Identifying outliers and assessing the accuracy of amino acid racemization measurements for geochronology: II. Data screening

Amino acid racemization (AAR) is a cost-effective method for dating the large numbers of specimens required for time-averaging studies. Because the aim of time-averaging studies is to determine the structure of the age distribution, any data screening must be done cautiously and systematically. Methods to quantitatively assess the quality of AAR data and to identify aberrant specimens are under-developed. Here we examine a variety of screening criteria for identifying outliers and determining the suitability of specimens for numerical dating including: high serine concentrations (modern contamination), covariance of aspartic acid (Asp) and glutamic acid (Glu) concentrations (diagenetic influences), replication of measurements (specimen heterogeneity), and the relation between Asp and Glu d/l values (internal consistency). This study is based on AAR analyses of 481 late Holocene shells of four molluscan taxa (Ethalia, Natica, Tellina, and Turbo) collected from shallow sediment cores from the central Great Barrier Reef. Different outliers are flagged by the different screening criteria, and 6% of specimens were found to be unsuitable for time-averaging analyses based on screening the raw AAR data. We recommend a hybrid approach for identifying outliers and specimens for numerical dating.     

Radiocarbon-calibrated multiple amino acid geochronology of Holocene molluscs from Bramble and Rib Reefs (Great Barrier Reef,Australia)

Calibrated amino acid racemisation methods allow paleobiologists to quantify the age distributions of fossil assemblages. Focussing on 110 Scissulina dispar and 110 Liloa sp. specimens collected from Bramble and Rib Reefs (central Great Barrier Reef, Australia), we create calibration curves for seven amino acids for each taxon. Using these curves we calculate seven quasi-independent age estimates for each specimen. We evaluate each calibration curve for consistency and use the weighted mean and uncertainty of the quasi-independent ages as the specimen age for geochronological analyses. We extend the “Y” criterion for screening specimens and describing the precision of an AAR dataset from two amino acids to any number of amino acids. Using weighted mean ages and Y < 0.2 we demonstrate that the top 1.4 m of Bramble and Rib Reefs preserve remarkably well-mixed shell assemblages spanning from living to ∼3400 years old with median ages of 373 and 326 years old, respectively.     

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.     

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.     

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.     

Regional beryllium-10 production rate calibration for late-glacial northeastern North America

The major uncertainty in relating cosmogenic-nuclide exposure ages to ages measured by other dating methods comes from extrapolating nuclide production rates measured at globally scattered calibration sites to the sites of unknown age that are to be dated. This uncertainty can be reduced by locating production rate calibration sites that are similar in location and age to the sites to be dated. We use this strategy to reconcile exposure age and radiocarbon deglaciation chronologies for northeastern North America by compiling ¹⁰Be production rate calibration measurements from independently dated late-glacial and early Holocene ice-marginal landforms in this region. ¹⁰Be production rates measured at these sites are 6–12% lower than predicted by the commonly accepted global ¹⁰Be calibration data set used with any published production rate scaling scheme. In addition, the regional calibration data set shows significantly less internal scatter than the global calibration data set. Thus, this calibration data set can be used to improve both the precision and accuracy of exposure dating of regional late-glacial events. For example, if the global calibration data set is used to calculate exposure ages, the exposure-age deglaciation chronology for central New England is inconsistent with the deglaciation chronology inferred from radiocarbon dating and varve stratigraphy. We show that using the regional data set instead makes the exposure age and radiocarbon chronologies consistent. This increases confidence in correlating exposure ages of ice-marginal landforms in northeastern North America with glacial and climate events dated by other means.     

Chronostratigraphy and morphological changes in Cerion land snail shells over the past 130 ka on Long Island,Bahamas

Despite the nearly 600 named species of the land snail Cerion, studies of the geological and paleontological framework of modern species are few. To address this deficiency, the biostratigraphic succession of Cerion was investigated at several areas on Long Island, Bahamas. A chronostratigraphic framework was developed through whole-rock and Cerion land snail aminostratigraphies. About 175 individual Cerion shells from last interglacial and Holocene deposits were age-ranked using stratigraphic position and amino acid racemization (AAR) geochronology. AAR ages were generated using an existing AAR-¹⁴C age model for Cerion from the central Bahamas. The age structure of Cerion fossils in sediments was determined with AAR ages, and the magnitude of “dead carbon” anomalies was evaluated using this chronological approach.Temporal changes in gross shell morphology were examined from four study areas. The last interglacial, marine isotope stage/substage (MIS) 5e (Aminozone E) is characterized by generally large shells and in some cases, bimodal sets of very small (α shells) and very large forms (β shells) coexisting in the same stratigraphic levels (primarily soils), which may encompass the transition from between MIS 5e and 5d/c. Similar bimodality of nearly identical α and β shell forms and sizes is observed at other late MIS 5e sites from the furthest reaches of Great Bahama Bank (including Long, Exumas, Eleuthera, and New Providence Islands). The widespread distribution of α and β forms in soils capping MIS 5e marine and eolian deposits implies that there may have been a synchronous, regional morphological convergence on Great Bahama Bank. None of these forms are observed in Holocene deposits of Aminozone A.The earliest MIS 1 Cerion appear in a oolite deposited 6500 a BP, and are of intermediate size compared to the Pleistocene α and β forms. As MIS 1 progressed, the diversity of shell sizes and shapes increased into modern times. The greater variety of shell forms over the past 1000–2000 a suggests that humans may have played a role in the introduction and redistribution of Cerion across the region. The potential for frequent and widespread human introductions, combined with the propensity of Cerion to hybridise freely may explain the farrago of shell sizes and shapes in the recent snail faunas of Long Island and other Bahama islands.     

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.     

United States Quaternary coastal sequences and molluscan racemization geochronology – What have they meant for each other over the past 45 years?

The field of amino acid racemization (AAR) geochronology had its beginnings in the 1960's with the analysis of Quaternary mollusks of known relative age from United States Atlantic coast sites. Subsequent AAR studies of sites from Florida, California and then the entire western and eastern coasts of the U.S. have documented two important concepts: 1) in both uplifted marine terrace and subsurface sections, it can be demonstrated that D/L values increase with increasing geologic age; 2) D/L values in samples of equal age increase with decreasing latitude (increasing temperature). These two north–south coastlines with broad latitude ranges (Pacific sites span more than 20°, Atlantic sites more than 15°) provide an ideal, rare framework to test these principles, and the contrast in thermal histories of these two coasts (one maritime, the other more continental) adds additional insights into issues of aminozone correlation over latitude ranges as small as 2°. The trend of D/L values vs. latitude (isochrons) is established using calibrations based primarily on U–Th coral dating, the best of these calibrated trends seen for multiple sites on the Pacific coast. Pacific coast isochrons follow smooth trends and have been used to create and evaluate kinetic models using the modern latitudinal temperature gradient for comparison. Atlantic coast isochrons are more difficult to reconcile with the modern temperature gradient and available U–Th coral ages, suggesting either complex effective temperatures or unknown diagenetic effects on the AAR results. In addition to these studies that used local or regional field studies to test and evaluate AAR methods, relative or numerical ages based on AAR studies on both coasts have contributed to research on coastal uplift or subsidence rates, coastal stratigraphy and sea-level history, age mixing, and diagenesis of carbonate fossils.     

Optically stimulated luminescence dating of single and multiple grains of quartz from perennially frozen loess in western Yukon Territory, Canada: Comparison with radiocarbon chronologies for the late Pleistocene Dawson tephra

Optically stimulated luminescence (OSL) dating of perennially frozen loess was tested on quartz grains extracted from deposits associated with the late Pleistocene Dawson tephra in western Yukon Territory, Canada. OSL samples were obtained from ice-rich loess bracketing the Dawson tephra, while radiocarbon (¹⁴C) samples were collected from the bulk sediments directly underlying the tephra and from a ground-squirrel burrow 2.7 m below the tephra. Here we report the OSL characteristics and ages of the extracted quartz grains, as well as additional radiocarbon ages for samples described in Froese [2002. Age and significance of the late Pleistocene Dawson tephra in eastern Beringia. Quaternary Science Reviews 21, 2137–2142; 2006. Seasonality of the late Pleistocene Dawson tephra and exceptional preservation of a buried riparian surface in central Yukon Territory, Canada. Quaternary Science Reviews 25, 1542–1551]. We refine the time of Dawson tephra deposition to between 25,420±70 and 25,290±80 ¹⁴C a BP. Bayesian analysis of constraining radiocarbon ages places the deposition of the Dawson tephra at between 30,433 and 30,032 cal a BP. Linear modulation (LM) OSL analysis of multi-grain aliquots of quartz showed that the initial part of the decay curve is dominated by a rapidly bleached (‘fast’) component; these samples, however, had relatively dim continuous wave (CW) OSL signals at the multi-grain aliquot (each composed of 80 grains) and single-grain scales of analysis. The single-aliquot regenerative-dose protocol was applied to multi-grain aliquots and single grains to obtain equivalent dose (D_e) values for samples collected from below and above the Dawson tephra. The D_e values were examined graphically and numerically, the latter using the central age, minimum age, and finite mixture models. For multi-grain aliquots, the central age model gave weighted mean D_e values between 30 and 50 Gy, which greatly underestimated the expected D_e of 74–81 Gy for both samples studied. Possible reasons for these underestimations are discussed, and a solution proposed based on single-grain analysis. Measurements of single grains produced D_e values in agreement with the expected D_e, and yielded OSL ages of 28±5 and 30±4 ka for the samples taken from above and below the Dawson tephra, respectively. Examination of individual grains with differing luminescence behaviors showed that a significant number of the measured quartz grains exhibited anomalous luminescence properties that would have compromised the results obtained from multi-grain aliquots. We therefore recommend analysis of individual grains to overcome the age-shortfall from multi-grain analysis of these and similar samples of quartz.     

Comparative dating of a Bison-bearing late-Pleistocene deposit,Térapa,Sonora, Mexico

A recently discovered Bison-bearing fossil locality at Térapa, Sonora, Mexico, had previously been dated to 440 ± 130 ka using whole rock ⁴⁰Ar/³⁹Ar on a basalt flow that impounds the deposit. This age is considerably older than the accepted age of about 240–160 ka for the migration of Bison into greater North America. The Térapa deposit also contains a mixture of fossils from extralimital or extinct tropical animals and temperate animals. Constraining the age of the deposit is critical to interpret the paleontologic and paleoclimatologic implications of this unique Sonoran fossil locality. Three additional geochronological methods have been applied to this deposit (infrared stimulated luminescence (IRSL), amino acid racemization (AAR), and radiocarbon) and the data from the original ⁴⁰Ar/³⁹Ar age were revisited. The IRSL data suggest that the impounding basalt flow and the sediments that abut it were emplaced 43 ka ago and that the oldest sediments were deposited shortly after. Two radiocarbon ages suggest the fossiliferous sediments were emplaced by 42 ka. Effective diagenetic temperatures inferred from the AAR results, combined with AAR data from a similar-age deposit in southern Arizona, are in accordance with the 40–43 ka age estimates. For the AAR results to corroborate the ⁴⁰Ar/³⁹Ar age, the effective diagenetic temperature for the area would need to be approximately 3 °C, which is unrealistically low for northern Mexico. The new geochronological results suggest the Térapa deposit and fossils are 40–43 ka old. The anomalously old ⁴⁰Ar/³⁹Ar age for the impounding basalt is probably the result of low ⁴⁰Ar* concentrations and inherited ⁴⁰Ar.     

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.     

Regional Be production rate calibration for the past 12 ka deduced from the radiocarbon-dated Grøtlandsura and Russenes rock avalanches at 69° N, Norway

Two rock avalanches in Troms County – the Grøtlandsura and Russenes – were selected as CRONUS-EU natural cosmogenic ¹⁰Be production-rate calibration sites because they (a) preserve large boulders that have been continuously exposed to cosmic irradiation since their emplacement; (b) contain boulders with abundant quartz phenocrysts and veins with low concentrations of naturally-occurring ⁹Be (typically < 1.5 ppb); and (c) have reliable minimum radiocarbon ages of 11,424 ± 108 cal yr BP and 10,942 ± 77 cal yr BP (1σ), respectively. Quartz samples (n = 6) from these two sites contained between 4.28 × 10⁴ and 5.06 × 10⁴ at ¹⁰Be/g using the 1.387 Myr ¹⁰Be half-life. Determination of these concentrations accounts for topographic and self-shielding, and effects on nuclide production due to isostatic rebound are shown to be negligible. Persistent, constant snow and moss cover cannot be proven, but if taken into consideration they may have reduced ¹⁰Be concentrations by 10%. Using the ¹⁰Be half-life of 1.387 Myr and the Stone scaling scheme, and accounting for snow- and moss-cover, we calculate an error-weighted mean total ¹⁰Be production rate of 4.12 ± 0.19 at/g/yr (1σ). A corresponding error-weighted mean spallogenic ¹⁰Be production rate is 3.96 ± 0.16 at/g/yr (1σ), respectively. These are in agreement within uncertainty with other ¹⁰Be production rates in the literature, but are significantly, statistically lower than the global average ¹⁰Be production rate. This research indicates, like other recent studies, that the production of cosmogenic ¹⁰Be in quartz is lower than previously established by other production-rate calibration projects. Similarly, our findings indicate that regional cosmogenic production rates should be used for determining exposure ages of landforms in order to increase the accuracy of those ages. As such, using the total ¹⁰Be production rate from our study, we determine an error-weighted mean surface-exposure age of a third rock avalanche in Troms County (the Hølen avalanche) to be 7.5 ± 0.3 kyr (1σ). This age suggests that the rock avalanche occurred shortly after the 8.2 kyr cooling event, just as the radiocarbon ages of the Grøtlandsura and Russenes avalanches confirm field evidence that those rock-slope failures occurred shortly after deglaciation.     

Hemolytic activity and fatty acids composition in the ichthyotoxic dinoflagellate Cochlodinium polykrikoides isolated from Bahía de La Paz, Gulf of California

The hemolytic activity of the dinoflagellate Cochlodinium polykrikoides from Bahía de La Paz, Gulf of California was investigated as part of the ichthyotoxic mechanism of this microalga. Two different kinds of erythrocytes, fish and human, were tested for the hemolytic assay. Since fatty acids have been associated with hemolytic activity in C. polykrikoides, the composition of fatty acids of this dinoflagellate was also analyzed. The concentration of C. polykrikoides causing 50% hemolysis (HE₅₀) was 4.88 and 5.27 × 10⁶ cells L⁻¹, for fish and human erythrocytes, respectively. According to the standard curve of saponin, an equivalence between the hemolytic activity of saponin and the dinoflagellate concentration was found with 1 μg saponin mL⁻¹ equivalent to 1 × 10⁶ cells L⁻¹ of C. polykrikoides. The polyunsaturated fatty acids: hexadecaenoic (16:0), docosahexaenoic (22:6 n3) and octadecapentaenoic (18:5 n3) were found in an abundance of 62% of total fatty acids.     

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.     

Mathematical expressions used in amino acid racemisation geochronology—A review

A variety of mathematical expressions that describe changes over time (t) in the extent of amino acid racemisation (AAR, expressed as the ratio of d- to l-amino acid isomers or epimers) have been used in Quaternary geochronology. The integrated rate equation was first used to estimate fossil age from D/L but its geochronological utility is disadvantaged by uncertainties regarding the conformity of AAR in fossil protein to apparent reversible first-order kinetics for the entire reaction history. ‘Non-linear’ models have subsequently been used to relate D/L to t. The logarithmic equation successfully applied to Atlantic Coastal Plain research has not achieved widespread application, perhaps due to the regional calibration required if sensitivity to temperature is to be modelled, or the difficulties encountered when extending the model to include fossils with D/L<0.1. Success producing a linear correlation between D/L transformed with a power function and t has seen this approach emerge as one of the most commonly applied in AAR geochronology in recent years. Like parabola curve fitting, which has been applied to trends in D/L versus t in a variety of fossils and geographic settings, power transformations may not be suitable for geochronological modelling during the latter stages of amino acid diagenesis. Several studies have demonstrated the utility of simple and contingent linear equations for relating D/L to t. Future research should aim to reduce reliance on independent calibration and explore the geochronological benefits of AAR in pools other than the total hydrolysable amino acids.     

A multidisciplinary effort to assign realistic source parameters to models of volcanic ash-cloud transport and dispersion during eruptions

During volcanic eruptions, volcanic ash transport and dispersion models (VATDs) are used to forecast the location and movement of ash clouds over hours to days in order to define hazards to aircraft and to communities downwind. Those models use input parameters, called “eruption source parameters”, such as plume height H, mass eruption rate Ṁ, duration D, and the mass fraction m₆₃ of erupted debris finer than about 4 or 63 μm, which can remain in the cloud for many hours or days. Observational constraints on the value of such parameters are frequently unavailable in the first minutes or hours after an eruption is detected. Moreover, observed plume height may change during an eruption, requiring rapid assignment of new parameters. This paper reports on a group effort to improve the accuracy of source parameters used by VATDs in the early hours of an eruption. We do so by first compiling a list of eruptions for which these parameters are well constrained, and then using these data to review and update previously studied parameter relationships. We find that the existing scatter in plots of H versus Ṁ yields an uncertainty within the 50% confidence interval of plus or minus a factor of four in eruption rate for a given plume height. This scatter is not clearly attributable to biases in measurement techniques or to well-recognized processes such as elutriation from pyroclastic flows. Sparse data on total grain-size distribution suggest that the mass fraction of fine debris m₆₃ could vary by nearly two orders of magnitude between small basaltic eruptions ( 0.01) and large silicic ones (> 0.5). We classify eleven eruption types; four types each for different sizes of silicic and mafic eruptions; submarine eruptions; “brief” or Vulcanian eruptions; and eruptions that generate co-ignimbrite or co-pyroclastic flow plumes. For each eruption type we assign source parameters. We then assign a characteristic eruption type to each of the world's  1500 Holocene volcanoes. These eruption types and associated parameters can be used for ash-cloud modeling in the event of an eruption, when no observational constraints on these parameters are available.     

The effect of carbon dioxide cooling on trends in the F2-layer ionosphere

The effect of carbon dioxide (CO₂) cooling on trends of h_mF₂ and N_mF₂ are investigated using a coupled thermosphere and ionosphere general circulation model. Model simulations indicate that CO₂ cooling not only causes contraction of the upper atmosphere and changes of neutral and ion composition but also changes dynamics and electrodynamics in the thermosphere/ionosphere. These changes determine the altitude dependence of ionospheric trends and complex latitudinal, longitudinal, diurnal, seasonal, and solar cycle variations of trends of h_mF₂ and N_mF₂. Under the CO₂ cooling effect, trends of N_mF₂ are negative with magnitude from 0% to −40% for doubled CO₂, depending on location, local time, season, and solar activity. The corresponding trends of h_mF₂ are mostly negative with a magnitude from 0 to −40 km, but can be positive with a magnitude from 0 to 10 km at night, with maximum positive trends occurring after midnight under solar minimum conditions.     

From regional seismic hazard to “scenario earthquakes” for seismic microzoning: A new methodological tool for the Celano Project

We present the results of a probabilistic seismic hazard assessment and disaggregation analysis aimed to understand the dominant magnitudes and source-to-site distances of earthquakes that control the hazard at the Celano site in the Abruzzo region of central Italy. Firstly, we calculated a peak ground acceleration map for the central Apennines area, by using a model of seismogenic sources defined on geological-structural basis. The source model definition and the probabilistic seismic hazard evaluation at the regional scale (central Apennines) were obtained using three different seismicity models (Gutenberg–Richter model; characteristic earthquake model; hybrid model), consistent with the available seismological information. Moreover, a simplified time-dependent hypothesis has been introduced, computing the conditional probability of earthquakes occurrence by Brownian passage time distributions.Subsequently, we carried out the disaggregation analysis, with a modified version of the SEISRISK III code, in order to separate the contribution of each source to the total hazard.The results show the percentage contribution to the Celano hazard of the various seismogenic sources, for different expected peak ground acceleration classes. The analysis was differentiated for close (distance from Celano <20 km) and distant (distance from Celano >20 km) seismogenic sources. We propose three different “scenario earthquakes”, useful for the site condition studies and for the seismic microzoning study: (1) large (M=6.6) local (Celano-epicentre distance 16 km) earthquake, with mean recurrence time of 590 years; (2) moderate (M=5.5) local (Celano-epicentre distance 7.5 km) earthquake, with mean recurrence time of 500 years; and (3) large (M=6.6) distant (Celano-epicentre distance 24 km) earthquake, with mean recurrence time of 980 years.The probabilistic and time-dependent approach to the definition of the “scenario earthquakes” changes clearly the results in comparison to traditional deterministic analysis, with effects in terms of engineering design and seismic risk reduction.     

Radiocarbon dating of small terrestrial gastropod shells in North America

Fossil shells of small terrestrial gastropods are commonly preserved in wetland, alluvial, loess, and glacial deposits, as well as in sediments at many archeological sites. These shells are composed largely of aragonite (CaCO₃) and potentially could be used for radiocarbon dating, but they must meet two criteria before their ¹⁴C ages can be considered to be reliable: (1) when gastropods are alive, the ¹⁴C activity of their shells must be in equilibrium with the ¹⁴C activity of the atmosphere, and (2) after burial, their shells must behave as closed systems with respect to carbon. To evaluate the first criterion, we conducted a comprehensive examination of the ¹⁴C content of the most common small terrestrial gastropods in North America, including 247 AMS measurements of modern shell material (3749 individual shells) from 46 different species. The modern gastropods that we analyzed were all collected from habitats on carbonate terrain and, therefore, the data presented here represent worst-case scenarios. In sum, ～78% of the shell aliquots that we analyzed did not contain dead carbon from limestone or other carbonate rocks even though it was readily available at all sites, 12% of the aliquots contained between 5 and 10% dead carbon, and a few (3% of the total) contained more than 10%. These results are significantly lower than the 20–30% dead carbon that has been reported previously for larger taxa living in carbonate terrain. For the second criterion, we report a case study from the American Midwest in which we analyzed fossil shells of small terrestrial gastropods (7 taxa; 18 AMS measurements; 173 individual shells) recovered from late-Pleistocene sediments. The fossil shells yielded ¹⁴C ages that were statistically indistinguishable from ¹⁴C ages of well-preserved plant macrofossils from the same stratum. Although just one site, these results suggest that small terrestrial gastropod shells may behave as closed systems with respect to carbon over geologic timescales. More work on this subject is needed, but if our case study site is representative of other sites, then fossil shells of some small terrestrial gastropods, including at least five common genera, Catinella, Columella, Discus, Gastrocopta, and Succinea, should yield reliable ¹⁴C ages, regardless of the local geologic substrate.