The distribution of meteoric <Superscript>36</Superscript>Cl/Cl in the United States: a comparison of models

The natural distribution of ³⁶Cl/Cl in groundwater across the continental United States has recently been reported by Davis et al. (2003). In this paper, the large-scale processes and atmospheric sources of ³⁶Cl and chloride responsible for controlling the observed ³⁶Cl/Cl distribution are discussed.The dominant process that affects ³⁶Cl/Cl in meteoric groundwater at the continental scale is the fallout of stable chloride from the atmosphere, which is mainly derived from oceanic sources. Atmospheric circulation transports marine chloride to the continental interior, where distance from the coast, topography, and wind patterns define the chloride distribution. The only major deviation from this pattern is observed in northern Utah and southern Idaho where it is inferred that a continental source of chloride exists in the Bonneville Salt Flats, Utah.In contrast to previous studies, the atmospheric flux of ³⁶Cl to the land surface was found to be approximately constant over the United States, without a strong correlation between local ³⁶Cl fallout and annual precipitation. However, the correlation between these variables was significantly improved (R ²=0.15 to R ²=0.55) when data from the southeastern USA, which presumably have lower than average atmospheric ³⁶Cl concentrations, were excluded. The total mean flux of ³⁶Cl over the continental United States and total global mean flux of ³⁶Cl are calculated to be 30.5±7.0 and 19.6±4.5 atoms m^–2 s^–1, respectively.The ³⁶Cl/Cl distribution calculated by Bentley et al. (1986) underestimates the magnitude and variability observed for the measured ³⁶Cl/Cl distribution across the continental United States. The model proposed by Hainsworth (1994) provides the best overall fit to the observed ³⁶Cl/Cl distribution in this study. A process-oriented model by Phillips (2000) generally overestimates ³⁶Cl/Cl in most parts of the country and has several significant local departures from the empirical data.

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Resumen Davis et al. (2003) han informado de la distribución natural de la proporción ³⁶Cl/Cl en las aguas subterráneas de la parte continental de los Estados Unidos de América [EUA]. En este artículo, se discute cuáles son los procesos a gran escala y las fuentes atmosféricas del ³⁶Cl y del cloruro que dan lugar a la distribución observada de ³⁶Cl/Cl.El proceso dominante que afecta a la relación ³⁶Cl/Cl en las aguas subterráneas de origen meteórico a escala continental es el aporte de cloruro estable desde la atmósfera, que procede principalmente de los océanos. La circulación atmosférica transporta el cloruro marino hacia el interior, donde la distancia a la costa, topografía y corrientes del viento definen la distribución del cloruro. La única desviación principal de este esquema tiene lugar al norte de Utah y en el sur de Idaho, donde se deduce que existe una fuente continental de cloruro en los Rellanos Salados de Bonneville (Salt Flats).En contraste con estudios previos (Knies et al. 1994; Phillips 2000), se ha descubierto que el flujo atmosférico de ³⁶Cl hacia la superficie terrestre es aproximadamente constante en todos los estados, sin deducirse una correlación fuerte entre el aporte de ³⁶Cl y la precipitación anual. Sin embargo, la correlación entre estas variables se ve mejorada de forma significativa, con coeficientes de regresión comprendidos entre 0,15 y 0,55, cuando se excluyen los datos recogidos en el sudeste de los EUA, que tienen concentraciones de ³⁶Cl atmosférico presuntamente inferiores a la media. El flujo medio total de ³⁶Cl calculado en la zona continental de los Estados Unidos vale 30,5±7,0 átomos por metro cuadrado y segundo, mientras que el flujo total global de ³⁶Cl es de 19,6±4,5 átomos por metro cuadrado y segundo.La distribución de ³⁶Cl/Cl calculada por Bentley et al. (1986) infravalora la magnitud y variabilidad observada en los valores medidos a lo largo de los Estados Unidos. El modelo propuesto por Hainsworth (1994) proporciona el mejor ajuste conjunto a la distribución observada de ³⁶Cl/Cl en este estudio. El modelo orientado a procesos de Phillips (2000) sobreestima por lo general la distribución de ³⁶Cl/Cl en la mayoría del país y difiere significativamente de algunos valores locales empíricos.

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Résumé La distribution naturelle du rapport ³⁶Cl/Cl dans les eaux souterraines des États-Unis a été récemment présentée par Davis et al. (2003). Dans ce travail, les processus à grande échelle et les sources atmosphériques de ³⁶Cl et de chlorure responsables du contrôle de la distribution observée du rapport ³⁶Cl/Cl sont discutés. Le processus dominant qui affecte le rapport ³⁶Cl/Cl dans les eaux souterraines dorigine météorique à léchelle continentale est lapport atmosphérique de chlorure stable, qui provient pour lessentiel de sources océaniques. La circulation atmosphérique transporte des chlorures marins vers lintérieur des continents, où la distribution de chlorure est définie par la distance à la côte, la topographie et les régimes des vents. La seule exception majeure à ce schéma est observée dans le nord de lUtah et le sud de lIdaho où lon suppose quil existe une source continentale de chlorure dans les bas-fonds salés de Bonneville. Au contraire de précédentes études (Knies et al. 1994; Phillips 2000), on trouve que le flux atmosphérique de ³⁶Cl vers le sol est approximativement constant sur lensemble des États-Unis, sans forte corrélation entre la retombée locale de ³⁶Cl et les précipitations annuelles. Cependant, la corrélation entre ces variables devient significative (R ²=0.15 à 0.55) lorsquon supprime les données du sud-est des États-Unis, dont on pense quelles présentent des concentrations en ³⁶Cl atmosphérique inférieures à la moyenne. Le flux total moyen de ³⁶Cl sur les États-Unis continentaux et le flux moyen global de ³⁶Cl sont respectivement évalués à 30.5 ± 7.0 et 19.6 ± 4.5 atomes.m^–2.s^–1. La distribution du rapport ³⁶Cl/Cl calculée par Bentley et al. (1986) sous-estime lordre de grandeur et la variabilité observés pour la distribution mesurée du rapport ³⁶Cl/Cl sur les États-Unis continentaux. Le modèle proposé par Hainsworth (1994) fournit le meilleur ajustement densemble à la distribution du rapport ³⁶Cl/Cl observée dans cette étude. Un modèle orienté vers les processus proposé par Phillips (2000) surestime dans lensemble le rapport ³⁶Cl/Cl dans la plupart des régions du pays et présente plusieurs désaccords locaux avec les données empiriques.

     

The geochemistry of sulphur in a mixed allogenic–autogenic karst catchment,Castleton, Derbyshire,UK

Analyses are presented of anion chemistry and sulphur isotopic compositions of sulphate in sinking streams and groundwaters in a mixed allogenic–autogenic karst catchment. Using the sulphur isotopic data, sources of sulphate from agriculture and the effects of sulphate reduction arising from slurry application can be distinguished from natural rock weathering sources. Within the aquifer, sulphate in known autogenic waters has isotopic compositions distinct from allogenic waters, the autogenic waters being dominated by sulphate from rainfall and rock weathering in these low agricultural intensity catchments. On this basis, water rising at low flow from Whirlpool Rising, Speedwell Cavern, has been identified as dominantly autogenic. Groundwater flow between the sinks and risings in Speedwell Cavern is believed to be along conduits following mineralized faults (rakes). During transit SO42−/Cl− in the water increases. Isotopic mass balance shows that this must be due to addition of sulphate from the oxidation of ore minerals by groundwater. Mass balance considerations show that the present rate of sulphide oxidation must be the result of enhancement by lead mining operations on the rakes. Copyright © 2000 John Wiley & Sons, Ltd.     

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.     

Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

Mapping the Land Cover of Mexico Using AVHRR Time‐Series Data Sets

Abstract

An important methodological and analytical requirement for analyzing spatial relationships between regional habitats and species distributions in Mexico is the development of standard methods for mapping the country's land cover/land use formations. This necessarily involves the use of global data such as that produced by the Advanced Very High Resolution Radiometer (AVHRR). We created a nine‐band time‐series composite image from AVHRR Normalized Difference Vegetation Index (NDVI) bi‐weekly data. Each band represented the maximum NDVI for a particular month of either 1992 or 1993. We carried out a supervised classification approach, using the latest comprehensive land cover/vegetation map created by the Mexican National Institute of Geography (INEGI) as reference data. Training areas for 26 land cover/vegetation types were selected and digitized on the computer's screen by overlaying the INEGI vector coverage on the NDVI image. To obtain specific spectral responses for each vegetation type, as determined by its characteristic phenology and geographic location, the statistics of the spectral signatures were subjected to a cluster analysis. A total of 104 classes distributed among the 26 land cover types were used to perform the classification. Elevation data were used to direct classification output for pine‐oak and coastal vegetation types. The overall correspondence value of the classification proposed in this paper was 54%; however, for main vegetation formations correspondence values were higher (60‐80%). In order to obtain refinements in the proposed classification we recommend further analysis of the signature statistics and adding topographic data into the classification algorithm.     

Hydro‐meteorological drivers and sources of suspended sediment flux in the pro‐glacial zone of the retreating Castle Creek Glacier,Cariboo Mountains,British Columbia,Canada

Glaciers are major agents of erosion that increase sediment load to the downstream fluvial system. The Castle Creek Glacier, British Columbia, Canada, has retreated ~1.0 km in the past 70 years. Suspended sediment concentration (SSC) and streamflow (Q) were monitored independently at five sites within its pro‐glacial zone over a 60 day period from July to September 2011, representing part of the ablation season. Meteorological data were collected from two automatic weather stations proximal to the glacier. The time‐series were divided into hydrologic days and the shape and magnitude of the SSC response to hydro‐meteorological conditions (‘cold and wet’, ‘hot and dry’, ‘warm and damp’, and ‘storm’) were categorized using principal component analysis (PCA) and cluster analysis (CA). Suspended sediment load (SSL) was computed and summarized for the categories. The distribution of monitoring sites and results of the multivariate statistical analyses describe the temporal and spatial variability of suspended sediment flux and the relative importance of glacial and para‐glacial sediment sources in the pro‐glacial zone. During the 2011 study period, ~ 60% of the total SSL was derived from the glacial stream and sediment deposits proximal to the terminus of the glacier; during ‘storm’ events, that contribution dropped to ~40% as the contribution from diffuse and point sources of sediment throughout the pro‐glacial zone and within the meltwater channels increased. While ‘storm’ events accounted for just 3% of the study period, SSL was ~600% higher than the average over the monitoring period, and ~20% of the total SSL was generated in that time. Determining how hydro‐meteorological conditions and sediment sources control sediment fluxes will assist attempts to predict how pro‐glacial zones respond to future climate changes. Copyright © 2015 John Wiley & Sons, Ltd.     

Linking gold mineralization to regional-scale drivers of mineral systems using in situ U–Pb geochronology and pyrite LA-ICP-MS element mapping

Proterozoic orogens commonly host a range of hydrothermal ores that form in diverse tectonic settings at different times. However, the link between mineralization and the regional-scale tectonothermal evolution of orogens is usually not well understood, especially in areas subject to multiple hydrothermal events.Regional-scale drivers for mineral systems vary between the different classes of hydrothermal ore, but all involve an energy source and a fluid pathway to focus mineralizing fluids into the upper crust. The Mount Olympus gold deposit in the Proterozoic Capricorn Orogen of Western Australia, was regarded as an orogenic gold deposit that formed at ca. 1738 Ma during the assembly of Proterozoic Australia. However,the trace element chemistry of the pyrite crystals closely resembles those of the Carlin deposits of Nevada,with rims that display solid solution gold accompanied by elevated As, Cu, Sb, Hg, and Tl, surrounding gold-poor cores. New SHRIMP UeP b dating of xenotime intergrown with auriferous pyrite and ore-stage alteration minerals provided a weighted mean~(207) Pb*/~(206) Pb* date of 1769 ± 5 Ma, interpreted as the age of gold mineralization. This was followed by two discrete episodes of hydrothermal alteration at 1727 ± 7 Ma and 1673 ± 8 Ma. The three ages are linked to multiple reactivation of the crustal-scale Nanjilgardy Fault during repeated episodes of intracratonic reworking. The regional-scale drivers for Carlin-like gold mineralization at Mount Olympus are related to a change in tectonic regime during the final stages of the intracratonic 1820 -1770 Ma Capricorn Orogeny. Our results suggest that substantial sized Carlin-like gold deposits can form in an intracratonic setting during regional-scale crustal reworking.     

Seismic velocities of granulite-facies xenoliths from Central Ireland: Implications for lower crustal composition and anisotropy

V_p and V_s values have been measured experimentally and calculated for granulite-facies lower crustal xenoliths from central Ireland close to the Caledonian Iapetus suture zone. The xenoliths are predominantly foliated and lineated metapelitic (garnet–sillimanite–K-feldspar) granulites. Their metapelitic composition is unusual compared with the mostly mafic composition of lower crustal xenoliths world-wide. Based on thermobarometry, the metapelitic xenoliths were entrained from depths of c. 20–25 ± 3.5 km and rare mafic granulites from depths of 31–33 ± 3.4 km. The xenoliths were emplaced during Lower Carboniferous volcanism and are considered to represent samples of the present day lower crust.V_p values for the metapelitic granulites range between 6.26 and 7.99 km s^{− 1} with a mean value of 7.09 ± 0.4 km s^{− 1}. Psammite and granitic orthogneiss samples have calculated V_p values of 6.51 and 6.23 km s^{− 1}, respectively. V_s values for the metapelites are between 3.86 and 4.34 km s^{− 1}, with a mean value of 4.1 ± 0.15 km s^{− 1}. The psammite and orthogneiss have calculated V_s values of 3.95 and 3.97 km s^{− 1}, respectively.The measured seismic velocities correlate with density and with modal mineralogy, especially the high content of sillimanite and garnet. V_p anisotropy is between 0.15% and 13.97%, and a clear compositional control is evident, mainly in relation to sillimanite abundance. Overall V_s anisotropy ranges from 1% to 11%. Poisson's ratio (σ) lies between 0.25 and 0.35 for the metapelitic granulites, mainly reflecting a high V_p value due to abundant sillimanite in the sample with the highest σ. Anisotropy is probably a function of deformation associated with the closure of the Iapetus ocean in the Silurian as well as later extension in the Devonian. The orientation of the bulk strain ellipsoid in the lower crust is difficult to constrain, but lineation is likely to be NE–SW, given the strike-slip nature of the late Caledonian and subsequent Acadian deformation.When corrected for present-day lower crustal temperature, the experimentally determined V_p values correspond well with velocities from the ICSSP, COOLE I and VARNET seismic refraction lines. Near the xenolith localities, the COOLE I line displays two lower crustal layers with in situ V_p values of 6.85–6.9 and 6.9–8.0 km s^{− 1}, respectively. The upper (lower velocity) layer corresponds well with the metapelitic granulite xenoliths while the lower (higher velocity) layer matches that of the basic granulite xenoliths, though their metamorphic pressures suggest derivation from depths corresponding to the present-day upper mantle.