Calibration of GA1550 biotite standard for K/Ar and 40Ar/39Ar dating

The mineral separate GA1550 biotite has become an international standard for K/Ar and ⁴⁰Ar/³⁹Ar dating studies, although it was prepared as an intralaboratory standard at ANU to monitor tracer depletion from a gas pipette. It is one of a small number of samples that has been calibrated against ³⁸Ar tracers, some of which had been mixed with known amounts of atmospheric argon, so that a so-called primary calibration has been performed. By measuring GA1550 biotite against additional tracers from the same batch we have determined the radiogenic argon content of this sample as 1.342 (± 0.007) × 10^? 9 mol/g, and together with the measured K content of 7.645 (± 0.050) weight percent, we derive a best estimate for the K/Ar age as 98.5 ± 0.5 Ma, where the error is derived from averaging the ages determined relative to the ³⁸Ar tracer.     

The Lower Albian (Lower Cretaceous) Monk's Bay Sandstone Formation (formerly the Carstone) of the Isle of Wight: Its distribution, litho- and biostratigraphy

The Monk's Bay Sandstone Formation (MBSF) is the new name for the Lower Albian ferruginous sandstone that was formerly known as the Carstone of the Isle of Wight. The new term was proposed to remove any confusion with the Carstone, of similar age and lithology, described from the separate Lower Cretaceous sedimentary basin of Eastern England. This paper formalises the nomenclatural change outlined in the Lower Cretaceous Framework Report, ratified by the Geological Society Stratigraphy Commission.The MBSF, representing a major mid-Albian transgressive event, is described from a series of boreholes drilled by the British Geological Survey across the Isle of Wight, and from additional coastal exposures, together with reinterpretations of sections described in earlier works.The age range of the MBSF is determined in relation to recent biostratigraphical schemes supported with new data from the previously unknown presence of foraminifera. Deposits, belonging to the Leymeriella regularis Subzone, were previously considered to be absent from the succession and represent the stratigraphical gap separating the formation from the underlying Sandrock Formation. However a first occurrence of tubular foraminifera resembling Hyperammina/‘Rhizammina cf dichotomata’ suggest that the oldest part of the formation in the northeast of the island may be of regularis Subzone age. This unconformity is correlated with the sequence boundary LG4 of Hesselbo and the presence of the Sonneratia kitchini Subzone at the base of the MBSF on the Isle of Wight suggests that this boundary should be placed at the lower of two candidate horizons within the successions of the Weald.The formation is restricted to the Isle of Wight but is coeval with similar coarse-grained sediments, e.g. the Carstone and ‘JunctionBeds’ to the north. The palaeogeography of the formation and the relationship with these similar deposits and the implications for the timing of mid-Albian structural events is briefly discussed. The identification of older Lower Greensand Group sediments beneath the MBSF in boreholes north of the Isle of Wight structure, together with new survey data indicating north-south orientated faulting affecting the early Cretaceous implies a tectonic element to the distribution the Lower Greensand Group sediments. Taken together these imply a complex interaction of tectonics and transgressive events throughout the Aptian and Albian over this structural high.     

The stratigraphical distribution of mid-Cretaceous Foraminifera near Ventnor, Isle of Wight

Ventnor No. 2 Borehole, located near Ventnor, Isle of Wight, penetrated the basal part of the Chalk Group and the Selborne Group before terminating in the upper part of the Lower Greensand Group (Sandrock Formation). The borehole was examined for Foraminifera, and although they were not seen in the Sandrock Formation and Monks Bay Sandstone Formation, the remainder of the borehole yielded moderately low diversity assemblages dominated by agglutinated species. Foraminiferal zones 3-6 (H dentatus to M. fallax/M. rostratum macrofaunal zones) were identified in the Gault Formation and zones 6 (lower) to 6a (M. fallax/M. rostratum to A. briacensis macrofaunal zones) were identified in the Upper Greensand Formation. Assemblages from the overlying West Melbury Marly Chalk Formation were used to identify foraminiferal zones BGS1-BGS3 (M. mantelli and M. dixoni macrofaunal zones).     

Size, speciation and lability of NOM-metal complexes in hyperalkaline cave dripwater

Transport of trace metals by natural organic matter (NOM) is potentially an important vector for trace metal incorporation in secondary cave precipitates [speleothems], yet little is known about the size distribution, speciation and metal binding properties of NOM in cave dripwaters. A hyperalkaline cave environment (ca. pH 11) was selected to provide information on colloid-metal interactions in cave waters, and to address the lack of high-pH data in natural systems in general. Colloidal (1 nm-1 μm) NOM in hyperalkaline cave dripwater from Poole’s Cavern, UK, was characterised by flow field-flow fractionation (FlFFF) coupled to UV and fluorescence detectors and transmission electron microscopy (TEM) coupled to X-ray energy-dispersive spectroscopy (X-EDS); trace-metal lability was examined by diffusive gradients in thin films (DGT). Colloidal aggregates and small particulates (>1 μm) imaged by TEM were morphologically heterogeneous with qualitative elemental compositions (X-EDS spectra; n = 41) consistent with NOM aggregates containing aluminosilicates, and iron and titanium oxides. Globular organic colloids, with diameters between ca. 1 and 10 nm were the most numerous colloidal class and exhibited high UV-absorbance (254 nm) and fluorescence intensity (320:400 nm excitation: emission) in optical regions characteristic of humic-like compounds. Metal binding with humic substances was modelled using the WHAM 6.1 (model VI) and visual MINTEQ 3.0 (NICA-Donnan) speciation codes. At pH 11, both models predicted dominant humic binding of Cu (ca. 100%) and minimal binding of Ni and Co (ca. <1-7%). A DGT depletion experiment (7 days duration) with the hyperalkaline dripwater showed that the available proportion of each metal was much lower than its total concentration. Metal availability for DGT in the initial stages (24 h) was consistent with weaker binding of alkaline earth metals by humic substances (Ba > Sr > V > Cu > Ni > Co), compared to the transition metals. Integrated over the entire experiment, the DGT-available proportion of transition metals (Ni > Cu & V >> Co) differed greatly from the expected hierarchy from WHAM and MINTEQ, indicating unusually strong complexation of Co. Total metal concentrations of Cu, Ni, and Co in raw and filtered PE1 dripwater samples (n = 53) were well correlated (Cu vs. Ni, R² = 0.8; Cu vs. Co, R² = 0.5) and were strongly reduced (> ca. 50%) by filtration at ca. 100 and 1 nm, indicating a common colloidal association. Our results demonstrate that soil-derived colloids reach speleothems, despite transport through a karst zone with potential for adsorption, and that NOM is a dominant complexant of trace metals in high pH speleothem-forming groundwaters.     

Observations of fluid‐dependent shear‐wave splitting in synthetic porous rocks with aligned penny‐shaped fractures‡

P‐ and S‐wave velocity and attenuation coefficients (accurate to ±0.3% and ±0.2 dB/cm, respectively) were measured in synthetic porous rocks with aligned, penny‐shaped fractures using the laboratory ultrasonic pulse‐echo method. Shear‐wave splitting was observed by rotating the S‐wave transducer and noting the maximum and minimum velocities relative to the fracture direction. A block of synthetic porous rock of fracture density 0.0201 ± 0.0068 and fracture size 3.6 ± 0.38 mm (measured from image analysis of X‐ray CT scans) was sub‐sampled into three 20–30 mm long, 50 mm diameter core plugs oriented at 0°, 45° and 90° to the fracture normal (transversely isotropic symmetry axis). Full waveform data were collected over the frequency range 500–1000 kHz for both water and glycerin saturated cores to observe the effect of pore fluid viscosity at 1 cP and 100 cP, respectively. The shear‐wave splitting observed in the 90° core was 2.15 ± 0.02% for water saturated and 2.39 ± 0.02% for glycerin saturated, in agreement with the theory that suggests that the percentage splitting should be 100 times the fracture density and independent of the saturating fluid. In the 45° core, by contrast, splitting was 0.00 ± 0.02% for water saturation and ?0.77 ± 0.02% for glycerin saturation. This dependence on fracture orientation and pore fluid viscosity is consistent with the poro‐visco‐elastic theory for aligned, meso‐scale fractures in porous rocks. The results suggest the possible use of shear‐ or converted‐wave data to discriminate between fluids on the basis of viscosity variations.     

A transitioning Arctic surface energy budget: the impacts of solar zenith angle, surface albedo and cloud radiative forcing

Snow surface and sea-ice energy budgets were measured near 87.5°N during the Arctic Summer Cloud Ocean Study (ASCOS), from August to early September 2008. Surface temperature indicated four distinct temperature regimes, characterized by varying cloud, thermodynamic and solar properties. An initial warm, melt-season regime was interrupted by a 3-day cold regime where temperatures dropped from near zero to ?7°C. Subsequently mean energy budget residuals remained small and near zero for 1 week until once again temperatures dropped rapidly and the energy budget residuals became negative. Energy budget transitions were dominated by the net radiative fluxes, largely controlled by the cloudiness. Variable heat, moisture and cloud distributions were associated with changing air-masses. Surface cloud radiative forcing, the net radiative effect of clouds on the surface relative to clear skies, is estimated. Shortwave cloud forcing ranged between ?50 W m^?2 and zero and varied significantly with surface albedo, solar zenith angle and cloud liquid water. Longwave cloud forcing was larger and generally ranged between 65 and 85 W m^?2, except when the cloud fraction was tenuous or contained little liquid water; thus the net effect of the clouds was to warm the surface. Both cold periods occurred under tenuous, or altogether absent, low-level clouds containing little liquid water, effectively reducing the cloud greenhouse effect. Freeze-up progression was enhanced by a combination of increasing solar zenith angles and surface albedo, while inhibited by a large, positive surface cloud forcing until a new air-mass with considerably less cloudiness advected over the experiment area.     

Non-stationarity of the signal and noise characteristics of seasonal precipitation anomalies

In order to improve seasonal-to-interannual precipitation forecasts and their application by decision makers, there is a clear need to understand when, where, and to what extent seasonal precipitation anomalies are driven by potentially predictable surface–atmosphere interactions versus to chaotic interannual atmospheric dynamics. Using a simple Monte Carlo approach, interannual variability and linear trends in the SST-forced signal and potential predictability of boreal winter precipitation anomalies is examined in an ensemble of twentieth century AGCM simulations. Signal and potential predictability are shown to be non-stationary over more than 80% of the globe, while chaotic noise is shown to be stationary over most of the globe. Correlation analysis with respect to magnitudes of the four leading modes of global SST variability suggests that interannual variability and trends in signal and potential predictability over 35% of the globe is associated with ENSO-related SST variability; signal and potential predictability are not significantly associated with SST modes characterized by a global SST trend, North Atlantic SST variability, and North Pacific SST variability, respectively. Results suggest that mechanisms other than SST variability contribute to the non-stationarity of signal and noise characteristics of hydroclimatic variability over mid- and high-latitude regions.     

Morphometric analysis of aeolian bedforms in the Namib Sand Sea using ASTER data

The ASTER Global Digital Elevation Model (GDEM) has made elevation data at 30 m spatial resolution freely available, enabling reinvestigation of morphometric relationships derived from limited field data using much larger sample sizes. These data are used to analyse a range of morphometric relationships derived for dunes (between dune height, spacing, and equivalent sand thickness) in the Namib Sand Sea, which was chosen because there are a number of extant studies that could be used for comparison with the results. The relative accuracy of GDEM for capturing dune height and shape was tested against multiple individual ASTER DEM scenes and against field surveys, highlighting the smoothing of the dune crest and resultant underestimation of dune height, and the omission of the smallest dunes, because of the 30 m sampling of ASTER DEM products. It is demonstrated that morphometric relationships derived from GDEM data are broadly comparable with relationships derived by previous methods, across a range of different dune types. The data confirm patterns of dune height, spacing and equivalent sand thickness mapped previously in the Namib Sand Sea, but add new detail to these patterns. Copyright © 2011 John Wiley & Sons, Ltd.     

Carbon mass-balance modelling and carbon isotope exchange processes in dynamic caves

Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of ¹³C and ¹²C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ¹³C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO₂, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO₂ concentrations and tested against the carbon isotope data. Air advection forces winter pCO₂ to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO₂ from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. ¹³C-enrichment of dripwater whose δ¹³C_DIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ¹³C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO₂ evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic ¹³C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO₂ between cave water and cave air. This implies that speleothem δ¹³C values may not be simply interpreted either in terms of hydrology or soil processes.     

A 2000-yr-long multi-proxy lacustrine record from eastern Baffin Island, Arctic Canada reveals first millennium AD cold period

We generate a multi-proxy sub-centennial-scale reconstruction of environmental change during the past two millennia from Itilliq Lake, Baffin Island, Arctic Canada. Our reconstruction arises from a finely subsectioned ²¹⁰Pb- and ¹⁴C-dated surface sediment core and includes measures of organic matter (e.g., chlorophyll a; carbon–nitrogen ratio) and insect (Diptera: Chironomidae) assemblages. Within the past millennium, the least productive, and by inference coldest, conditions occurred ca. AD 1700–1850, late in the Little Ice Age. The 2000-yr sediment record also reveals an episode of reduced organic matter deposition during the 6th–7th century AD; combined with the few other records comparable in resolution that span this time interval from Baffin Island, we suggest that this cold episode was experienced regionally. A comparable cold climatic episode occurred in Alaska and western Canada at this time, suggesting that the first millennium AD cold climate anomaly may have occurred throughout the Arctic. Dramatic increases in aquatic biological productivity at multiple trophic levels are indicated by increased chlorophyll a concentrations since AD 1800 and chironomid concentrations since AD 1900, both of which have risen to levels unprecedented over the past 2000 yr.