Testing the effect of oxidizing pre-treatments on amino acids in benthic and planktic foraminifera tests

Amino acid racemization (AAR) is a geochronological method that uses the ratio of D- to L-configurations in optically active amino acids from carbonate fossils to determine the time elapsed since the death of an organism. Although AAR techniques have been widely applied to foraminiferal tests, there have been limited dedicated assessments of the potential of isolating a bleach-resistant, intra-crystalline fraction of proteins to improve the reliability of AAR in this biomineral system. In this study, we evaluate the effect of two oxidative pre-treatments (hydrogen peroxide and bleach) on amino acid concentrations and D/L values in sub-modern benthic foraminifers (Ammonia spp. and Haynesina germanica) and well-preserved mid Holocene and mid Pleistocene planktic foraminifers (Pulleniatina obliquiloculata, Globorotalia truncatulinoides, and Globorotalia tumida). The oxidative pre-treatments successfully reduced the amino acid content of the foraminiferal tests to a residual fraction, and with the exception of Ammonia spp., neither pre-treatment substantially affected the relative proportion of individual amino acids. The bleaching pre-treatment does not consistently alter D/L values when compared to peroxide pre-treatment, but it does tend to reduce the subsample variability in D/L values, albeit only to a small degree in an inconsistent fashion. Therefore, we recommend that a relatively weak oxidative pre-treatment with 3% hydrogen peroxide is sufficient for foraminifera-based AAR applications.     

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.     

A Cerion-based chronostratigraphy and age model from the central Bahama Islands: Amino acid racemization and 14C in land snails and sediments

The taxonomy of the land-snail genus Cerion, and the relevance of hundreds of shell forms to phylogenetic and evolutionary processes has been the subject of much discussion over the past few decades. Fundamental to understanding evolutionary trends is the independent confirmation of the age, biostratigraphic, and chronostratigraphic order of a comprehensive set of fossil forms. Amino acid racemization (AAR) is a geochronological tool applicable to dating living and fossil Cerion shells. The extent of racemization of aspartic acid (Asp D/L) and glutamic acid (Glu D/L) were determined for 507 Cerion shells dating between the early last interglaciation (marine isotope stage (MIS) 5e, c. 125 ka) and the present from the Bahamas. The AAR data based on Cerion support the established morphostratigraphic succession of deposits younger than MIS 5e and provide greater resolution, particularly for biostratigraphic successions of Holocene age. Age models were constructed for Asp and Glu using D/L values paired with ¹⁴C ages and historical collection dates from 23 Cerion shells. In addition to the relative-age time series, the Holocene age models developed from D/L Glu and Asp apply to the last 7 ka and geographically within the central Bahamas. In two case studies, large numbers of AAR-generated ages provide insights into the age structure of accretionary soils and rates and age constraints on evolutionary processes related to Cerion land snails.     

Racemization of amino acids in fossil bones and teeth from the Olduvai Gorge region,Tanzania, East Africa

Investigation of amino acid racemization in fossil bones and teeth from the Olduvai Gorge region, Tanzania, indicates that aspartic acid racemization can be used to date samples which are less than ～80,000–100,000 years old in this area. In older samples, significant secondary aspartic acid is apparently present and thus these samples have lower than expectedD/L aspartic acid ratios. Isoleucine in older samples, however, is apparently syngenetic with the samples, so the epimerization of isoleucine to alloisoleucine can be used with certain limitations to date fossil bones and teeth from the older stratigraphic sections in the Olduvai region.     

Amino acid racemization dating of fossil bones,I. inter-laboratory comparison of racemization measurements

Enantiomeric measurements for aspartic acid, glutamic acid, and alanine in twenty-one different fossil bone samples have been carried out by three different laboratories using different analytical methods. These inter-laboratory comparisons demonstrate that D/L aspartic acid measurements are highly reproducible, whereas the enantiomeric measurements for the other amino acids show a wide variation between the three laboratories. At present, aspartic acid measurements are the most suitable for racemization dating of bone because of their superior analytical precision.     

Amino acid racemization in four species of ostracodes: Taxonomic,environmental, and microstructural controls

Here we quantified the aspartic acid and glutamic acid racemization rates of the four main ostracode species (Herpetocypris reptans, Candona neglecta, Ilyocypris gibba and Cyprideis torosa) present in several Iberian Peninsula localities covering a wide chronological range (ca. 1 Ma to present). At low D/L values (at Asp D/L < 0.40; and Glu D/L = 0.09–0.18), H. reptans racemized at higher rates than C. neglecta, C. torosa and I. gibba. In contrast, for Asp D/L > 0.4 and Glu D/L > 0.18, H. reptans, C. neglecta and C. torosa showed similar racemization rates. I. gibba exhibited the lowest D/L values in old samples (Middle and Lower Pleistocene). We attribute these differences in amino acid racemization rates mainly to variations in valve protein composition. We found that the microstructure of the valves of each species (size, morphology, and arrangement of crystals) differed, but did not appear to change over time (at least for the last ca. 1 Ma). Such differences may also be linked to the type of proteins involved in the respective calcification processes of these organisms. On the basis of our results, and given that other studies have demonstrated that the majority of inter-crystalline proteins are leached early after death (a few centuries or millennia), we propose that the degradation rates of the most resistant inter- and intra-crystalline proteins in each species differ depending on the protein composition of the valves. Although further research is required, we suggest that amino acid racemization in each ostracode species might be related to valve microstructure.     

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.     

Protein diagenesis in Patella shells: Implications for amino acid racemisation dating

The inter- and intra-crystalline fractions of Patella vulgata limpets recovered from archaeological sites in Northern Spain (covering Neolithic, Mesolithic, Magdalenian, Solutrean, and Aurignacian periods) were examined for amino acid composition and racemisation over time. The calcitic apex and rim areas of the shells were found to probably be composed of similar proteins, as the D/L values and amino acids were comparable and varied in the same way with increasing age; however, the mineral structures present in these areas differed. The aragonitic intermediate part of the shell showed a distinctly different amino acid composition and mineral structure. The main protein leaching from the inter-crystalline fraction occurred within the first 6000 yr after the death of the organism. In contrast, the intra-crystalline fraction — comprised of a different protein composition than the inter-crystalline fraction — appeared to behave as a closed system for at least 34 ka, as reflected by the lack of a significant decrease in the amino acid content; however, changes in the amino acid percentages occurred during this period. The concentration of aspartic acid remained almost constant with age both in inter- and intra-crystalline proteins, and its contribution to the total amino acid content increased with age at the expense of other amino acids such as glutamic acid, serine, glycine and alanine. Temperature is thought to play a key role in the amino acid racemisation of P. vulgata and could explain why in the localities belonging to the Gravettian and Solutrean period, which formed during relatively cold conditions, D/L values were similar to those detected in shells from sites formed during the Magdalenian.     

Aminostratigraphy of surface and subsurface Quaternary sediments,North Carolina coastal plain,USA

The Quaternary stratigraphy and geochronology of the Albemarle Embayment of the North Carolina (NC) Coastal Plain is examined using amino acid racemization (AAR) in marine mollusks, in combination with geophysical, lithologic, and biostratigraphic analysis of 28 rotasonic cores drilled between 2002 and 2006. The Albemarle Embayment is bounded by structural highs to the north and south, and Quaternary strata thin westward toward the Suffolk paleoshoreline, frequently referred to as the Suffolk Scarp. The Quaternary section is up to ～90 m thick, consists of a variety of estuarine, shelf, back-barrier, and lagoonal deposits, and has been influenced by multiple sea-level cycles. The temporal resolution of the amino acid racemization method is tested statistically and with the stratigraphic control provided by this geologic framework, and it is then applied to the correlation and age estimation of subsurface units throughout the region. Over 500 specimens (primarily Mercenaria and Mulinia) from the subsurface section have been analyzed using either gas chromatographic (GC) or reverse-phase liquid chromatographic (RPLC) techniques. The subsurface stratigraphic data are compared with AAR results from numerous natural or excavated exposures from the surrounding region, as well as results from NC beach collections, to develop a comprehensive aminostratigraphic database for the entire Quaternary record within the NC coastal system. Age mixing, recognized in the beach collections, is also seen in subsurface sections, usually where major seismic reflections or core lithology indicate the presence of stratigraphic discontinuities. Kinetic models for racemization are tested within the regional stratigraphic framework, using either radiocarbon or U-series calibrations or comparison with regional biostratigraphy. Three major Pleistocene aminozones [AZ2, AZ3, and AZ4] are found throughout the region, all being found in superposition in several cores. Each can be subdivided, yielding a total of at least eight stratigraphically and statistically distinct aminozones. Kinetic modeling, supplemented with local calibration, indicates that these aminozones represent depositional events ranging from ～80 ka to nearly 2 Ma. Three prominent seismic reflections are interpreted to represent the base of the early, middle, and late Pleistocene, respectively, roughly 2 Ma, 800 ka, and 130 ka. The large number of samples and the available stratigraphic control provide new insights into the capabilities and limitations of aminostratigraphic methods in assessing relative and numerical ages of Atlantic Coastal Plain Quaternary deposits.     

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.     

Variations in racemization/epimerization ratios and amino acid content of Glycymeris shells in raised marine deposits in the Mediterranean

In this study we compare the organic geochemistry of fossil and modern Glycymeris shells. Amino acids were preserved within the shells. The amino acid content of the shells was similar at all the sites studied. Amino acid racemization and epimerization of Glycymeris shells are suitable techniques for dating Pleistocene raised marine deposits. As reported in other studies, we found that isoleucine epimerization analysis has a greater capacity to discriminate between sites of different age than glutamic acid and aspartic acid. However, particular constraints regarding the use of amino acid dating concern intrashell variability, so to avoid divergent results, it is necessary to sample the same part of the shell, namely the complex cross lamellar region near the umbo. The dating of high-energy coastal marine deposits calls for extensive field work in order to ensure the collection of a large number of samples in order to obtain robust results and reject spurious values. Shell accumulations on the shore-line are conditioned by several factors. The high coefficients of variation for epimerization values and their distribution pattern can be attributed mainly to time-linked taphonomical processes (time-averaging) that gave rise to the shell-bearing bed. However, reworking from former highstand sea level deposits, which usually occupy higher topographic levels, is not a common occurrence. Therefore, as a result of time-averaging and post-depositional processes, it is difficult to identify substages in stacked shell beds in raised beach deposits belonging to the same marine oxygen isotope stage by means of amino acid racemization/epimerization.     

Converting A/I values (ion exchange) to D/L values (reverse phase) for amino acid geochronology

Several analytical techniques have been used in amino acid geochronology to measure the relative abundances of D- and L-enantiomers. During the past two decades, reverse-phase (RP) liquid chromatography has become most common, whereas ion-exchange (IE) liquid chromatography was widely used prior to the mid-1990s. This study is based on intra-lab paired analyses of RP and IE liquid chromatography to mathematically convert A/I (allo-isoleucine:isoleucine) values determined with IE to corresponding D/L values for comparison with new RP results. Pooled results of 340 paired IE and RP analyses show that A/I values can be confidently converted to equivalent D/L values for aspartic acid, glutamic acid, alanine, valine and isoleucine, with 2σ uncertainties of ±24–41% depending on the amino acid. For specific sample types including gastropod, bivalve, eggshell and whole rock, A/I can readily be converted to D/L aspartic acid and D/L glutamic acid with 2σ uncertainties of ±20% and 26%, respectively, using sample-type-specific relations. A/I is also reliably converted to D/L valine and D/L isoleucine with 2σ uncertainties of ±31 and 35%, respectively. Regression equations are provided to convert A/I to an equivalent D/L value for five amino acids, thereby enabling the large literature base of AAR results from IE chromatography to be compared and integrated with AAR results from RP chromatography.     

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.     

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.     

Role of glacial Arctic Ocean ice sheets in Pleistocene oxygen isotope and sea level records

A comparison of the oxygen isotope signal in deep-sea benthic foraminifera with the record of glacio-eustatic sea level for the last 160,000 years reveals that the amplitude of the benthic δ¹⁸O records predicts more continental ice volume than appears to be reflected in lowered sea level stands. These differences between the benthic δ¹⁸O ice volume estimates and radiometrically-dated records of eustatic sea level are consistent with the presence of a large floating Arctic Ocean ice mass during glacial intervals. The presence of an Arctic Ocean ice sheet during glacial intervals may account for the two climatic modes observed in oxygen isotope records which span the entire Pleistocene. The early Pleistocene (1.8 to 0.9 Myr B.P.) interval is characterized by low-amplitude, high-frequency δ¹⁸O fluctuations between glacial and interglacial periods, while the late Pleistocene (0.9 Myr B.P. to present) is characterized by large-amplitude, low-frequency δ¹⁸O changes. These two climatic modes can be explained by the initiation of earth orbital conditions favoring the co-occurrence of glacial period Arctic Ocean ice sheets and large continental ice sheets approximately 900,000 years before present.     

Evaluating Quaternary dating methods: Radiocarbon,U-series,luminescence, and amino acid racemization dates of a late Pleistocene emu egg

A whole emu egg, with infilling sediment believed to be coeval with egg laying and burial, was found in late Pleistocene lunette sediments near Lake Eyre, central Australia. The stratigraphic context and initial amino acid racemization (AAR) results suggested an age between 25 ka and 35 ka, ideal for a multiple cross-dating comparison. The sediment infilling the egg provided material for luminescence dating that minimized problems of association. Age estimations from AAR, ¹⁴C and U series methods were obtained from the eggshell and optically stimulated luminescence (OSL) of the infilling sediment. All methods agreed within their respective dating uncertainties confirming the utility of all four methods. They indicate an age for the emu egg of 31.24 ± 0.34 ka.     

Using tephrostratigraphy and cryptotephrostratigraphy to re-evaluate and improve the Middle Pleistocene age model for marine sequences in northeast Japan (Chikyu C9001C)

We refine the tephrostratigraphy and cryptotephrostratigraphy of the Middle Pleistocene deep-sea sediments in the C9001C cores and reconstruct the age model of the cores to provide a standard stratigraphy for the NW Pacific Ocean area. In the lower half of the cores (corresponding to marine isotopic stages [MISs] 9–18), we newly identify nine concentrations (spikes) of glass shards (numbered G17–G25 from top to bottom) below sixteen previously reported spikes (numbered G1–G16) in the upper half of the cores (MISs 1–9). We correlated two spikes (both cryptotephras) with known widespread tephras: G18 with Naruohama-IV (MIS 10d; 357 ka) and G19 with Kasamori 5 (MIS 12b–c; 434–458 ka). Although the two cryptotephra spikes cannot be distinguished by the major- and trace-element compositions of glass shards, these correlations are based upon their stratigraphic occurrence within separate glacial periods (MISs 10 and 12) as indicated by the δ¹⁸O stratigraphy of the C9001C sequence. Based on the stratigraphic positions of the Naruohama-IV and Kasamori 5 tephras, we assign the sediment units corresponding to MISs 10, 11, and 12, and revise the previous assignment of core segments corresponding to MISs 7, 8, and 9. The resulting tephra-based age model is consistent with the last occurrence of Proboscia curvirostris, but it is inconsistent with the first occurrence of Emiliania huxleyi. According to the new age model, the sedimentation rate during MISs 18–2 has ranged from 0.21 m/ky (during MIS 17) to 0.74 m/ky (during MISs 8 and 9), however, the sedimentation rate was never as high as the rate of 1.1 m/ky indicated by an earlier age model.     

Three approaches to radiocarbon calibration of amino acid racemization in Mulinia lateralis from the Holocene of the Chesapeake Bay,USA

A radiocarbon-calibrated aminochronology, based on the bivalve Mulinia lateralis, is presented for Chesapeake Bay core MD03-2661, a 25 m piston core drilled near Kent Island (38°53.21′N; 76°23.89′W) during the 2003 USGS Marion-Dufresne cruise. Three separate approaches were used to calibrate amino acid racemization (AAR) data for aspartic acid with radiocarbon data. For the first approach, a direct or paired analysis calibration incorporated eight articulated specimens, thereby allowing for the application of AAR and radiocarbon analysis of the same specimen and effectively eliminating both intrashell variability and time averaging as factors in the calibration. A second direct approach relied on valves that were bilaterally split to facilitate both AAR and radiocarbon dating, thus effectively eliminating time averaging effects from this calibration. For the third indirect approach, nine independent radiocarbon dates were combined with 129 Asx D/L ratios from the same core depths to produce an indirect calibration model, from which intershell variability and time averaging could be estimated. Variability in AAR ratios was recognized from a myriad of sources, including analytical error, intrashell variability, inherent variability, time averaging, and contamination. The majority of this variability was controlled for through experimental design or by the application of these three independent calibration approaches. The direct calibration of articulated shells and the indirect calibration yielded virtually identical age models, well within their respective 95% confidence intervals. This study establishes an aminostratigraphic reference section for the Holocene record of the Chesapeake Bay and demonstrates the usefulness of multiple calibration approaches and the potential utility of AAR for future studies of sedimentary processes and chronologies in the bay.     

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.     

Analysis of trends in annual streamflow to the Arctic Ocean

There is increasing interest in the magnitude of the flow of freshwater to the Arctic Ocean due to its impacts on the biogeophysical and socio‐economic systems in the north and its influence on global climate. This study examines freshwater flow based on a dataset of 72 rivers that either directly or indirectly contribute flow to the Arctic Ocean or reflect the hydrologic regime of areas contributing flow to the Arctic Ocean. Annual streamflow for the 72 rivers is categorized as to the nature and location of the contribution to the Arctic Ocean, and composite series of annual flows are determined for each category for the period 1975 to 2015. A trend analysis is then conducted for the annual discharge series assembled for each category. The results reveal a general increase in freshwater flow to the Arctic Ocean with this increase being more prominent from the Eurasian rivers than from the North American rivers. A comparison with trends obtained from an earlier study ending in 2000 indicates similar trend response from the Eurasian rivers, but dramatic differences from some of the North American rivers. A total annual discharge increase of 8.7 km³/y/y is found, with an annual discharge increase of 5.8 km³/y/y observed for the rivers directly flowing to the Arctic Ocean. The influence of annual or seasonal climate oscillation indices on annual discharge series is also assessed. Several river categories are found to have significant correlations with the Arctic Oscillation, the North Atlantic Oscillation, or the Pacific Decadal Oscillation. However, no significant association with climate indices is found for the river categories leading to the largest freshwater contribution to the Arctic Ocean.