Stratigraphy of total metals in PIRLA sediment cores

Sediment cores from 30 low-alkalinity lakes in northern New England (NE), New York (NY), the northern Great Lakes States (NGLS) of Minnesota, Michigan, and Wisconsin, and Florida (FL) have been dated by ²¹⁰Pb and analyzed for water and organic content, eight major elements (Al, Ti, Fe, Mn, Ca, Mg, Na, K) plus four trace metals (Pb, Zn, Cu, and V). Variations in the percentages of major elements through time are dominated by long-term independent variations in the abundance of SiO₂, FeO, and to a lesser extent Ca and Al. Additional variations are caused by varying proportions of inorganic matter. Major variations in chemistry are generally unrelated to documented distrubances in the watersheds; most disturbances are minor fires or selective logging.Accelerated accumulation of Pb from atmospheric sources into sediment first occurs in sediment dated between 1800 and 1850 in NY and NE, slightly later in the NGLS region, and about 1900 in FL. Modern accumulation rates in all areas are comparable (ca. 1 to 4 g cm^–2 yr^–1). Accumulation rates of Pb in some lakes have declined significantly from 1975 to 1985. Atmospheric deposition of anthropogenic Zn and Cu is also indicated by generally increasing accumulation rates in sediment cores, but the record is not as clear nor are chemical profiles in all lakes parallel to the trends in atmospheric emissions inferred on the basis of fossil fuel consumption, smelting, and other industrial activities. Inter-lake variations in profiles of Cu and Zn are large. Vanadium accumulation rates increase by the 1940s in NY and NE, but not until the 1950s in the NGLS region. This timing correlates with regional trends in the combustion of fuel oil, a major source of atmospheric V.Acidification of some of the lakes is suggested by decreases in the concentration and accumulation rates of Mn, Ca, and Zn in recent sediment, relative to other elements of catchment origin. The decreases generally occur slightly before the onset of acidification as indicated by diatoms. Increased sediment accumulation rates for Fe may indicate the acidification of watershed soils. The use of the accumulation rate of TiO₂ as an indicator of rates of erosion and for normalization of trace metal accumulation rates is in question for lakes where the flux of TiO₂ from the atmosphere varies and is a significant fraction of the total flux of TiO₂ to the sediment.This is the thirteenth of a series of papers to be published by this journal which is a contribution of the Paleoecological Investigation of Recent Lake Acidification (PIRLA) project. Drs. D. F. Charles and D. R. Whitehead are guest editors for this series.     

Analysis of noble gases in water using a quadrupole mass spectrometer in static mode

A quadrupole-based mass spectrometer used in static mode has been employed to determine noble gas concentrations of water samples by isotope dilution. Water samples are degassed and spiked with minor isotopes of each noble gas. After separation of the various gas components, the isotopic ratios are measured in the mass spectrometer. Because a spike is added to each sample, the recovery of each gas component does not have to be quantitative. Equilibration temperatures are calculated from the gas concentrations, based on noble gas solubility data. An accuracy of ±1°C, from the air equilibration temperature, is attainable for air-saturated water samples prepared under controlled conditions in the laboratory. The method has been applied to groundwaters from the London Basin Chalk aquifer. The noble-gas-derived temperatures are consistent with climatic conditions prevailing at the periods of recharge.     

Environmental controls on clay mineralogy of an Early Jurassic mudrock (Blue Lias Formation,southern England)

We present a dataset including clay mineralogy, gamma-ray spectrometry, organic matter content and magnetic susceptibility of the Hettangian to lowest Sinemurian successions of Dorset and Somerset, southern UK (Blue Lias Formation, Bristol Channel and Wessex basins). In both areas, the clay assemblages comprise predominantly detrital illite, kaolinite and illite/smectite mixed layers. Clays probably originated from the erosion of the Hercynian massifs, the relative proportions of kaolinite and illite being modulated by arid-humid climatic fluctuations. The organic matter (OM) content (types II to IV) ranges up to 12% in both areas. A clear stratigraphical trend in clay mineral assemblages is apparent in Somerset, whereas in Dorset sharp contrasts between adjacent horizons and a greater dilution by carbonate mask the long-term evolution. Correlations between both areas based on similar vertical trends in clay mineral abundance support the suggestion of a hiatus within the angulata Zone of the Dorset succession. As expected, the kaolinite/illite ratio correlates with the Th/K ratio deduced from gamma-ray spectrometry. However, significant departures from the correlation occur in OM-rich intervals, suggesting that Th may be partly adsorbed on to OM particles. Surprisingly, high magnetic susceptibility correlates with abundant kaolinite, not with Fe-rich clays, indicating either that kaolinite is accompanied by a soil-inherited magnetisable phase (possibly iron oxide) or that illite-rich rocks are more strongly diluted by carbonate than are kaolinite-rich strata.     

Geological setting and chemistry of kimberlite clan rocks in the Dharwar Craton, India

Diamond exploration in India over the past decade has led to the discovery of over 80 kimberlite-inferred and lamproite-related intrusions in three of the four major Archean cratons that dominate the subcontinent. These intrusions are Proterozoic (1.1 Ga), and are structurally controlled: locally (at the intersections of faults); regionally (in a 200 km wide, 1000 km long diamond corridor); and globally (in the reconstructed supercontinent of Rodinia). The geochemistry of 57 samples from 13 intrusions in the southern Dharwar Craton of Andhra Pradesh has been determined by XRF spectrometry. The bodies are iron-rich with mg#=50–70 and are neither archetypal kimberlites nor ideal lamproites; this may be the underlying reason that conventional exploration techniques have thus far failed to locate the primary sources of India's historically famous diamonds. The two major fields of kimberlite-clan rocks (KCR) in the Dharwar Craton, Wajrakur and Narayanpet, are separated by a NW–SE trending, transcontinental (Mumbai-Chennai) gravity lineament. About 80% of intrusions in Wajrakur are diamondiferous, but diamonds have not yet been reported in Narayanpet. The gravity anomaly may mark the boundary of an architectural modification in the keel of the sub-continental lithosphere, a suggestion that is supported by differences in kimberlite mineralogy, chemistry, mantle xenoliths, structural setting and crustal host rocks.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Snow distribution from SSM/I and its relationships to the hydroclimatology of the Mackenzie River Basin,Canada

The spatial and temporal distribution of snow cover extent (SCE) and snow water equivalent (SWE) play vital roles in the hydrology of northern watersheds. We apply remotely sensed Special Sensor Microwave Imager (SSM/I) data from 1988 to 2007 to explore the relationships between snow distribution and the hydroclimatology of the Mackenzie River Basin (MRB) of Canada and its major sub-basins. The Environment Canada (EC) algorithm is adopted to retrieve the SWE from SSM/I data. Moderate Resolution Imaging Spectroradiometer (MODIS) 8-day maximum snow cover extent products (MOD10A2) are used to estimate the different thresholds of retrieved SWE from SSM/I to classify the land cover as snow or no snow for various sub-basins in the MRB. The sub-basins have varying topography and hence different thresholds that range from 10 mm to 30 mm SWE. The accuracy of snow cover mapping based on the combination of several thresholds for the different sub-basins reaches ≈ 90%. The northern basins are found to have stronger linear relationships between the date on which snow cover fraction (SCF) reaches 50% or when SWE reaches 50% and mean air temperatures, than the southern basins. Correlation coefficients between SCF, SWE, and hydroclimatological variables show the new SCF products from SSM/I perform better than SWE from SSM/I to analyze the relationships with the regional hydroclimatology. Statistical models relating SCF and SWE to runoff indicate that the SCF and SWE from EC algorithms are able to predict the discharge in the early snow ablation seasons in northern watersheds.     

Laboratory kinetics of C2H radical reactions with ethane, propane, and n-butane at T = 96-296 K: implications for Titan

The kinetics of the reactions of C₂H radical with ethane (k₁), propane (k₂), and n-butane (k₃) are studied over the temperature range of T = 96-296 K with a pulsed Laval nozzle apparatus that utilizes a pulsed laser photolysis-chemiluminescence technique. The C₂H decay profiles in the presence of both the alkane reactant and O₂ are monitored by the CH(A²Δ) chemiluminescence tracer method. The results, together with available literature data, yield the following Arrhenius expressions: k₁(T) = (0.51 ± 0.06) × 10⁻¹⁰ exp[(−76 ± 30)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-800 K), k₂(T) = (0.98 ± 0.32) × 10⁻¹⁰exp[(−71 ± 60)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-361 K), and k₃(T) = (1.23 ± 0.26) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ (T = 96-297 K). At T = 296 K, k₁ is measured as a function of total pressure and has little or no pressure dependence. The results from this work support a direct hydrogen abstraction mechanism for the title reactions. Implications to the atmospheric chemistry of Titan are discussed.     

Predicted relative sea-level changes (18,000 years B.P. to present) caused by late-glacial retreat of the Antarctic Ice Sheet

Predictions of global changes in relative sea level caused by retreat of the Antarctic Ice Sheet from its 18,000 yr B.P. maximum to its present size are calculated numerically. When combined with the global predictions of relative sea-level change resulting from retreat of the Northern Hemisphere ice sheets, the results may be compared directly to observations of sea-level change on the Antarctic continent as well as at distant localities. The comparison of predictions to the few observations of sea-level change on Antarctica supports the view that the Antarctic Ice Sheet was larger 18,000 years ago than at present. The contribution of the Antarctic Ice Sheet to the total eustatic sea-level rise is assumed to be 25 m (25% of the assumed total eustatic rise). If as little as 0.7 m of this 25-m rise occurred between 5000 yr B.P. and the present, few mid-oceanic islands would emerge. If the Antarctic Ice Sheet attained its present dimensions by 6000 yr B.P., however, and if the volume of the ocean has remained constant for the past 5000 years, numerous islands throughout the Southern Hemisphere would emerge. It is suggested that a thorough study of Pacific islands, believed by some to have slightly emerged shorelines of Holocene age, would yield useful information about ocean volume changes during the past 5000 years, and hence on the glacial history of the Antarctic Ice Sheet.     

Subsurface flow measurements using passive flux meters in variably-saturated cold-regions landscapes

To date, passive flux meters have predominantly been applied in temperate environments for tracking the movement of contaminants in groundwater. This study applies these instruments to reduce uncertainty in (typically instantaneous) flux measurements made in a low-gradient, wetland dominated, discontinuous permafrost environment. This method supports improved estimation of unsaturated and over-winter subsurface flows which are very difficult to quantify using hydraulic gradient-based approaches. Improved subsurface flow estimates can play a key role in understanding the water budget of this landscape.