How well do we understand production of 36Cl in limestone and dolomite?

We have evaluated all parameters for the calculation of cosmogenic ³⁶Cl production rates and thus surface exposure ages in dolomite and limestone. We found that we can use either of both published negative muon stopping rates until more information is available. The largest uncertainty of the age estimation in the upper meter of rock comes from the ³⁶Cl production rate from Ca spallation and, in the case of 50–100 ppm Cl content, from the production rate of epithermal neutrons, which we estimate at 760 ± 150 neutrons/g_air/yr (1σ). For a sample with representative amounts of Ca and Cl (20 wt% Ca and 50 ppm Cl, or 40 wt% Ca and 100 ppm Cl), the age can be calculated with a precision of 7–10% in the top 1.5 m of the depth profile. Further improvement of ³⁶Cl calculations depends on new calibration of ³⁶Cl production from Ca spallation, re-evaluation of ³⁶Cl production by low-energy neutron capture on ³⁵Cl, as well as of the muon flux and muon capture based on the most recent measurement data.     

First results on determination of cosmogenic 36Cl in limestone from the Yenicekale Complex in the Hittite capital of Hattusha (Turkey)

We have measured ³⁶Cl in three rock surfaces of the Yenicekale building complex in Hattusha (Bo?azköy, Turkey). Hattusha was the capital of Hittite Empire which lasted from about 1650/1600 to 1200 BC. At Yenicekale, Hittite masons flattened the summit of an outcropping limestone knoll to form an artificial platform as the foundation for a building. Next they built a circuit wall along the lateral precipices of the flattened bedrock platform. We took one sample from the limestone bedrock platform and two samples from limestone building blocks of the circuit wall for cosmogenic ³⁶Cl analysis. Calculated exposure ages are 20 ± 1 ka for the sample from the bedrock platform and 24 ± 1 ka and 52 ± 2 ka for the circuit wall blocks. These exposure ages are significantly older than the age expected based on the estimated time of construction between 3.2 ka and 3.7 ka. We conclude that the sampled surfaces contain significant inherited cosmogenic ³⁶Cl. We cannot directly determine exposure ages for the building complex based on these three samples. On the other hand we may use the measured concentrations to determine how much of the rock was removed from the platform during flattening. To this end we modeled the variation of ³⁶Cl production with depth at Yenicekale using the results from the bedrock sample. We conclude that the Hittite masons removed only around 3 m from top of the limestone block. This means that the volume of rock removed from the bedrock platform is significantly less than the volume in the circuit wall atop the platform. They did not gain enough rock from this flattening to make the building. In agreement with this, the first results of our detailed microfacies analysis indicate that many of the building blocks are not of the same facies as the underlying limestone and must have been quarried elsewhere. Although we were not able to exposure date the Yenicekale complex due to the presence of inherited ³⁶Cl, our data suggest that Hittite masons excavated (most of) the building stones not at Yenicekale, but in quarries outside of Hattusha and then transported them to the construction site. These quarries have not yet been identified.     

Cosmogenic 21Ne exposure dating of young basaltic lava flows from the Newer Volcanic Province,western Victoria,Australia

Cosmogenic ²¹Ne was utilised to determine exposure ages of young subaerial basaltic lava flows from the Newer Volcanic Province, western Victoria, Australia. The ages (36–53 ka) determined from co-existing cosmogenic ²¹Ne and ³He in olivines separated from basalts are consistent within analytical uncertainties with ages previously determined by cosmogenic ³⁶Cl exposure dating. This paper illustrates the potential of cosmogenic neon exposure ages in studying the eruption, surface morphology, and erosion history of young volcanic rocks, which are difficult to date using other conventional methods, such as K-Ar or ⁴⁰Ar/³⁹Ar dating. The present study demonstrates that combined cosmogenic ³He and ²¹Ne dating, specifically measured cosmogenic ³He/²¹Ne ratios, on the same samples, is powerful for evaluating the validity of calculated cosmogenic ³He and ²¹Ne surface exposure ages.     

Determination of chlorine concentrations in whole rock: Comparison between prompt-gamma activation and isotope-dilution AMS analysis

Accurate determination of chlorine concentrations in terrestrial rocks is of importance for the interpretation of terrestrial in-situ cosmogenic ³⁶Cl. Neutron capture by ³⁵Cl, together with production from Ca and K, is one of the three major production pathways of ³⁶Cl in rocks. Here, we present an inter-comparison of chlorine determinations by two procedures. The first approach is an independent Cl determination by prompt-gamma (neutron) activation analysis (PGAA). The second method is isotope-dilution based on isotopically enriched stable chlorine carrier added during chemical sample preparation for accelerator mass spectrometry (ID-AMS). Twenty-six (26) whole rock samples have been processed for PGAA and ID-AMS analysis. This study constitutes the first published inter-comparison for concentrations below 100 μgCl/g. Our results show no significant difference in Cl concentrations between methods. This agreement indicates good retention of chloride during the procedure we employ for whole rock sample dissolution. No significant loss of stable chlorine from either the spike or the sample occurs before isotopic equilibrium is reached, prior to AgCl precipitation. Uncertainties, which are <5% for both methods, affect the uncertainty of the total ³⁶Cl production rate less than 2% for our samples.The Cl concentration measured by PGAA can be used to calculate the amount of isotopically enriched spike for AMS-ID sample preparation with the aim to optimize ³⁶Cl analysis. Furthermore, PGAA offers an advance for the interpretation of ³⁶Cl measurements. It allows measurement of concentrations of major, minor and trace elements including the elements for ³⁶Cl production (Cl, K, Ca, Ti, and Fe), as well as of neutron absorbers and neutron moderators (H, B, Sm and Gd). These measurements are performed simultaneously and with a precision necessary for calculating the relative contributions to ³⁶Cl production from the different mechanisms.     

Cosmogenic 3He exposure dating of the Quaternary basalts from Fogo,Cape Verdes: Implications for rift zone and magmatic reorganisation

We have used cosmogenic ³He to date pre- and post-collapse lava flows from southwestern Fogo, Cape Verdes, in order to date rift zone magmatic reorganisation following the lateral collapse of the flank of the Monte Amarelo volcano. The post-collapse flows have exposure ages ranging from 62 to 11 ka. The analysis of multiple flow tops on each lava flows, often at different elevations, provides an internal check for age consistency and the exposures ages conform with stratigraphic level. The exposure ages suggest that volcanic activity along the western branch of the triple-armed rift zone was more or less continuous from before 62 ka to approximately 11 ka. The absence of magmatic activity for the last 11 kyr reflects a structural reconfiguration of the volcano and may be related to renewed flank instability. This volcanic hiatus is similar in duration to that observed in the Canary Islands. Replicate ³He exposure ages of a pre-collapse flow (123.0 ± 5.2 ka) brackets the time of the Monte Amarelo collapse between 62 ka and 123 ka. Reproducible cosmogenic ³He exposure ages of less than 123 ka from flows away from major erosion features demonstrates that the technique is a viable alternative to the radiocarbon, K/Ar and ⁴⁰Ar/³⁹Ar chronometers for dating recent volcanism in arid climate zones.     

Dating Holocene lavas on Stromboli,Italy using cosmogenic He

In-situ cosmogenic ³He exposure ages of pyroxene phenocrysts from basalts from the Upper Neostromboli formation in southwest Stromboli date its eruption at 7.0 ± 0.3 ka (1σ, n = 3, Ginostra site) and 6.8 ± 0.2 ka (1σ, n = 10, Timpone del Fuoco site) respectively. Correlation of our new data to previous K/Ar and palaeomagnetic ages from the northwestern Neostromboli phase suggests that it erupted within a confined period between roughly 6 and 14 ka. The low uncertainty on the ³He_cos ages as well as on individual exposure ages (4.4–8.7%) demonstrates that ³He_cos exposure dating is a viable tool for dating Holocene basalt lavas. The ages compare favourably to uncertainties obtained for radiocarbon dating of similar rocks.     

Evaluation of cosmogenic 3He and 21Ne production rates in olivine and pyroxene from two Pleistocene basalt flows,western Grand Canyon,AZ, USA

Combining cosmogenic ³He and ²¹Ne (³He_c and ²¹Ne_c) measurements on both pyroxene and olivine from the Pleistocene Bar Ten flows (85–107 ka) greatly increases our ability to evaluate the accuracy of ³He_c and ²¹Ne_c production rates and, therefore, ³He_c and ²¹Ne_c surface exposure ages. Comparison of ³He_c and ²¹Ne_c age-pairs yielded by experimentally determined production rates and composition-based model calculations indicates that the former give more accurate surface exposure ages than the latter in this study. However, experimental production rates should be adjusted to the composition of the minerals being analyzed to obtain the best agreement between ³He_c and ²¹Ne_c ages for any given sample. ²¹Ne_c/³He_c values are 0.400 ± 0.029 and 0.204 ± 0.014 for olivine and pyroxene, respectively, in Bar Ten lava flows, in agreement with previously published values, and indicate that ²¹Ne_c/³He_c in olivine and pyroxene is not affected by erosion and remains constant with latitude, elevation, and time (up to 10 Myr). Samples with ²¹Ne_c/³He_c that do not agree with these values may indicate the presence of non-cosmogenic helium and/or neon. The neon three-isotope diagram can also indicate whether or not all excess neon in mineral separates comes from cosmogenic sources. An error-weighted regression for olivine defines a spallation line [y = (1.033 ± 0.031)x + (0.09876 ± 0.00033)], which is indistinguishable from that for pyroxene (Schäfer et al., 1999). We have derived a production rate of 25 ± 8 at/g/yr for ²¹Ne_c in clinopyroxene (En_43–44) based on the ⁴⁰Ar/³⁹Ar age of the upper Bar Ten flow. Our study indicates that the production rate of ²¹Ne_c in olivine may be slightly higher than previously determined. Cosmogenic ³He and ²¹Ne remain extremely useful, particularly when paired, in determining accurate eruption ages of young olivine- and pyroxene-rich basaltic lava flows.     

Constraints on the nature of the subvolcanic reservoir at South Sister volcano,Oregon from U-series dating combined with sub-crystal trace-element analysis of plagioclase and zircon

We present sub-crystal-scale ²³⁸U–²³⁰Th zircon ages and ²³⁸U–²³⁰Th–²²⁶Ra plagioclase ages of bulk mineral separates from the Holocene (2.0–2.3 ka) eruptions of the Rock Mesa (RM) and Devil's Hills (DH) rhyolites at South Sister volcano, Oregon. We link these age data with sub-crystal trace-element analyses of zircon and plagioclase to provide insight into the subvolcanic system at South Sister, as an example of a small-volume continental arc volcano. Our results document the presence of coeval yet physically-distinct regions within the magma reservoir and constrain the timescales over which these heterogeneities existed. Zircons from the RM and DH dominantly record ages from 20 to 80 ka, with some grains recording ages > 350 ka, whereas plagioclase records ²³⁰Th–²²⁶Ra ages of 2.3–6.8 ka (RM) and 4.0–9.6 ka (DH-3) and a ²³⁸U–²³⁰Th age of 10 ± 34 ka (DH-3). We interpret zircons with ages < 350 ka as antecrysts inherited from a longer lived upper-crustal magma reservoir from which the rhyolites were generated, based on crystallization ages coeval with earlier periods of silicic volcanism at South Sister, the undersaturated nature of the RM and DH magmas with respect to zircon, and Ti-in-zircon temperatures consistent with low-temperature (< 815 °C) crystallization. In contrast, plagioclase ages are near the eruption age and dominantly preserve information about the recent (< 10 ka), higher-temperature evolution of the host magmas. Although zircon and plagioclase record different crystallization ages, each phase crystallized over the same time period in the RM compared to DH rhyolites. Linking these crystal age data with sub-crystal trace-element analyses demonstrates that zircon and plagioclase have distinct trace-element characteristics between eruptions, which require that the RM and DH crystals (and therefore magmas) were derived from distinct regions that had evolved independently for > 50 ka within a heterogeneous magmatic system and coexisted as physically-distinct, dominantly-liquid bodies prior to eruption. Thus, we favor a model where rhyolites are generated in independent batches by accumulation of evolved liquids in a heterogeneous, largely crystalline reservoir. Similarities in crystal age and chemical data to that at other young silicic systems (e.g., Mount St. Helens, Okataina Caldera Complex) suggest that this model may be more generally applicable to silicic magmas.     

Anomalous cosmogenic 3He production and elevation scaling in the high Himalaya

The production rate of cosmogenic ³He in apatite, zircon, kyanite and garnet was obtained by cross-calibration against ¹⁰Be in co-existing quartz in glacial moraine boulders from the Nepalese Himalaya. The boulders have ¹⁰Be ages between 6 and 16 kyr and span elevations from 3200 to 4800 m. In all of these minerals ³He correlates with ¹⁰Be and is dominantly cosmogenic in origin. After modest correction for non-cosmogenic components, ³He/¹⁰Be systematics imply apparent sea-level high-latitude (SLHL) apparent production rates for ³He of 226 atoms g^? 1 yr^? 1 in zircon, 254 atoms g^? 1 yr^? 1 in apatite, 177 atoms g^? 1 yr^? 1 in kyanite, and 153 atoms g^? 1 yr^? 1 in garnet. These production rates are unexpectedly high compared with rates measured elsewhere in the world, and also compared with proposed element-specific production rates. For apatite and zircon, the data are sufficient to conclude that the ³He/¹⁰Be ratio increases with elevation. If this reflects different altitudinal scaling between production rates for the two isotopes then the SLHL production rates estimated by our approach are overestimates. We consider several hypotheses to explain these observations, including production of ³He via thermal neutron capture on ⁶Li, altitudinal variations in the energy spectrum of cosmic-ray neutrons, and the effects of snow cover. Because all of these effects are small, we conclude that the altitudinal variations in production rates of cosmogenic ³He and ¹⁰Be are distinct from each other at least at this location over the last ～ 10 kyr. This conclusion calls into question commonly adopted geographic scaling laws for at least some cosmogenic nuclides. If confirmed, this distinction may provide a mechanism by which to obtain paleoelevation estimates.     

Cosmogenic 3He and 21Ne dating of biotite and hornblende

Stable cosmogenic isotopes such as ³He and ²¹Ne are useful for dating of diverse lithologies, quantifying erosion rates and ages of ancient surfaces and sediments, and for assessing complex burial histories. Although many minerals are potentially suitable targets for ³He and ²¹Ne dating, complex production systematics require calibration of each mineral–isotope pair. We present new results from a drill core in a high-elevation ignimbrite surface, which demonstrates that cosmogenic ³He and ²¹Ne can be readily measured in biotite and hornblende. ²¹Ne production rates in hornblende and biotite are similar, and are higher than that in quartz due to production from light elements such as Mg and Al. We measure ²¹Ne_hbl/²¹Ne_qtz = 1.35 ± 0.03 and ²¹Ne_bio/²¹Ne_qtz = 1.3 ± 0.02, which yield production rates of 25.6 ± 3.0 and 24.7 ± 2.9 at g^? 1 yr^? 1 relative to a ²¹Ne_qtz production rate of 19.0 ± 1.8 at g^? 1 yr^? 1. We show that nucleogenic ²¹Ne concentrations produced via the reaction ¹⁸O(α,n)²¹Ne are manageably small in this setting, and we present a new approach to deconvolve nucleogenic ²¹Ne by comparison to nucleogenic ²²Ne produced from the reaction ¹⁹F(α,n)²²Ne in F-rich phases such as biotite. Our results show that hornblende is a suitable target phase for cosmogenic ³He dating, but that ³He is lost from biotite at Earth surface temperatures. Comparison of ³He concentrations in hornblende with previously measured mineral phases such as apatite and zircon provides unambiguous evidence for ³He production via the reaction ⁶Li(n,α)³H → ³He. Due to the atypically high Li content in the hornblende (~ 160 ppm) we estimate that Li-produced ³He represents ~ 40% of total ³He production in our samples, and must be considered on a sample-specific basis if ³He dating in hornblende is to be widely implemented.     

Thermal history and origin of the Tanzanian Craton from Pb isotope thermochronology of feldspars from lower crustal xenoliths

Common and radiogenic Pb isotopic compositions of plagioclase and anti-perthitic feldspars from granulite-facies lower crustal xenoliths from the Labait Volcano on the eastern margin of the Tanzanian Craton have been measured via laser ablation MC-ICP-MS. Common Pb in plagioclase and a single stage Pb evolution model indicate that the lower crust of the Tanzanian Craton was extracted from mantle having a ²³⁸U/²⁰⁴Pb of 8.1 ± 0.3 and a ²³²Th/²³⁸U of 4.3 ± 0.1 at 2.71 ± 0.09 Ga (all uncertainties are 2σ). Since 2.4 Ga, some orthoclase domains within anti-perthites have evolved with a maximum ²³⁸U/²⁰⁴Pb of 6 and ²³²Th/²³⁸U of 4.3. The spread in Pb isotopic composition in the anti-perthitic feldspars yields single crystal Pb–Pb isochrons of ～ 2.4 Ga, within uncertainty of U–Pb zircon ages from the same sample suite. The Pb isotopic heterogeneities imply that these granulites resided at temperatures < 600 °C in the lower crust of the Tanzanian Craton from ca. 2.4 Ga to the present. In concert with the chemistry of surface samples, mantle xenoliths, and lower crustal xenoliths, our data imply that the cratonic lithosphere in Tanzania formed ca. ～ 2.7 Ga, in a convergent margin setting, and has remained undisturbed since 2.7 Ga.     

Luminescence dating of archaeosediments: A comparison of K-feldspar and plagioclase IRSL ages

IRSL single-aliquot dating of three feldspar fractions from a Howieson's Poort (SA) industry site has been investigated. In the case of the plagioclase fraction (ρ > 2.62 g cm^?3) equivalent dose is similar to that of the other fractions (i.e. ρ < 2.58 g cm^?3, high-K-feldspar; and 2.58 < ρ < 2.62 g cm^?3; low-K-feldspar). However, the g values measured for this fraction is such that the fading-corrected age is overestimated. The K content of each fraction was estimated by SEM. The DRC-corrected ages for the two lighter feldspar fractions are consistent with the archaeological interpretation. This study shows that reliable single-aliquot luminescence ages can be obtained using K-feldspar and Na-plagioclase.     

High-precision 40Ar/39Ar age of the Jänisjärvi impact structure (Russia)

The ～ 14 km diameter Jänisjärvi impact structure is located in Svecofennian Proterozoic terrain in the southeastern part of the Baltic shield, Karelia, Russia. Previous radioisotopic dating attempts gave K/Ar and ⁴⁰Ar/³⁹Ar ages of 700 ± 5 Ma and 698 ± 22 Ma, respectively, with both results being difficult to interpret. Recent paleomagnetic results have challenged these ages and proposed instead ages of either 500 Ma or 850–900 Ma. In order to better constrain the age of the Jänisjärvi impact structure, we present new ⁴⁰Ar/³⁹Ar data for the Jänisjärvi impact melt rock. We obtained five concordant isochron ages that yield a combined isochron age of 682 ± 4 Ma (2σ) with a MSWD of 1.2, P = 0.14, and ⁴⁰Ar/³⁶Ar intercept of 475 ± 3. We suggest that this date indicates the age of the impact and therefore can be used in conjunction with existing paleomagnetic results to define the position of the Baltica paleocontinent at that time. Argon isotopic results imply that melt homogenization was achieved at the hundred-micrometer scale certainly, because of the low-silica content of the molten target rock that allows fast ⁴⁰Ar^? diffusion in the melt. However, the large range of F(⁴⁰Ar^?_inherited) (4.1% to 11.0%) observed for seven grains shows that complete isotopic homogenization was not reached at the centimeter and perhaps the millimeter scale. The F(⁴⁰Ar^?_inherited) results are also in good agreement with previous Rb and Sr isotopic data.     

Inter-comparison of cosmogenic in-situ He, Ne and Cl at low latitude along an altitude transect on the SE slope of Kilimanjaro volcano (3°S, Tanzania)

Because the intensity and energy spectrum of the cosmic ray flux are affected by atmospheric depth and geomagnetic-field strength, cosmogenic nuclide production rates increase considerably with altitude and to a lesser degree with latitude. The scaling methods used to account for spatial variability in production rates assume that all cosmogenic nuclides have the same altitude dependence. In this study we evaluate whether the production rates of cosmogenic ³⁶Cl, ³He and ²¹Ne change differently with altitude, which is plausible due to the different threshold energies of their production reactions. If so, nuclide-specific scaling factors would be required.Concentrations of the three cosmogenic nuclides were determined in mafic phenocrysts over an altitude transect between 1000 and 4300 m at Kilimanjaro volcano (3°S). Altitude dependence of relative production rates was assessed in two ways: by determination of concentration ratios and by calculation of apparent exposure age ratios for all nuclide pairs. The latter accounts for characteristics of ³⁶Cl that the stable nuclides ³He and ²¹Ne do not possess (radioactive decay, high sensitivity to mineral composition and significant contributions from production reactions other than spallation). All ratios overlap within error over the entire transect, and altitudinal variation in relative production rates is not therefore evident. This suggests that nuclide-specific scaling factors are not required for the studied nuclides at this low-latitude location. However, because previous studies have documented anomalous altitude-dependent variations in ³He production at mid-latitude sites, the effect of latitude on cross-calibrations should be further evaluated.We determined cosmogenic ²¹Ne/³He concentration ratios of 0.1864 ± 0.0085 in pyroxenes and 0.377 ± 0.018 in olivines, agreeing with those reported in previous studies.Despite the absence of independently determined ages for the studied lava surfaces, the consistency in the dataset should enable progress to be made in the determination of the production rates of all three nuclides as soon as the production rate of one of the nuclides has been accurately defined.To our knowledge this is the first time that ³⁶Cl has been measured in pyroxene. The Cl extraction method was validated by measuring ³⁶Cl in co-existing plagioclase phenocrysts in one of the samples.     

A long-term rock uplift rate for eastern Crete and geodynamic implications for the Hellenic subduction zone

The island of Crete in the forearc of the Hellenic subduction zone has a rugged topography with local relief exceeding 2 km. Based on the elevation of marine shorelines, rates of rock uplift during the Late Holocene were previously estimated to range between 1 and 4 mm/a in different parts of the island. These rates may, however, not be representative for longer timescales, because subduction earthquakes with up to 9 m of vertical coseismic displacement have affected Crete in the Late Holocene. Here we use a well preserved sequence of marine terraces near Kato Zakros in eastern Crete to determine the rate of rock uplift over the last ∼600 ka. Field investigations and topographic profiles document a flight of more than 13 marine bedrock terraces that were carved into limestones of the Tripolitza unit. Preliminary age constraints for the terraces were obtained by ¹⁰Be exposure dating of rare quartz-bearing sandstone clasts, which are present on some terraces. The ¹⁰Be ages of these samples, which have been corrected for an inherited nuclide component, yielded exposure ages between ∼100 ka and zero. Combined with geomorphologic evidence the two oldest ¹⁰Be ages suggest that the terraces T₄ and T₅, with shoreline angles at an elevation of ∼68 and ∼76 m above sea level, respectively, formed during the marine isotope stage 5e about 120 ka ago. The correlation of the higher terraces (T₆ to T₁₃) with regional sea-level highstands indicates sustained rock uplift at a rate of ∼0.5 m/ka since at least ∼600 ka. As normal faulting has dominated the tectonics of Crete during the last several million years, upper crustal shortening can be ruled out as a cause for rock uplift. We argue that the sustained uplift of the island results from the continuous underplating of sediments, which are transferred from the subducting African plate to the base of the crust beneath Crete.     

40Ar / 39Ar geochronology constraints on late miocene weathering rates in Minas Gerais,Brazil

⁴⁰Ar / ³⁹Ar incremental heating ages for twenty one grains of cryptomelane, collected at 0, 42, 45, and 60 m depths in the Cachoeira Mine weathering profile, Minas Gerais, permit calculating long-term (10 Ma time scale) weathering rate (saprolitization rate) in SE Brazil. Pure well-crystallized cryptomelane grains with high K contents (3–5 wt.%) yield reliable geochronological results. The ⁴⁰Ar / ³⁹Ar plateau ages obtained decrease from the top to the bottom of the profile (12.7 ± 0.1 to 7.6 ± 0.1 Ma at surface; 7.6  ± 0.2 to 6.1 ± 0.2 Ma at 42 m; and 7.1 ± 0.2 to 5.9 ± 0.1 Ma at 45 m; 6.6 ± 0.1 to 5.2 ± 0.1 Ma at 60 m), yielding a weathering front propagation rate of 8.9 ± 1.1 m/m.y. From the geochronological results and the mineral transformations implicit by the current mineralogy in the weathering profiles, it is possible to calculate the saprolitization rate for the Cachoeira Mine lithologies and for adjacent weathering profiles developed on granodiorites and schists. The measured weathering front propagation rate yields a saprolitization rate of 24.9 ± 3.1 t/km²/yr. This average long-term (> 10 Ma) saprolitization rate is consistent with mass balance calculations results for present saprolitization rates in weathering watersheds. These results are also consistent with long-term saprolitization rates estimated by combining cosmogenic isotope denudation rates with mass balance calculations.     

Strong climate and tectonic control on plagioclase weathering in granitic terrain

Investigations to understand linkages among climate, erosion and weathering are central to quantifying landscape evolution. We approach these linkages through synthesis of regolith data for granitic terrain compiled with respect to climate, geochemistry, and denudation rates for low sloping upland profiles. Focusing on Na as a proxy for plagioclase weathering, we quantified regolith Na depletion, Na mass loss, and the relative partitioning of denudation to physical and chemical contributions. The depth and magnitude of regolith Na depletion increased continuously with increasing water availability, except for locations with mean annual temperature < 5 °C that exhibited little Na depletion, and locations with physical erosion rates < 20 g m^? 2 yr^? 1 that exhibited deep and complete regolith Na depletion. Surface Na depletion also tended to decrease with increasing physical erosion. Depth-integrated Na mass loss and regolith depth were both three orders of magnitude greater in the fully depleted, low erosion rate sites relative to other locations. These locations exhibited strong erosion-limitation of Na chemical weathering rates based on correlation of Na chemical weathering rate to total Na denudation. Sodium weathering rates in cool locations with positive annual water balance were strongly correlated to total Na denudation and precipitation, and exhibited an average apparent activation energy (Ea) of 69 kJ mol^? 1 Na. The remaining water-limited locations exhibited kinetic limitation of Na weathering rates with an Ea of 136 kJ mol^? 1 Na, roughly equivalent to the sum of laboratory measures of Ea and dissolution reaction enthalpy for albite. Water availability is suggested as the dominant factor limiting rate kinetics in the water-limited systems. Together, these data demonstrate marked transitions and nonlinearity in how climate and tectonics correlate to plagioclase chemical weathering and Na mass loss.     

A combined glass dissolution/diffusion experiment in Boom Clay at 30 °C

At the appropriate times, silica diffusion in clay is possibly the rate determining process for the dissolution of vitrified waste disposed of in a clay layer. For testing this hypothesis, combined glass dissolution/silica diffusion experiment are performed. SON68 glass coupons doped with the radioactive tracer ³²Si are sandwiched between two cores of humid Boom Clay, heated to 30 °C. Due to glass dissolution, ³²Si is released and diffuses into the clay. At the end of an experiment, the mass loss of the glass coupon is measured and the clay core is sliced to determine the diffusion profile of the ³²Si released from the glass in the clay.Both mass loss and the ³²Si diffusion profile in the clay are described well by a model combining glass dissolution according to a linear rate law with silica diffusion in the clay. Fitting the experiments to this model leads to an apparent silica diffusion coefficient in the clay between 7 × 10⁻¹³ m²/s and 1.2 × 10⁻¹² m²/s. Previously determined values from diffusion experiments at 25 °C are around 6 × 10⁻¹³ m²/s (In-Diffusion experiments) and 2 × 10⁻¹³ m²/s (percolation experiments). The maximal glass dissolution rate for glass next to clay is around 1.6 × 10⁻⁷ g glass/m² s (i.e. 0.014 g glass/m² day). In undisturbed clay, the measured silica concentration is around 5 mg/L. Combining these values with the previously measured (In-Diffusion experiments) product of accessible porosity and retardation factor, leads in two ways to a silica glass saturation concentration in clay between 8 and 10 mg Si/L.Another candidate for the rate determining process of the dissolution of vitrified waste disposed in a clay layer is silica precipitation. Although silica precipitation due to glass dissolution has been shown experimentally at 90 °C, extending the model with silica precipitation does not lead to much better fits, nor could meaningful values of a possible precipitation rate be obtained.     

The current performance of the in situ 14C extraction line at ETH

We present the new ¹⁴C extraction line at ETH Zürich. This system is designed to extract in situ-produced cosmogenic ¹⁴C from terrestrial quartz samples, and to obtain pure CO₂ gas for analysis with a gas ion source Accelerator Mass Spectrometry (AMS) system. Samples are degassed at 1550–1600 °C without the use of a fluxing agent. Gas purification is achieved by a series of cryogenic traps and passage through hot Ag and Cu wool/mesh. Graphitization and, thus, sample dilution is not required. Tests to determine the CO₂ recovery after gas extraction and cleaning yielded consistently good recovery rates of >99.8% (n = 7). The ¹⁴C blank contribution from the all-metal tubing system is negligible. Our preliminary procedural blank estimate – deriving mostly from the hot extraction furnace – is <5 × 10^{5 14}C atoms. Extraction tests on two quartz samples by stepped-heating show a quantitative separation of atmospheric ¹⁴C at ≤500 °C from the in situ component above 1200 °C. Based on these data, we estimate to achieve a complete ¹⁴C extraction from a quartz sample.     

Nanoscale porosity in SAFOD core samples (San Andreas Fault)

With transmission electron microscopy (TEM) we observed nanometer-sized pores in four ultracataclastic and fractured core samples recovered from different depths of the main bore hole of the San Andreas Fault Observatory at Depth (SAFOD). Cutting of foils with a focused ion beam technique (FIB) allowed identifying porosity down to the nm scale. Between 40 and 50% of all pores could be identified as in-situ pores without any damage related to sample preparation. The total porosity estimated from TEM micrographs (1–5%) is comparable to the connected fault rock porosity (2.8–6.7%) estimated by pressure-induced injection of mercury. Permeability estimates for cataclastic fault rocks are 10^? 21–10^? 19 m² and 10^? 17 m² for the fractured fault rock. Porosity and permeability are independent of sample depth. TEM images reveal that the porosity is intimately linked to fault rock composition and associated with deformation. The TEM-estimated porosity of the samples increases with increasing clay content. The highest porosity was estimated in the vicinity of an active fault trace. The largest pores with an equivalent radius > 200 nm occur around large quartz and feldspar grains or grain-fragments while the smallest pores (equivalent radius < 50 nm) are typically observed in the extremely fine-grained matrix (grain size < 1 μm). Based on pore morphology we distinguish different pore types varying with fault rock fabric and alteration. The pores were probably filled with formation water and/or hydrothermal fluids at elevated pore fluid pressure, preventing pore collapse. The pore geometry derived from TEM observations and BET (Brunauer, Emmett and Teller) gas adsorption/desorption hysteresis curves indicates pore blocking effects in the fine-grained matrix. Observations of isolated pores in TEM micrographs and high pore body to pore throat ratios inferred from mercury injection suggest elevated pore fluid pressure in the low permeability cataclasites, reducing shear strength of the fault.