238U 230Th Research Articles

Zircon double-dating, trace element and O isotope analysis to decipher late Pleistocene explosive-effusive eruptions from a zoned ocean-island magma system, Ascension Island

In this first detailed study of zircon from Ascension Island, South Atlantic, we take a novel approach combining trace element and O isotope compositional data with double-dating (disequilibrium 238U–230Th and (U–Th)/He) to decipher timescales and dynamics of magmatic processes. The Echo Canyon (EC) sequence comprises small-volume explosive-effusive eruptions of trachyte that tapped a compositionally zoned magma system. Associated volcanic hazards may be constrained from the age of volcanism, duration of magma storage, and magma source and plumbing system character. Zircon U–Th–Pb dating of lithic lava clasts has revealed recurrent evolved volcanism at 1.34 and 0.6 Ma, and 95 ka. The (U–Th)/He zircon cooling ages indicate that most of the EC explosive-effusive sequence erupted in a brief episode at ca. 95 ka. Additionally, uniform 238U–230Th zircon crystallisation ages suggest moderately protracted magma storage with melt present at depth for at most 103–104 years before eruption. The enriched character of zircon trace element compositions, relative to MORB, in the absence of a continental crustal signature in the oxygen isotope values (δ18O range 2.67–5.63‰), suggests the presence of an enriched component in the EC magma source. Furthermore, low δ18O zircon compositions imply assimilation of high temperature hydrothermally altered country rock by the source magma. The mineral assemblage in crystal-poor pumices indicates equilibrium storage conditions: zircon saturation and Ti-in-zircon crystallisation temperatures are consistent with alkali feldspar-melt temperatures. Significantly, zircon crystals were preserved both as macrocryst inclusions and in the groundmass of EC explosive and effusive deposits. These rocks preserve evidence of magma evolution by fractional crystallisation. This process led to pre-eruptive compositional stratification, which is evidenced in the range of whole-rock major and trace element compositions and zircon Zr/Hf values. Notably, zircon crystallisation and cooling ages derived from pumice, lava, and accidental lithic lava clasts in highly explosive pyroclastic deposits, have revealed episodes of evolved magmatism that would otherwise have gone undetected. In addition, the zircon trace element and isotope compositions, in combination with the range of crystallisation ages, evidence progressively deeper tapping of less evolved magma stored in discrete lenses. Thus, a combined zircon geochronological-geochemical approach can place constraints on the ca. 0.6 Ma recurrence of past explosive-effusive pulses of millennial to decamillennial duration and their enriched magma sources. This information is relevant for assessing hazards and informing monitoring and forecasting efforts to assist in managing associated risks for small ocean island volcanoes with particularly vulnerable populations and infrastructure.

Timing and recurrence intervals for voluminous silicic eruptions from Amatitlán caldera (Guatemala)

Defining a precise timeline for past eruptions from explosive volcanoes in continental arcs is imperative to forecast future hazards and mitigate volcanic disasters in these often densely populated regions. However, establishing reliable ages for Quaternary eruptions in the Central American Volcanic Arc has been challenging due to the common lack or alteration of suitable K-rich phases for 40Ar/39Ar geochronology, but also from their position in time beyond the reach of 14C dating. This especially holds for the active Amatitlán caldera in Guatemala, from which at least six explosive silicic eruptions have produced tephra blanketing neighboring regions that are today inhabited by millions of people. Zircon, a common datable accessory mineral in Amatitlán caldera magmas, is used here to retrieve eruption ages by applying the novel zircon double-dating method (ZDD) that integrates 238U–230Th disequilibrium dating and (U–Th)/He thermochronology. This approach yielded the first-ever radioisotopic ages of 24 ± 3 ka and 48 ± 6 ka (1σ), respectively, of two of Amatitlán caldera's most recent eruptions (J-tephra and E-tephra). Remarkably, both zircon crystallization and ZDD eruption ages for the older and voluminous T-tephra and L-tephra units significantly post-date existing plagioclase 40Ar/39Ar dates by ca. 26 and 70 kyr, respectively. The ZDD eruption age for T-tephra is 93 ± 4 ka, whereas zircon crystallization ages for L-tephra yield a maximum model eruption age of ca. 124 ka. The strong eruption age divergence between ZDD and plagioclase 40Ar/39Ar dating argues for the presence of inherited or xenocrystic plagioclase in Amatitlán caldera eruptive products. Statistical analysis based on the updated eruptive history suggests a recurrence interval of ca. 17 kyr, which is significantly shorter than previously estimated. The new age data, thus, suggest a more frequent eruptive activity of Amatitlán caldera than formerly thought and underscores the necessity to better understand the current underlying magmatic system and to constrain its past eruptive history more precisely.

Testing the initial 230Th/232Th for “Known Age Carbonate” and its significance for 230Th dating and paleoclimate research

The 230Th dating (238U–234U–230Th dating method) has become one of the most important dating methods for Quaternary research. However, the 230Th/232Th ratio of 4.4 ± 2.2ⅹ10−6 is widely used for age correction in 230Th dating method. Here, we collected active speleothems with exactly known age and zero-year-old calcium carbonate from caves and dated them by 230Th dating. Our data indicated that the initial 230Th/232Th ratio can be one order of magnitude higher than the ratio of 4.4 ± 2.2 × 10−6. High initial 230Th/232Th ratio may result in false and comparatively old calculated age than the real age of young samples with low 238U concentration. So, the accurate initial 230Th/232Th ratio of active speleothem deposited in the same cave, instead of the general initial 230Th/232Th ratio, is essential for the precise age correction of young speleothem samples of low 238U concentration. Finally, we proposed a procedure to correlate modern observation and speleothem based paleoclimate reconstruction, on the basis of precise 230Th age which corrected by the true initial 230Th/232Th ratio.

Novel method for determining <sup>234</sup>U–<sup>238</sup>U ages of Devils Hole 2 cave calcite (Nevada)

Abstract. Uranium–uranium (234U–238U) disequilibrium dating can determine the age of secondary carbonates over greater time intervals than the well-established 230Th–234U dating method. Yet it is rarely applied due to unknowns in the initial δ234U (δ234Ui) value, which result in significant age uncertainties. In order to understand the δ234Ui in Devils Hole 2 cave, Nevada, we have determined 110 δ234Ui values from phreatic calcite using 230Th–234U disequilibrium dating. The sampled calcite was deposited in Devils Hole 2 between 4 and 590 ka, providing a long-term look at δ234Ui variability over time. We then performed multi-linear regression among the δ234Ui values and correlative δ18O and δ13C values. The regression can be used to estimate the δ234Ui value of Devils Hole calcite based upon its measured δ18O and δ13C values. Using this approach and the measured present-day δ234U values of Devils Hole 2 calcite, we calculated 110 independent 234U–238U ages. In addition, we used newly measured δ18O, δ13C, and present-day δ234U values to calculate 10 234U–238U ages that range between 676 and 731 ka, thus allowing us to extend the Devils Hole chronology beyond the 230Th–234U-dated chronology while maintaining an age precision of ∼ 2 %. Our results indicate that calcite deposition at Devils Hole 2 cave began no later than 736 ± 11 kyr ago. The novel method presented here may be applied to future speleothem studies in similar hydrogeological settings, given appropriate calibration studies.

A history of violence: magma incubation, timing and tephra distribution of the Los Chocoyos supereruption (Atitlán Caldera, Guatemala)

ABSTRACTThe climactic Los Chocoyos (LCY) eruption from Atitlán caldera (Guatemala) is a key chronostratigraphic marker for the Quaternary period given the extensive distribution of its deposits that reached both the Pacific and Atlantic Oceans. Despite LCY tephra being an important marker horizon, a radioisotopic age for this eruption has remained elusive. Using zircon (U–Th)/He geochronology, we present the first radioisotopically determined eruption age for the LCY of 75 ± 2 ka. Additionally, the youngest zircon crystallization 238U–230Th rim ages in their respective samples constrain eruption age maxima for two other tephra units that erupted from Atitlán caldera, W‐Fall (130 +16/−14 ka) and I‐Fall eruptions (56 +8.2/−7.7 ka), which under‐ and overlie LCY tephra, respectively. Moreover, rim and interior zircon dating and glass chemistry suggest that before eruption silicic magma was stored for >80 kyr, with magma accumulation peaking within ca. 35 kyr before the LCY eruption during which the system may have developed into a vertically zoned magma chamber. Based on an updated distribution of LCY pyroclastic deposits, a new conservatively estimated volume of ~1220 ± 150 km3 is obtained (volcanic explosivity index VEI > 8), which confirms the LCY eruption as the first‐ever recognized supereruption in Central America.

Magma plumbing system for the Millennium Eruption at Changbaishan volcano, China: Constraints from whole-rock U–Th disequilibrium

A caldera-forming eruption in 946 CE, known as the Millennium Eruption (ME), at Changbaishan (or Baekdusan) volcano, located on the border between China and North Korea, was one of the largest explosive eruptions on Earth in the last 2000 years. In this study, we obtained new whole-rock Sr, Nd, and Pb isotopic data and 238U–230Th disequilibrium data of representative volcanic products of the ME, as well as those of a pre-ME (4–5 ka) eruption, to understand the evolution of the magma plumbing system related to the caldera-forming eruption. The volcanic products of the ME have SiO2 contents ranging from ~54 to ~75 wt%, and the whole-rock (230Th/232Th) ratios tend to decrease systematically from basaltic trachy-andesite through trachyte to comendite. The relatively high (230Th/232Th) ratios of the felsic (trachytic and comenditic) volcanic products suggest that they were formed primarily from fractional crystallization of mafic magmas, rather than from partial melting of crustal materials. The basaltic trachy-andesite sample has a distinctly high (230Th/232Th) ratio and the least radiogenic Pb isotopic ratios among ME volcanic products, suggesting that the mafic magma was recently introduced into the main felsic magma system and is hypothesized to have triggered the eruption. The lower (230Th/232Th) ratios of the comendite samples than those of the trachyte samples, as well as published U-series disequilibrium data, suggest that the comendite magmas were produced by mixing old (> ~ 23 ka) and young (<~6 ka) comenditic magmas. The old comendite magma was the main component of ME volcanic products. Pre-ME pantelleritic magmas with distinctly low (230Th/232Th) and high 87Sr/86Sr ratios from those of ME magmas may have formed a short-lived magma chamber until ~4–5 ka, which was isolated from the long-lived, main comendite magma chamber.

Evaluating uranium radiochronometry by single-collector mass spectrometry for nuclear forensics: a multi-instrument investigation

Radiochronometric data, a key signature in evaluating the provenance and process history of nuclear material out of regulatory control, are conventionally acquired via multi-collector mass spectrometry. Here we explore the potential of age-dating by single-collector mass spectrometry. To evaluate model age accuracy/precision across different instrument designs, we performed 230Th–234U and 231Pa–235U radiochronometry of CRM 125-A using two single-collector and one multi-collector plasma source mass spectrometers. Single-collector instruments produce accurate model ages for this uranium standard and thus hold promise for nuclear forensics radiochronometry. Increased acquisition of age information via multiple instrument designs will bolster the global response to nuclear interdictions.

Improved protactinium spike calibration method applied to 231Pa–235U age-dating of certified reference materials for nuclear forensics

The application of multiple radiochronometers in a forensic investigation of bulk uranium provides increased confidence for interpreting age-dating results. We have developed a streamlined method for the purification of Pa and Th from bulk uranium and have applied this method in analyzing uranium certified reference materials (CRMs) IRMM-1000 and CRM U100, using the 231Pa–235U and 230Th–234U radiochronometers. Our improved 233Pa spike calibration technique has replaced the time-intensive, conventional calibration using geologic rock standards. Paired Pa–U and Th–U age-dating analyses of CRM U100 produce concordant results. In contrast, analyses of IRMM-1000 demonstrate reproducibly-discordant Th–U and Pa–U age-dates.

Aragonite–calcite veins of the ‘Erzberg’ iron ore deposit (Austria): Environmental implications from young fractures

AbstractThe well‐known Erzberg site represents the largest siderite (FeCO3) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO3 (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The 238U–234U–230Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO3 polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO3 precipitation and CO2 outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.

Application of the 226Ra–230Th–234U and 227Ac–231Pa–235U radiochronometers to UF6 cylinders

Uranium-series radiometric dating was performed on two well-pedigreed UF6 cylinder samples containing highly enriched uranium that were in use at the Portsmouth Gaseous Diffusion Plant between the mid-1970s and mid-1980s. Daughter–parent (i.e. 231Pa–235U, 230Th–234U) radiometric ages determined on solid heel materials (e.g. UO2F2, UF4) recovered from the emptied cylinders are unrealistically old due to the preferential sequestration of progeny isotopes relative to uranium within the solid heels. However, limited elemental fractionation amongst the progeny isotopes themselves in the heel material allowed for realistic age constraints on the fill dates of the UF6 cylinders to be extracted from the granddaughter–daughter systems (i.e. 226Ra–230Th, 227Ac–231Pa).

Influence of Th-rich mineral phases on U–Th radioactive disequilibrium ages of sulfide deposits from the Okinawa Trough

Many samples of hydrothermal sulfide minerals from the Okinawa Trough yield 234U–230Th radioactive disequilibrium ages that are inconsistent with the ages of coexistent barite obtained using electron spin resonance (ESR) method. These results contrast strongly against results obtained for the Southern Mariana Trough, for which the U–Th radioactive disequilibrium ages are roughly consistent with the ESR ages. Sulfide minerals from the Okinawa Trough show large variation in U and Th abundances, suggesting open-system behavior. We infer that the interaction of hydrothermal fluids with thick terrigenous sediment caused large-scale migration of U and Th in the Okinawa Trough. The (234U/230Th) – (232Th/230Th) plots for the sulfide samples from the Hatoma Knoll and the Izena Hole show two mixing trends for each site. The presence of Th-rich phase with high (230Th/234U) ratio seems to cause incorrect age estimates of the sulfide deposits.

The application of radiochronometry during the 4th collaborative materials exercise of the nuclear forensics international technical working group (ITWG)

In a recent international exercise, 10 international nuclear forensics laboratories successfully performed radiochronometry on three low enriched uranium oxide samples, providing 12 analytical results using three different parent-daughter pairs serving as independent chronometers. The vast majority of the results were consistent with one another and consistent with the known processing history of the materials. In general, for these particular samples, mass spectrometry gave more accurate and more precise analytical results than decay counting measurements. In addition, the concordance of the 235U–231Pa and 234U–230Th chronometers confirmed the validity of the age dating assumptions, increasing confidence in the resulting conclusions.

U-series disequilibria in minerals from Gandak River sediments (Himalaya)

The impact of mineralogical sorting on U-Th-Ra variations observed for the Ganga sediments in the Himalayan alluvial plain due to transport and deposition processes highlights the importance to better understand the U-series isotopic system in Himalayan minerals. For this purpose, U, Th, and Ra concentrations, along with 238U–234U–230Th–226Ra radioactive disequilibria, were measured in several pure mineral fractions, i.e. monazite, zircon, titanite, ilmenite, rutile, garnet, magnetite, quartz, biotite and muscovite, separated from one bank sediment of the Gandak River (Ganga Basin). The data, obtained through a double digestion protocol in high-pressure and high-temperature vessels, confirm that U and Th concentrations and isotopic ratios of the sediments are mainly influenced by a few minor mineral species that are very enriched in U and Th, namely, monazite, titanite and epidote, as well as major minerals with lower U and Th concentrations, such as quartz. More importantly, the data clearly indicate that, similarly to whole rock samples, the U-Th-Ra systematics of individual minerals have likely recorded complex U-Th-Ra fractionations. In particular, the 226Ra enrichment observed in the biotite and clay fractions likely results from the affinity of Ra for phyllosilicate minerals, while the 230Th and, to a lesser extent the 234U enrichment observed for the other minerals might result from a nuclide adsorption process on the Fe-oxide coatings present on the grains or directly on the mineral surface. The linear trend outlined by the minerals phases in the (226Ra/230Th) vs (230Th/234U) diagram suggests that 230Th is probably mobilized from zircons, the only fraction presenting (230Th/234U)<1, and from monazites, and redistributed among the all minerals during weathering. Such a scenario suggest that zircon weathering, evidenced in this study, must have been very recent, estimated <2000years by a modeling approach, including simulation of nuclides mobility by alpha-recoil ejection and loss and gain processes.

US-DOE and CIAE international cooperation in age-dating uranium standards

In 2014 the United States Department of Energy and the China Institute of Atomic Energy collaborated in a study measuring the model ages of uranium certified reference materials. Lawrence Livermore National Laboratory (LLNL) and Los Alamos National Laboratory (LANL), and the Chinese Institute of Atomic Energy (CIAE) determined 230Th–234U model ages for uranium certified reference materials U010 and U850. The aim of this work was to collaborate with CIAE and compare methods for measuring the age of bulk uranium materials using the 230Th–234U radiochronometer. Accurate results for age-dating depend on the accurate calibration of the tracer materials (e.g., 229Th and 233U) used for the isotope dilution mass spectrometry (IDMS) analyses. To facilitate inter-comparison of results, samples of a 230Th standard reference material were distributed to each laboratory for 229Th tracer inter-calibration. The resulting 230Th–234U model ages from this collaboration for U010 ranged from March 1956 to January 1959, which agree with the known material production date of June 5th, 1958. The determined model ages for U850 were from December 1955 to October 1957, which agree with the material production date of December 31, 1957. All three laboratories used independent methods to determine model ages for uranium standards that agree with known production ages and with previously reported results.

Application of the 226Ra–230Th–234U and 227Ac–231Pa–235U radiochronometers to uranium certified reference materials

Uranium certified reference materials (CRM) issued by New Brunswick Laboratory were subjected to dating using four independent uranium-series radiochronometers. In all cases, there was acceptable agreement between the model ages calculated using the 231Pa–235U, 230Th–234U, 227Ac–235U or 226Ra–234U radiochronometers and either the certified 230Th–234U model date (CRM 125-A and CRM U630), or the known purification date (CRM U050 and CRM U100). The agreement between the four independent radiochronometers establishes these uranium certified reference materials as ideal informal standards for validating dating techniques utilized in nuclear forensic investigations in the absence of standards with certified model ages for multiple radiochronometers.

238U–230Th–226Ra–210Pb–210Po Disequilibria Constraints on Magma Generation, Ascent, and Degassing during the Ongoing Eruption of Kīlauea

238U–230Th–226Ra–210Pb–210Po Disequilibria Constraints on Magma Generation, Ascent, and Degassing during the Ongoing Eruption of Kīlauea

U–Th–Ra variations in Himalayan river sediments (Gandak river, India): Weathering fractionation and/or grain-size sorting?

Understanding the origin of U–Th–Ra variations in the Ganga river sediments is a prerequisite for correctly using U-series nuclides to constrain the sediment transport times in Himalayan rivers. For this purpose, U, Th, and Ra concentrations, along with 238U–234U–230Th–226Ra radioactive disequilibria, were analyzed in bank, bedload and suspended sediments from the Gandak river, one of the main tributaries of the Ganga river. The data confirm that U and Th budgets of the Himalayan sediments are significantly influenced by minor resistant minerals, such as zircon, garnet and Ti-bearing minerals, the dissolution of which required the use of a high-pressure acid digestion process. Most importantly, the results indicate that the variations in (238U/232Th) and (230Th/232Th) activity ratios and 238U–234U–230Th–226Ra disequilibria in sediments along the river alluvial plain mainly reflect modifications in the mineralogical and grain-size compositions rather than the degree of weathering during transport. The (238U/232Th) and (230Th/232Th) activity ratios in the bank and bed sediments are related to variations in the minor primary minerals strongly enriched in U and Th (i.e., zircon, REE-bearing minerals and Ti-bearing minerals), whereas the activity ratios in the suspended load are related to variations in the proportions of clay, Fe-oxyhydroxides and the silt-sand fraction, which contains U- and Th-bearing minor minerals. The data also indicate that 238U–234U–230Th–226Ra disequilibria are strongly influenced by secondary mineral phases: the 230Th budget is likely mainly controlled by Fe-oxyhydroxides, and the 226Ra budget is likely mainly controlled by clay minerals. Therefore, the variations in the 238U–234U–230Th–232Th system in the sediments of the Gandak river cannot simply be interpreted as the result of fractionation due to chemical transformation of the bulk sediment during its transport within the alluvial plain and/or the result of radioactive decay. Consequently, they cannot be used to infer long sediment transport times within the Gandak plain (10–100ka), as previously proposed. Such analytical and interpretative artifacts are certainly not specific to the present study on the Gandak basin. These issues will certainly be encountered anytime this technique is applied to alluvial systems in which the U and Th budgets of the sediments are influenced by “heavy” minerals that can be sorted during the transport of sediments within the plain.

Regolith evolution on the millennial timescale from combined U–Th–Ra isotopes and in situ cosmogenic 10Be analysis in a weathering profile (Strengbach catchment, France)

U–Th–Ra disequilibria, cosmogenic in situ 10Be concentrations and major and trace element concentrations have been analyzed in a 2 m-deep weathering profile sampled at the summit of the granitic Strengbach catchment (France). The data have been used to independently estimate both the long-term regolith production and denudation rates and the weathering and erosion rates. Modeling of the 238U–234U–230Th–226Ra disequilibrium variations in the lower part of the profile yields a regolith production rate of 12±4 mm/kyr (30 ± 10 T/km2/yr), while modeling of the high-resolution 10Be concentration profile leads to an exposure age of 19.7±2.2 kyr, an inherited concentration of 15,000 ± 1,000 at/g in quartz and a mean denudation rate of 22 ± 10 mm/kyr (37 ± 15 T/km2/yr). The consistency between production and denudation rates suggests that, on a millennial timescale, the regolith mass balance at the summit of the catchment is close to a steady state, even if the watershed may have been impacted by Quaternary climatic changes and by recent anthropogenic perturbations (e.g., 20th century acid rain and recent afforestation efforts). The results also indicate that physical erosion is likely the dominant long-term process of regolith denudation in the catchment. Furthermore, the comparison of the long-term production and denudation rates and of weathering and erosion rates determined from the depth profile analyses with the current weathering and erosion rates estimated at the outlet of the watershed based on monitoring of the water chemistry and sediment fluxes suggests that physical erosion may have varied more than the chemical weathering flux during the last 150 kyr. Although very few other sites with U-series, in situ 10Be and stream monitoring data are available for comparison, the current data suggest that (1) the mass balance steady state of regolith might be commonly achieved in soil mantled landscapes, and (2) physical erosion has varied much more than chemical weathering in mid-mountain catchments over the last 10–150 kyr. These results highlight the importance of the combined analysis of U-series nuclides and in situ 10Be in the same weathering profile for the determination of key geomorphic parameters, which are important to constraining landscape stability and the responses of landscapes to natural or anthropogenic forcing.

Isotopic constraints on the genesis and evolution of basanitic lavas at Haleakala, Island of Maui, Hawaii

To understand the dynamics of solid mantle upwelling and melting in the Hawaiian plume, we present new major and trace element data, Nd, Sr, Hf, and Pb isotopic compositions, and 238U–230Th–226Ra and 235U–231Pa–227Ac activities for 13 Haleakala Crater nepheline normative basanites with ages ranging from ∼900 to 4100yr B.P. These basanites of the Hana Volcanics exhibit an enrichment in incompatible trace elements and a more depleted isotopic signature than similarly aged Hawaiian shield lavas from Kilauea and Mauna Loa. Here we posit that as the Pacific lithosphere beneath the active shield volcanoes moves away from the center of the Hawaiian plume, increased incorporation of an intrinsic depleted component with relatively low 206Pb/204Pb produces the source of the basanites of the Hana Volcanics. Haleakala Crater basanites have average (230Th/238U) of 1.23 (n=13), average age-corrected (226Ra/230Th) of 1.25 (n=13), and average (231Pa/235U) of 1.67 (n=4), significantly higher than Kilauea and Mauna Loa tholeiites. U-series modeling shows that solid mantle upwelling velocity for Haleakala Crater basanites ranges from ∼0.7 to 1.0cm/yr, compared to ∼10 to 20cm/yr for tholeiites and ∼1 to 2cm/yr for alkali basalts. These modeling results indicate that solid mantle upwelling rates and porosity of the melting zone are lower for Hana Volcanics basanites than for shield-stage tholeiites from Kilauea and Mauna Loa and alkali basalts from Hualalai. The melting rate, which is directly proportional to both the solid mantle upwelling rate and the degree of melting, is therefore greatest in the center of the Hawaiian plume and lower on its periphery. Our results indicate that solid mantle upwelling velocity is at least 10 times higher at the center of the plume than at its periphery under Haleakala.

Systematics of U–Th disequilibrium in calcrete profiles: Lessons from southwest India

Pedogenic carbonates (calcretes) have often been proposed as possible markers of the pedogenetic processes in soils under semi-arid climate. However, precise chronological constraints on their formation are required in order to investigate the climatic and paleo-environmental conditions that prevailed during and after their formation, and to improve our understanding of the physical and chemical conditions that promoted their development and preservation. Moreover, these authigenic calcium carbonate precipitates provide us with an interesting test of the U–Th radioactive disequilibrium dating method, the reliability of which has been demonstrated extensively in aragonitic corals and calcitic continental speleothems, but which remains much more questionable in highly porous, chemically and mineralogically complex media such as soil profiles. We report here 238U–234U–230Th radioactive disequilibrium analyses measured by Thermo-Ionization Mass Spectrometry in calcretes from two sites in southwest India. Since calcretes are impure carbonates mixed with various amounts of parent rock and weathered minerals, all ages must be computed using the isochron technique, involving the extraction of several coeval subsamples from the same soil horizon and U–Th analyses after total dissolution (TSD) method, in order to correct for the detrital component. 232Th is usually used as index of the detrital contamination, and the isochron age is derived from the isotopic composition (230Th/238U; 234U/238U) of the pure authigenic carbonate end-member of the mixing line.Our results show that each set of samples taken from decimetric blocks is characterized by a well-defined isochron line in a 3-D Osmond diagram (232Th/238U; 230Th/238U; 234U/238U). The regression lines obtained for most of the samples show probabilities of fit satisfying the mathematical assumptions of the isochron model (in most cases ≫0.05), and mean square weighted deviations (MSWD) values around 1. The compositions of the end-members are highly variable between the different isochrons, both for the carbonate phase, indicating various ages of cristallisation, and for the detrital phase, indicating various origins and compositions. Notably, our data demonstrate that the detrital component is in all cases out of secular equilibrium, by contrast with the standard paradigm of “dirty carbonate” dating, which is based on the assumption of average continental crust Th/U elemental ratio, and secular equilibrium values of the (230Th/238U) and (234U/238U) ratios. At the first site (Coimbatore), we obtain U–Th ages between 304±38ka and 44±2.9ka (2σ) from the base to the top of the profile. These suggest discontinuous precipitation of the different facies in good agreement with micromorphological observations. At the second study site (Gundlupet), the carbonate nodules sampled from two different profiles, yield consistent ages of 200ka, which suggests that precipitation of nodular carbonate occurred across the entire pediment toposequence during a single event. Surprisingly, in mere contradiction with the standard model of impure carbonate dating, two puzzling samples display “vertical isochrons”, i.e., variable 232Th/238U without any variation of the 230Th/238U and 234U/238U ratios. Such patterns require extremely high 232Th/238U ratios, in an as yet unidentified detrital phase.Taken at face value, these results suggest that no clear correlation can be inferred between the precipitation of these pedogenic carbonates and major orbitally-driven climate variations recorded in other archives during the last glacial/interglacial cycles.