GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

Geochemistry of a spring-dense karst watershed located in a complex structural setting, Appalachian Great Valley, West Virginia, USA

The distribution and chemistry of the springs in the Tuscarora Creek watershed is controlled by both geologic structure and karst dissolution. The watershed is located in eastern West Virginia in the structurally complex Great Valley of the Appalachian Valley and Ridge province. The upper portion of the stream parallels strike along a mapped fault zone and is bordered by clastic rocks that comprise North Mountain. The lower reaches of the stream flow cross-strike through Cambro-Ordovician carbonates. The controlling chemical signature in the spring water is carbonate dissolution. Little evidence was seen for the recharge from adjacent clastic rocks although differences in the Ca/Mg molar ratio between springs indicated the presence of localized spring basins in headwater reaches. Na, Cl and Ca generally increased from upstream to downstream in the cross-strike reaches. Comparison of stream and cumulative spring discharge was consistent with significant groundwater base-flow contribution directly to the creek, particularly in the strike-parallel region. The largest spring in the watershed (>162 L/s) was sampled during and after a large storm event along with the adjacent creek. The creek displayed a typical dilution response with each flood pulse, whereas the spring had only a limited or delayed response. The overall chemical and thermal stability of the spring, relative to the creek, indicated the lack of significant direct hydraulic connection between the two. The conceptual model for the area includes localized flowpaths in the headwater region where the stream flow is parallel to strike and a thrust fault. In addition to the shallow localized flowpaths, a deeper, more regional flowpath likely exists for a large spring further downstream.     

The Composite Nature of the Provo Level of Lake Bonneville, Great Basin, Western North America

Deposits of a transgressive-phase Lake Bonneville stillstand or oscillation are found just below the elevation of the regressive-phase Provo shoreline at numerous exposures throughout the Bonneville basin. Existence of these subProvo shoreline deposits provides a new explanation for the massive size of Provo depositional and erosional landforms, which can no longer be explained by a long stillstand at the Provo shoreline. Provo coastal landforms are large because they are superimposed on subProvo landforms. Results also help to clarify divergent interpretations regarding the relative age of the Provo shoreline and the number of times it was occupied by the water plane. Occupation of approximately the same level during both the transgressive and the regressive phase of Lake Bonneville may be coincidental, or it may indicate that a bedrock sill controlled outflow at subProvo as well as Provo time. Rise to the Bonneville level could have occurred after massive slope failure plugged the outlet pass.     

The effect of habitat and environmental history on otolith chemistry of barramundi Lates calcarifer in estuarine populations of a regulated tropical river

We examine the microchemistry of otoliths of cohorts of a fished population of the large catadromous fish, barramundi Lates calcarifer from the estuary of a large tropical river. Barramundi from the estuary of the large, heavily regulated Fitzroy River, north-eastern Australia were analysed by making transects of ⁸⁷Sr/⁸⁶Sr isotope and trace metal/Ca ratios from the core to the outer edge. Firstly, we examined the Sr/Ca, Ba/Ca, Mg/Ca and Mn/Ca and ⁸⁷Sr/⁸⁶Sr isotope ratios in otoliths of barramundi tagged in either freshwater or estuarine habitats that were caught by the commercial fishery in the estuary. We used ⁸⁷Sr/⁸⁶Sr isotope ratios to identify periods of freshwater residency and assess whether trace metal/Ca ratios varied between habitats. Only Sr/Ca consistently varied between known periods of estuarine or freshwater residency. The relationships between trace metal/Ca and river flow, salinity, temperature were examined in fish tagged and recaptured in the estuary. We found weak and inconsistent patterns in relationships between these variables in the majority of fish. These results suggest that both individual movement history within the estuary and the scale of environmental monitoring were reducing our ability to detect any patterns. Finally, we examined fish in the estuary from two dominant age cohorts (4 and 7 year old) before and after a large flood in 2003 to ascertain if the flood had enabled fish from freshwater habitats to migrate to the estuary. There was no difference in the proportion of fish in the estuary that had accessed freshwater after the flood. Instead, we found that larger individuals with of each age cohort were more likely to have spent a period in freshwater. This highlights the need to maintain freshwater flows in rivers. About half the fish examined had accessed freshwater habitats before capture. Of these, all had spent at least their first two months in marine salinity waters before entering freshwater and some did not enter freshwater until four years of age. This contrasts with the results of several previous studies in other parts of the range that found that access to freshwater swamps by larval barramundi was important for enhanced population productivity and recruitment.     

Isotope Ratio Determination in the Earth and Environmental Sciences: Developments and Applications in 2003

This annual review documents developments and applications in the field of isotope ratio determination, as reflected in the literature for the Earth and environmental sciences for the year 2003. Particular emphasis is placed upon the relationship between the two dominant analytical techniques-thermal ionisation mass spectrometry (TIMS) and multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS)-and the rapidly changing nature of their roles in isotope analysis. Additionally, the review covers developments in single-collector ICP-MS and TOF technologies, new sample preparation procedures and the characterisation of isotopic reference materials, together with fundamental investigations of mass spectrometer performance.     

Freshwater organic deposits and stratified sediments between Early and Late Midlandian (Devensian) till sheets,at Aghnadarragh,County Antrim,Northern Ireland

The following events have been identified from a complex sequence of Midlandian (Devensian) sediments recently exposed at Aghnadarragh, County Antrim: (1) A lower till interpreted as Early Midlandian was deposited by a major lowland ice sheet which moved south-eastwards from central Ulster across the Lough Neagh depression. (2) Deglacial conditions were followed by a periglacial phase characterised by ice-wedge growth and sedimentation by gravelly debris flows. The latter contain the oldest known remains of Mammuthus primigenius in Ireland. (3) An Early Midlandian interstadial is represented by a woody detritus peat, with evidence of Betula, Pinuos and Picea woodlands and a rich beetle fauna. Wood from this horizon has been shown to be beyond the range of radiocarbon dating (>48 180 BP). (4) Interstadial conditions were succeeded by a cold, non-glacial phase dominated by in-channel gravelly flows and deposition of organic muds which contain plant and insect fossils. These horizons are older than 46 850 BP. (5) An upper, non-drumlinised till was deposited during the Late-Midlandian by a major lowland ice sheet which moved generally eastwards across the Lough Neagh Lowlands from central Ulster. This glaciation probably reached its maximum at ca 20–24 ka. (6) Drumlin formation occurred in the Lough Neagh Lowlands towards the end of the Late-Midlandian. The limiting moraines are dated to 17 ka. The lower till at Aghnadarragh is the first positive record of a major lowland ice sheet in Ireland during the early part of the last cold stage. The Early Midlandian interstadial peats have not been documented elsewhere in Ireland and correlate broadly with the Chelford Interstadial complex of the English Midlands. Related exposures elsewhere in Ulster confirm that the middle part of the last cold stage was free of major lowland ice masses but deposits of this period are absent from Aghnadarragh.     

Storm pulse chemographs of saturation index and carbon dioxide pressure: implications for shifting recharge sources during storm events in the karst aquifer at Fort Campbell,Kentucky/Tennessee,USA

Continuous records of discharge, specific conductance, and temperature were collected through a series of storm pulses on two limestone springs at Fort Campbell, western Kentucky/Tennessee, USA. Water samples, collected at short time intervals across the same storm pulses, were analyzed for calcium, magnesium, bicarbonate, total organic carbon, and pH. Chemographs of calcium, calcite saturation index, and carbon dioxide partial pressure were superimposed on the storm hydrographs. Calcium concentration and specific conductance track together and dip to a minimum either coincident with the peak of the hydrograph or lag slightly behind it. The CO₂ pressure continues to rise on the recession limb of the hydrograph and, as a result, the saturation index decreases on the recession limb of the hydrograph. These results are interpreted as being due to dispersed infiltration through CO₂-rich soils lagging the arrival of quickflow from sinkhole recharge in the transport of storm flow to the springs. Karst spring hydrographs reflect not only the changing mix of base flow and storm flow but also a shift in source of recharge water over the course of the storm.

---

Resumen Se ha registrado en continuo la descarga, conductancia específica y temperatura de una serie de episodios de tormenta en dos manantiales en calizas ubicados en Fort Campbell, en el oeste de Kentucky/Tennessee (Estados Unidos de América). Se ha analizado muestras de agua recogidas en breves intervalos de tiempo durante los episodios de tormenta, determinando el calcio, magnesio, bicarbonato, carbono orgánico total y pH. Se ha superpuesto quimiogramas de calcio, índice de saturación en calcita y presión parcial de dióxido de carbono en los hidrogramas de las tormentas. La concentración de calcio y la conductancia específica se comportan de forma similar y presentan un mínimo que coincide también con un pico del hidrograma o que se retrasa ligeramente con respecto a él. La presión de dióxido de carbono sigue aumentando en la rama de recesión del hidrograma y, como consecuencia, disminuye el índice de saturación de la rama de recesión del hidrograma. Se interpreta que estos resultados son debidos a la infiltración dispersa a través de suelos enriquecidos en dióxido de carbono que retrasan el flujo rápido desde la recarga en los sumideros hasta su afloramiento en los manantiales. Los hidrogramas en manantiales kársticos reflejan no sólo la mezcla cambiante del flujo de base y el de tormenta, sino también el cambio en el origen del agua de recarga durante el curso de la tormenta.

---

Résumé Lenregistrement en continu du débit, de la conductivité et de la température de leau a été réalisé au cours dune série de crues à deux sources émergeant de calcaires, à Fort Campbell (Kentucky occidental, Tennessee, États-Unis). Des échantillons deau, prélevés à de courts pas de temps lors de ces crues, ont été analysés pour le calcium, le magnésium, les bicarbonates, le carbone organique total et le pH. Les chimiogrammes de calcium, dindice de saturation de la calcite et de la pression partielle en CO₂ ont été superposés aux hydrogrammes de crue. La concentration en calcium et la conductivité de leau se suivent bien et passent par un minimum correspondant au pic de lhydrogramme ou légèrement retardé. La pression partielle en CO₂ continue de croître au cours de la récession de lhydrogramme de même que lindice de saturation de la calcite décroît. Ces résultats sont interprétés comme étant dus à linfiltration dispersée au travers de sols riches en CO₂, décalée par rapport à larrivée de lécoulement rapide provenant de la recharge, à partir dune perte, de lécoulement de crue vers les sources. Les hydrogrammes de sources karstiques ne reflètent pas seulement le mélange variable de lécoulement de base et de lécoulement de crue, mais également un changement dorigine de leau de la recharge au cours de lépisode de crue.