Identifying outliers and assessing the accuracy of amino acid racemization measurements for geochronology: I. Age calibration curves

Numerical ages derived from amino acid racemization (AAR) geochronology are typically based on calibration curves that relate the extent of AAR to the age of independently dated specimens. Here, we compare options for developing calibration curves and quantifying age uncertainties using AAR data from 481 late Holocene shells, and AMS ¹⁴C analyses of 36 shells of four molluscan taxa (Ethalia, Natica, Tellina, and Turbo) collected from shallow sediment cores from a back-reef lagoon of the central Great Barrier Reef. The four taxa differed substantially in the quality of their geochronogical results. Explicitly including data from specimens alive at the time of collection improves calibration curves, but weighting numerical ages based on their uncertainty has no effect. Calibration curve statistics do not adequately assess calibration uncertainty. The relation between ages inferred from different amino acids is recommended for identifying aberrant specimens and quantifying the uncertainty of inferred ages. For this study, the AAR ages based on two amino acids (aspartic acid and glutamic acid) exceed 200 yr or 20% of their mean inferred age in 15% of the specimens. Once these were removed, the mean age error (1σ) for individual specimens based on two amino acids analyzed in duplicate subsamples ranged from 53 to 142 yr for Tellina and Turbo, respectively, or about a 30% age error for these relatively young shells. This compares favorably with analytical errors estimated at 50 yr or 5%. The presence of notable outliers undetectable using data from single amino acids emphasizes the importance of analyzing multiple amino acids.     

Coupled ESR and U-series dating of early Pleistocene Gigantopithecus faunas at Mohui and Sanhe Caves,Guangxi, southern China

Several caves of the Guangxi Zhuang Autonomous Region, southern China, have delivered Gigantopithecus blacki remains, an extinct Pleistocene giant ape, in association with abundant mammalian faunas. To determine their geological ages, fossil teeth from Mohui and Sanhe Caves were dated using the coupled ESR/U-series method. The teeth from Mohui Cave gave age estimates of 1.69 ± 0.22 Ma and 1.29 ± 0.11 Ma. The Sanhe Cave samples had age estimates ranging from 910 ± 200 ka to 600 ± 150 ka with error weighted mean ages of 890 ± 130 ka and 720 ± 90 ka for the layers 5 and 4, respectively. Our results and previous paleomagnestism data place the Gigantopithecus fauna at Mohui Cave between Olduvai and Jaramillo subchrons and suggest that it was coeval with Chuifeng, Longgupo and Liucheng assemblages. The Sanhe fauna is younger, of late early Pleistocene age, and can be dated to the period between Jaramillo subchron and B/M boundary.     

Amino acid racemization in mono-specific foraminifera from Quaternary deep-sea sediments

The deep-sea environment is among the most stable on Earth, making it well suited for amino acid geochronology. Foraminifera with calcareous tests are distributed across the World Ocean and are often recovered in sufficient abundance from sediment cores to derive robust mean amino acid D/L values of multiple replicates from each stratigraphic level. The extent of racemization (D/L) can be compared with independent age control, which in most cases is based on correlation with global marine oxygen-isotope stages and radiocarbon ages from the same stratigraphic levels. In this study, we report the results of amino acid racemization analysis of multiple foraminifera species from well-dated sediment cores taken from the Pacific, Atlantic, and Arctic oceans. The composite of results analyzed to date (179 samples, each composed of an average of 8.6 subsamples = 1531 analyses) show that D/L values generally increase systematically down core, and are similar for samples of comparable ages from different deep-sea sites. Previously published equations that relate D/L values of aspartic and glutamic acids to post-depositional temperature and sample age for Pulleniatina obliquiloculata generally conform to the D/L trends for species analyzed in this study. Laboratory heating experiments were used to quantify the difference in the rate of racemization between P. obliquiloculata and other taxa. For example, aspartic acid in P. obliquiloculata racemizes an average of 12–16% faster than in the common high-latitude species, Neogloboquadrina pachyderma (s). Apparently, the unexpectedly high D/L values previously reported for N. pachyderma (s) older than 35 ka from the Arctic Ocean cannot be attributed to taxonomic effects.     

Direct U–Th dating of vertebrate fossils with minimum sampling destruction and application to museum specimens

Although vertebrate fossils are commonly abundant in museum palaeontological collections, they are only rarely accompanied by contextual data (e.g., stratigraphic and taphonomic information) that allow them to be placed independently into reliable temporal frameworks critical for testing significant evolutionary and extinction hypotheses. Moreover, where critical samples do exist in such collections, sampling for direct geochronological analyses becomes a significant concern, especially where such sampling is destructive in nature. Here we apply a direct fossil dating, micro-drilling sampling approach that minimises damage to and destruction of precious museum specimens. We carried out a systematic U–Th dating study (n = 28 ages) of an isolated museum specimen of the extinct Palorchestes azael (megafaunal ‘marsupial tapir’) originally collected in 1977 from Tea Tree Cave, Chillagoe, northeastern Australia. We obtained 21 U–Th ages and constructed ²³⁰Th-age profiles across three teeth exposed in cross-section, using micro-drilling and thermal ionisation mass spectrometry. Individual sample masses were as little as 0.18 mg (U concentration 33–82 ppm), meaning that the sampling resulted in only minimal destruction of the specimen. The results show no evidence of U leaching, suggesting that the dates represent reliable minimum ages. For independent age control, we also dated calcite that had encrusted the sample (thus, providing a minimum age; n = 6) and an older calcite clast that had been reworked into the surrounding breccia at the time of burial (thus, providing a maximum age; n = 1). U–Th ages of the teeth are older than the calcite overgrowths and younger than the reworked calcite, consistent with their demonstrable relative age relationships. Collectively, the results unequivocally bracket the age of the fossil between 199.1 ± 8.9 ka and 137.4 ± 1.1 ka (2σ), adding another rare datum to inform the timing and geographic distribution of last occurrences of the species. The benefits of our dating approach of museum fossil specimens are threefold: 1) it is minimally destructive even compared with laser-ablation method; 2) the use of U vs. apparent age approach allows direct testing for potential U leaching as occasionally seen in fossil dating; and 3) the combination of fossil and associated speleothem dating provides the most robust means of securely bracketing the age of fossils that lack firm stratigraphic control.     

Radiocarbon-calibrated amino acid racemization ages from Holocene sand dollars (Peronella peronii)

Amino acid racemization (AAR) is widely used as a cost-effective method to date molluscs in time-averaging and taphonomic studies, but it has not been attempted for echinoderms despite their paleobiological importance and distinct biomineralization. Here we demonstrate the applicability of AAR geochronology for dating Holocene Peronella peronii (Echinodermata: Echinoidea) collected from Sydney Harbour (Australia). Using standard HPLC methods we determined the extent of AAR in 74 Peronella tests and performed replicate analyses on 23 tests. Replicate analyses from the outer edge of 23 tests spanning the observed range of D/L values yielded median coefficients of variation <4% for Asp, Glu, and Phe D/L values, which is comparable to the analytical precision. Correlations between THAA D/L values across 178 independently prepared subsamples of 74 individuals are also very high (Spearman ρ ≥ 0.95) for these three amino acids. The ages of 20 individuals spanning the observed range of D/L values were determined using ¹⁴C analyses, and Bayesian model averaging was used to determine the best AAR age model. Only three models fit to Glu D/L contributed to the final averaged age model. Modeled ages ranged from 14 to 5496 years, and the median 95% confidence interval for the 54 AAR ages was ±29% of the modelled age. In comparison, the median 2σ confidence interval for nine graphite target ¹⁴C ages was ±8% of the median age estimate and the median 2σ confidence interval for 20 carbonate target ¹⁴C ages was ±26% of the median age estimate. Overall Peronella yield high-quality D/L values and appear to be a good target for AAR geochronology.     

Testing the limitations of artificial protein degradation kinetics using known-age massive Porites coral skeletons

High-temperature isothermal heating of biominerals has commonly been used to artificially accelerate protein degradation in order to extrapolate kinetic parameters to the lower temperatures experienced in vivo and in the burial environment. It is not easy to test the accuracy of these simulations due to the difficulty of finding samples of known age held at a known temperature. We compare protein degradation in the intra-crystalline organic matrix of heated (80 °C, 110 °C, and 140 °C) massive Porites sp. coral to that directly measured in the skeleton of colonies growing at ∼26 °C and deposited over the last five centuries. This provides the opportunity to critically evaluate the underlying assumption that high-temperature experiments accurately mimic degradation processes and kinetics occurring in a ‘naturally aged’ biomineral. In all samples the intra-crystalline protein fraction was isolated and the L- and D- concentration of multiple amino acids measured using reverse-phase high-performance liquid chromatography (RP-HPLC). There was no evidence of a failure of the closed system in the high-temperature experiments (assessed by X-ray diffraction, thermogravimetric analyses and determination of leached amino acid concentration). We compared conventional methods for estimation of kinetic parameters with a new ‘model-free’ approach that makes no assumptions regarding the underlying kinetics of the system and uses numerical optimisation to estimate relative rate differences. The ‘model-free’ approach generally produced more reliable estimates of the observed rates of racemization in ‘naturally aged’ coral, although rates of hydrolysis (as estimated from the release of free amino acids) were usually over-estimated. In the amino acids for which we were able to examine both racemization and hydrolysis (aspartic acid/asparagine, glutamic acid/glutamine and alanine), it was clear that hydrolysis was less temperature sensitive than racemization, which may account for the differences in degradation patterns observed between the ‘naturally aged’ coral and high-temperature data. It is clearly important to estimate the individual temperature dependence of each of the parallel reactions.     

40Ar/39Ar constraints on some French landmark Late Pliocene to Early Pleistocene large mammalian paleofaunas: Paleoenvironmental and paleoecological implications

To improve the French Plio-Pleistocene biostratigraphy scheme based on mammal biozone boundaries or “Mammal Neogene/Quaternary Zones” (MNQ) we collected volcanic material that could be dated using the ⁴⁰Ar/³⁹Ar method in five exceptional mammalian paleofauna sites located in the Massif Central (France). We present ⁴⁰Ar/³⁹Ar ages that we obtained for Perrier-Les Etouaires, Roca-Neyra, Chilhac, Senèze and le Creux de Peyrolles. We show that the overall stratigraphic position of these sites based on faunal assemblages is valid from the relative point of view. However, we greatly improve both the accuracy and precision of the age of these mammalian paleofaunas. We obtained ⁴⁰Ar/³⁹Ar ages varying between 2.78 ± 0.01 Ma (1σ external) for Les Etouaires (Lower MNQ 16b) and 1.47 ± 0.01 Ma for the Creux de Peyrolles site (MNQ 19). Based on these new dates we estimate the duration of several biozones including MNQ 16b, 17a and 17b. We suggest that the first Late Villafranchian biozone (MNQ 18) starts as early as the Reunion subchron or just after. The first occurrence of Equus stenonis in Roca-Neyra (i.e. 2.60 ± 0.02 Ma) is close to or synchronous with the Gauss–Matuyama transition (i.e. 2.59 Ma) and the Pliocene/Pleistocene boundary. The chronological framework we build shows the very rapid increase of the large grazers community in French faunal assemblages at the beginning of MNQ 17 (i.e. 2.6 to 2.4 Ma). This rapid faunal turnover is probably associated with a general decrease of woodland habitat in the Massif Central contemporaneous with the onset of the Northern Hemisphere glaciations. The faunal assemblages in France, Spain, and Italy covering the period between 2.1 and 2.0 Ma suggest that favorable conditions for early hominin settlement (mainly savannah prairies, grassland with open forest patches) existed in southwestern Europe at least 200 ka before the first traces of Homo in Eurasia. This period also shows the arrival of taxa originating in Asia and Africa, suggesting dispersal events within southwestern Europe well before the Olduvai subchron and with no indication (as yet) of Homo as a “fellow traveler”.     

230Th/U chronology of a paleolithic site at Xinglong Cave in the three-Gorge region of south China

Xinglong Cave, containing four human teeth, numerous mammalian fossils, stone artifacts and a Stegodon tusk with intentional and seemingly grouped engravings, is one of the most significant archaic Homo sapiens sites in south China, located 95 km south of Fengjie County, in Chongqing. In an attempt to constrain the age of the human relics, calcitic flowstone deposits with a significant detrital component were dated by U–Th methods using a leachate scheme. Total sample digestion MC-ICPMS dating was used to assess the reliability of the leachate technique. Six calcite samples from horizons beneath and above the fossil-bearing layer were dated. We obtained ages of 130 ± 9.1, 124 ± 11, 135 ± 12 and 127 ± 11 ka for the flowstones above the fossil layer with a weighted mean of 128.9 ± 5.2 ka. Two flowstone samples gave MC-ICPMS dates between 128.3 ± 3.3 and 152.4 ± 25.3 ka with an assumed detrital component to correct for the initial ²³⁰Th, which are consistent with results obtained using the L/L regression data from layer U-4 within uncertainty. All errors herein quoted at the 2σ level. Ages determined for the flowstone underlying the fossil-bearing layer were 221 ± 29 to 189 ± 19 ka with a weighted mean age of 199 ± 16 ka. These results are stratigraphically consistent within error limits and show that the cave was occupied by Fengjie Man within the time range of ∼200 to ∼130 ka. These new U-series ages of flowstones in association with human teeth and an engraved stegodon tusk at the Xinglong Cave site provide valuable geochronologic information for the study of the origin of modern humans in East Asia and earliest human art.     

Closed-system behaviour of the intra-crystalline fraction of amino acids in mollusc shells

When mollusc shells are analysed conventionally for amino acid geochronology, the entire population of amino acids is included, both inter- and intra-crystalline. This study investigates the utility of removing the amino acids that are most susceptible to environmental effects by isolating the fraction of amino acids encapsulated within mineral crystals of mollusc shells (intra-crystalline fraction). Bleaching, heating and leaching (diffusive loss) experiments were undertaken on modern and fossil Corbicula fluminalis, Margaritifera falcata, Bithynia tentaculata and Valvata piscinalis shells. Exposure of powdered mollusc shells to concentrated NaOCl for 48 h effectively reduced the amino acid content of the four taxa to a residual level, assumed to represent the intra-crystalline fraction. When heated in water at 140 °C for 24 h, only 1% of amino acids were leached from the intra-crystalline fraction of modern shells compared with 40% from whole shell. Free amino acids were more effectively retained in the intra-crystalline fraction, comprising 55% (compared with 18%) of the whole shell after 24 h at 140 °C. For fossil gastropods, the inter-shell variability in D/L values for the intra-crystalline fraction of a single-age population was reduced by 50% compared with conventionally analysed shells. In contrast, analysis of the intra-crystalline fraction of C. fluminalis does not appear to improve the results for this taxon, possibly due to variability in shell ultrastructure. Nonetheless, the intra-crystalline fraction in gastropods approximates a closed system of amino acids and appears to provide a superior subset of amino acids for geochronological applications.     

Intra-crystalline protein diagenesis (IcPD) in Patella vulgata. Part II: Breakdown and temperature sensitivity

Artificial diagenesis of the intra-crystalline proteins isolated from Patella vulgata was induced by isothermal heating at 140 °C, 110 °C and 80 °C. Protein breakdown was quantified for multiple amino acids, measuring the extent of peptide bond hydrolysis, amino acid racemisation and decomposition. The patterns of diagenesis are complex; therefore the kinetic parameters of the main reactions were estimated by two different methods: 1) a well-established approach based on fitting mathematical expressions to the experimental data, e.g. first-order rate equations for hydrolysis and power-transformed first-order rate equations for racemisation; and 2) an alternative model-free approach, which was developed by estimating a “scaling” factor for the independent variable (time) which produces the best alignment of the experimental data. This method allows the calculation of the relative reaction rates for the different temperatures of isothermal heating.High-temperature data were compared with the extent of degradation detected in sub-fossil Patella specimens of known age, and we evaluated the ability of kinetic experiments to mimic diagenesis at burial temperature. The results highlighted a difference between patterns of degradation at low and high temperature and therefore we recommend caution for the extrapolation of protein breakdown rates to low burial temperatures for geochronological purposes when relying solely on kinetic data.     

New 40Ar/39Ar ages for selected young (<1 Ma) basalt flows of the Newer Volcanic Province,southeastern Australia

The Pliocene-Holocene Newer Volcanic Province (NVP) of southeastern Australia is an extensive, relatively well-preserved, intra-plate basaltic lava field containing more than 400 eruptive centres. This study reports new, high-precision ⁴⁰Ar/³⁹Ar ages for six young (300–600 ka) basalt flows from the NVP and is part of a broader initiative to constrain the extent, duration, episodicity and causation of NVP volcanism. Six fresh, holocrystalline alkali basalt flows were selected from the Warrnambool-Port Fairy area in the Western Plains sub-province for ⁴⁰Ar/³⁹Ar dating. These flows were chosen on the basis of pre-existing K-Ar age constraints, which, although variable, indicated eruption during a period of apparent relative volcanic quiescence (0.8–0.06 Ma).⁴⁰Ar/³⁹Ar ages were measured on multiple aliquots of whole rock basalt samples. Three separate flows from the Mount Rouse volcanic field yielded concordant ⁴⁰Ar/³⁹Ar age results, with a mean eruption age of 303 ± 13 ka (95% CI). An older weighted mean age of 382 ± 24 ka (2σ) was obtained for one sample from the central Rouse-Port Fairy Flow, suggesting extraneous argon contamination. Two basalt flows from the Mount Warrnambool volcano also yielded analogous results, with an average ⁴⁰Ar/³⁹Ar age of 542 ± 17 ka (95% CI). The results confirm volcanic activity during the interval of relative quiescence. Most previous K-Ar ages for these flows are generally older than the weighted mean ⁴⁰Ar/³⁹Ar ages, suggesting the presence of extraneous ⁴⁰Ar. This study demonstrates the suitability of the ⁴⁰Ar/³⁹Ar incremental-heating method to obtain precise eruption ages for young, holocrystalline alkali basalt samples in the NVP.     

Fuerteventura – Assessment of a calibration site for cosmogenic 3He exposure dating with the 40Ar/39Ar incremental heating method

In situ Terrestrial Cosmogenic Nuclides (hereafter TCNs) are increasingly important for absolutely dating terrestrial events and processes. This study aimed at improving our knowledge of the production rate of Terrestrial Cosmogenic ³He formed in situ in rock surfaces at low latitude and sea level as well as re-evaluation of the Canary Islands as a calibration site for TCNs. For this purpose, we sampled basaltic lava flows from some of the youngest and yet undated volcanic sites and used the ⁴⁰Ar/³⁹Ar incremental heating method on groundmass samples and in situ cosmogenic ³He on olivine and clinopyroxene phenocrysts. ⁴⁰Ar/³⁹Ar analysis was done on a Hiden HAL Series 1000 triple filter quadrupole mass spectrometer with extraction furnace. Incremental heating data shows ages in the Late Pleistocene from 52.7 ± 21.6 ka to 398.6 ± 27.6 ka.We measured cosmogenic ³He concentrations in olivine and clinopyroxene phenocrysts from flow top samples on a MAP 215-50 sector mass spectrometer with a crushing device and a diode laser extraction system. Exposure age calculations yielded ages in the range 38.9 ± 4.0 ka to 62.3 ± 6.7 ka for the youngest lava flow and the data series is in broad agreement with the argon data up to 250 ka and reveals a more continuous time line of volcanism during the late Pleistocene on the island. However, the dataset was not sufficient for calculation of production rates for in situ Terrestrial Cosmogenic ³He as many samples showed signs of erosion. Calculated erosion rates range from none to as high as 7.3 mm/kyr assuming a rock density of 2.9 g/cm². This finding puts a constraint on the use of Fuerteventura as a calibration site for exposure histories older than 50–100 ka. A comparison with cosmogenic ³⁶Cl data supports these findings and indicates substantial weathering.     

Chronology of Early to Mid-Pleistocene sediments in the northern North Sea: New evidence from amino acid and strontium isotope analyses

Sediments deposited during glacial-interglacial cycles through the Early to Mid-Pleistocene in the North Sea are chronologically poorly constrained. To contribute to the chronology of these units, amino acid racemization (AAR) and strontium (Sr) isotope analyses have been performed on samples from four shallow borings and one oil well along a transect in the northern North Sea. D/L Asp (aspartic acid) values obtained through reverse-phase liquid chromatography in the benthic foraminiferal species Elphidium excavatum is focused on because of consistent results and a good stratigraphic distribution of this benthic species. For the Early Pleistocene, an age model for the well 16/1–8, from the central part of the northern North Sea based on Sr ages allows for dating of the prograding wedges filling the pre-Quaternary central basin. A regional calibration curve for the racemization of Asp in Elphidium excavatum is developed using published ages of radiocarbon-dated samples and samples associated with the previously identified Bruhnes/Matuyama (B/M) paleomagnetic boundary and a Sr age from this study. Based on all the available geochronological evidence, samples were assigned to marine oxygen isotope stages (MIS) with uncertainties on the order of 10–70 ka.Sr ages suggest a hiatus of <2 million years (Ma) possibly due to non-deposition or low sedimentation between the Utsira Formation (Pliocene) and the Early Pleistocene. An increase in sedimentation rates around 1.5 ± 0.07 Ma (∼MIS 51) may partly be due to sediment supply from rivers from the south-east and partly due to the extension of ice sheet around 1.36 ± 0.07 Ma from the Norwegian coast to the central North Sea. A possible basin-wide glaciation occurred around 1.1 Ma (∼ MIS 32) (upper regional unconformity/top of unit Q4 in this study), resulting in erosion and regional unconformity. Two interglacials in the Norwegian Channel have been dated: the Radøy Interglacial to 1.07 ± 0.01 Ma (possibly MIS 31, the ‘super interglacial’), and the Norwegian Trench Interglacial to 0.50 ± 0.02 Ma (possibly MIS 13). A massive till unit identified at the same stratigraphic level in all shallow borings may partly represent an extensive MIS 12 glaciation. This study shows that the combined use of amino acid racemization data and Sr isotope chronology can refine the chronological ambiguities of Quaternary North Sea sediments related partly to the impact of glacial processes.     

Carbonate eolianites,quartz sands,and Quaternary sea-level cycles,Western Australia: A chronostratigraphic approach

Marine and eolian carbonate deposits, grouped under the name “Tamala Limestone”, have been investigated along thousands of kilometers of coastal Western Australia (WA). Relative-age diagenetic features of carbonate sand dunes or “eolianites” indicate that coastal ridges decrease in age seaward, reflecting coastal accretion during successive sea-level stands. Yellow- to red-stained quartz sands are associated with eolianites as pits, lenses, extensive beds, and even 40-m-high dunes.A regional survey using whole-rock and land snail amino acid epimerization geochronology confirms the eolianite succession and provides a means of correlating widespread deposits along a steep climatic gradient and 16° of latitude. AMS ¹⁴C and uranium–thorium (U/Th) ages provide independent radiometric calibration of the amino acid ratios, and eolianite ages can be estimated using a parabolic kinetic model.Over 90% of the sampled eolianite deposits comprise Aminozones A, C, E (125 ka), F?, G, and H, and correlate with interglacials from <10 ka (Holocene) to ca. 500 ka. In contrast, at the type locality of the Tamala Limestone along the Zuytdorp Cliffs, the upper eolianite-paleosol units are characterized by advanced stages of cavernous weathering, pedogenesis, and recrystallization. In the same units, sediment and snail samples generally yield very low or non-detectable levels of amino acids. These factors along with the stratigraphic complexity of the deposits reflect an age much greater than a large majority of sites along the WA coastline. These findings encourage a revision of the existing classification and nomenclature of Quaternary carbonate deposits in WA, as well as a reexamination of the underlying mechanisms related to the formation and emplacement of both carbonate and quartz dunes.     

40Ar/39Ar dating of the SP and Bar Ten lava flows AZ,USA: Laying the foundation for the SPICE cosmogenic nuclide production-rate calibration project

Precise ⁴⁰Ar/³⁹Ar age determinations made on basalt groundmass collected from the SP and upper and lower Bar Ten lava flows in the San Francisco and Uinkaret volcanic fields of Arizona, USA, yield ages of 72 ± 4, 97 ± 10, and 123 ± 12 ka (2σ; relative to Renne et al., 2010, 2011, full external precision), respectively. Previous ages of the SP lava flow include a K–Ar age of 70 ± 8 ka and OSL ages of 5.5–6 ka. ⁴⁰Ar/³⁹Ar age constraints, relative to the optimization model of Renne et al. (2010, 2011), of 81 ± 50 and 118 ± 64 ka (2σ; full external precision) were previously reported for the upper and lower Bar Ten lava flows, respectively. The new ⁴⁰Ar/³⁹Ar ages are within uncertainty of previous age constraints, and are more robust, accurate, and precise. Preliminary cosmogenic ³He and ²¹Ne production rates from the Bar Ten flows reported by Fenton et al. (2009) are updated here, to account for the improved quality of the ⁴⁰Ar/³⁹Ar data. The new ⁴⁰Ar/³⁹Ar age for the SP flow yields cosmogenic ³He and ²¹Ne production rates for pyroxene (119 ± 8 and 26.8 ± 1.9 at/g/yr; error-weighted mean, 2σ uncertainty; Dunai (2000) scaling method) that are consistent with production rate values reported throughout the literature. The ⁴⁰Ar/³⁹Ar and cosmogenic ³He and ²¹Ne data support field observations indicating the SP flow has undergone negligible erosion. The SP flow contains co-existing phenocrysts of olivine and pyroxene, as well as xenocrysts of quartz in a fine-grained groundmass facilitating cross-calibration of cosmogenic production rates and production-rate (³He, ¹⁰Be, ¹⁴C, ²¹Ne, ²⁶Al, and ³⁶Cl). Thus, we propose the SP flow is an excellent location for a cosmogenic nuclide production-rate calibration site (SPICE: the SP Flow Production-Rate Inter-Calibration Site for Cosmogenic-Nuclide Evaluations).     

In situ cosmogenic 10Be production-rate calibration from the Southern Alps,New Zealand

We present a ¹⁰Be production-rate calibration derived from an early Holocene debris-flow deposit at about 1000 m above sea level in the central Southern Alps, New Zealand, in the mid-latitude Southern Hemisphere. Ten radiocarbon ages on macrofossils from a soil horizon buried by the deposit date the deposit to 9690 ± 50 calendar years before AD2008. Surface ¹⁰Be concentrations of seven large boulders partially embedded in the stable surface of the deposit are tightly distributed, yielding a standard deviation of ～2%. Conversion of the ¹⁰Be measurements to sea level/high-latitude values using each of five standard scaling methods indicates ¹⁰Be production rates of 3.84 ± 0.08, 3.87 ± 0.08, 3.83 ± 0.08, 4.15 ± 0.09, and 3.74 ± 0.08 atoms g^?1 a^?1, relative to the ‘07KNSTD’ ¹⁰Be AMS standard, and including only the local time-integrated production-rate uncertainties. When including a sea level high-latitude scaling uncertainty the overall error is ～2.5% (1σ) for each rate. To test the regional applicability of this production-rate calibration, we measured ¹⁰Be concentrations in a set of nearby moraines deposited before 18 060 ± 200 years before AD2008. The ¹⁰Be ages are only consistent with minimum-limiting ¹⁴C age data when calculated using the new production rates. This also suggests that terrestrial in situ cosmogenic-nuclide production did not change significantly from Last Glacial Maximum to Holocene time in New Zealand. Our production rates agree well with those of a recent calibration study from northeastern North America, but are 12–14% lower than other commonly adopted values. The production-rate values presented here can be used elsewhere in New Zealand for rock surfaces exposed during or since the last glacial period.     

Refining the Quaternary Geomagnetic Instability Time Scale (GITS): Lava flow recordings of the Blake and Post-Blake excursions

The Blake excursion was among the first recognized with directional and intensity behavior known mainly from marine sediment and Chinese loess. Age estimates for the directional shifts in sediments are poorly constrained to about 118−100 ka, i.e., at the marine isotope stage (MIS) 5e/5d boundary. Moreover, sediments at Lac du Bouchet maar, France and along the Portuguese margin reveal what may be a "post-Blake" excursion at about 105−95 ka. The excursional directions are associated with a prominent paleointensity minimum between about 125 and 95 ka in global stacked records. Lava flow recordings of the Blake excursion(s) have, however, been questionable because precise ages required for correlation with these sediment records are lacking. To establish new, independent records of the Blake excursion, and link these into a larger Quaternary GITS, we have undertaken ⁴⁰Ar/³⁹Ar incremental heating and unspiked K-Ar experiments on groundmass from the transitionally magnetized Inzolfato flow on Lipari Island. We also obtained ⁴⁰Ar/³⁹Ar incremental heating results for a lava flow on Amsterdam Island originally thought to record the Mono Lake excursion and from the transitionally magnetized El Calderon basalt flow, New Mexico that was K-Ar dated by Champion et al. (1988) at 128 ± 66 ka.Unspiked K-Ar ages of four samples from the Inzolfato flow are 102.5 ± 4.7, 101.3 ± 3.3, 97.1 ± 2.6, and 96.8 ± 3.1 ka and thus indistinguishable from one another. ⁴⁰Ar/³⁹Ar results are more complex, with three samples yielding discordant age spectra. Based on incremental heating data obtained in both the UW-Madison and Gif-sur-Yvette ⁴⁰Ar/³⁹Ar laboratories, a fourth sample yields six concordant age plateaus and a weighted mean age of 105.2 ± 1.4 ka that we take as the best estimate of time since the flow erupted. Five ⁴⁰Ar/³⁹Ar incremental heating experiments on the Amsterdam Island lava yield a plateau age of 120 ± 12 ka, whereas ages from two sites in the Calderon flow are 112 ± 23 and 101 ± 14 ka, together giving a weighted mean of 104 ± 12 ka. The age of 120 ± 12 ka from Amsterdam Island, though imprecise, correlates with the Blake excursion. In contrast, the 104–105 ka age obtained from both Lipari and New Mexico indicates that these lavas record a younger period of dynamo instability, most probably associated with the post-Blake excursion. These radioisotopic ages are consistent with the astronomical ages of two paleointensity minima in the PISO-1500 global stack. Our findings indicate that the Blake and post-Blake excursions are both global features of past geodynamo behavior and support the hypothesis that Brunhes chron excursions are temporally clustered into two groups of at least a half-dozen each spanning over 220 to 30 ka and 720 to 520 ka.     

A chronological framework for the Clyde Foreland Formation,Eastern Canadian Arctic,derived from amino acid racemization and cosmogenic radionuclides

The most extensive terrestrial outcrops of glacial and glaciomarine deposits in the Eastern Canadian Arctic are exposed in sea cliffs along the Clyde Foreland and Qivitu Peninsula of Baffin Island. Collectively known as the Clyde Foreland Formation (CFF), these stacked deposits record at least seven glacial advances. Despite having been the focus of numerous investigations spanning nearly 50 years, no numerical chronological framework for the age of the deposits has been established. Previous studies relied on biostratigraphy and amino acid racemization (AAR) geochronology and postulated that the oldest units were Late Pliocene to Mid-Pleistocene in age. In this paper, we use a cosmogenic radionuclide isochron approach to determine a minimum age for the burial of a paleosol preserved within the CFF. Abundant palynomorphs in the paleosol are dominated by cool-climate taxa. Combining the paleosol burial age with a compilation of published and new CFF AAR data for marine bivalves Hiatella arctica and Mya truncata, we statistically define seven CFF aminozones and develop a piecewise isoleucine AAR calibration model for Baffin Island. From this, we estimate the minimum age of each aminozone, although the propagation of errors through all calculations produces large uncertainties for each age estimate. The youngest three CFF units, known as the Kogalu, Kuvinilk, and Cape Christian members, were most likely deposited during glaciations in the Mid- to Late-Pleistocene. The paleosol formed prior to 1.15 ± 0.20 Ma, and the underlying aminozones represent sedimentation during Early Pleistocene or latest Pliocene glaciations and record early advances of Laurentide ice across Baffin Island.     

An (U-Th)/He age for the small Monturaqui impact structure,Chile

Single-crystal (U-Th)/He dating of 32 apatite and zircon crystals from an impact breccia yielded a weighted mean age of 663 ± 28 ka (n = 3; 4.2 % 2σ uncertainties) for the Monturaqui impact structure, Chile. This ~350 m diameter simple crater preserves a small volume of impactite consisting of polymict breccias that are dominated by reworked target rock clasts. The small size, young age and limited availability of melt material for traditional geochronological techniques made Monturaqui a good test to define the lower limits of the (U-Th)/He system to successfully date impact events. Numerical modeling of ⁴He loss in apatite and zircon crystals shows that, for even small craters such as Monturaqui, the short-lived compressional stage and shock metamorphic stage can account for the observed partial to full resetting of (U-Th)/He ages in accessory minerals. Despite the distinctly different ⁴He diffusion parameters of apatite and zircon, the 2σ-overlapping youngest ages are recorded in both populations of minerals, which supports the inference that the weighted mean of the youngest (U-Th)/He population is the age of formation of this impact structure.     

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.