feldspar thermometry indicates equilibration temperatures above 600°C, for pressures probably not over 3 kbar, as suggested by the Mn-rich garnet composition. A Rb-Sr whole-rock isochron age of 9.6 ± 0.4 Ma (1σ error) probably indicates the time of magma crystallization. ⁴⁰Ar-³⁹Ar ages of 6.6 ± 0.3 Ma on muscovite and 5.5 ± 0.4 Ma on biotite are cooling ages from which a moderate average uplift/denudation rate ( 1 mm/yr) may be calculated. Paucity of occurrence, distribution close to the LOFZ and a near minimum-melt composition all suggest that the leucogranite magma was derived by partial melting of the lower crust, perhaps by decompression melting at a time when uplift/denudation rates were high (4 mm/yr or more are required). Regional evidence for rapid Holocene uplift in the immediate vicinity of the LOFZ substantiates the feasibility of the proposed petrogenetic model, which may be valid in other strike-slip orogenic environments.     

U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.