Mixing volume calculations,sources and aging trends of Floridan aquifer water by uranium isotopic methods

The activity ratio (A.R.) of two naturally occurring isotopes of uranium, U-238 and U-234, varies significantly in aqueous environments. The A.R., used in conjunction with the uranium concentration, provides a ‘fingerprint’ of groundwater masses and, by use of these parameters, mixing volumes and flow patterns can be determined. This method was applied to two large limestone springs in central Florida; the mixing volumes and flow patterns calculated are notably similar to those derived by standard hydrologic methods.In deeper parts of the aquifer, the waters are found to have low uranium concentration and a pattern of higher A.R.'s suggestive of an aging effect.     

Integrated chemostratigraphy and biostratigraphy of the Windermere Supergroup, northwestern Canada: implications for Neoproterozoic correlations and the early evolution of animals

The thick, richly fossiliferous succession of the upper Windermere Supergroup, Mackenzie Mountains, northwestern Canada, provides a test of integrated biostratigraphic and chemostratigraphic frameworks in terminal Proterozoic correlation. The C- and Sr-isotopic abundances of lower Keele Formation carbonates approximate those for other pre-Varanger samples, confirming that the simple disc-like fossils of the underlying Twitya Formation predate all known diverse Ediacaran faunas. "Tepee" and Sheepbed carbonates record strong post-glacial isotopic excursions; in contrast, delta13C values for Gametrail through Risky carbonates vary only within the narrow range of about +l% to +2%. A second negative excursion occurs in Ingta Formation carbonates that immediately underlie the paleontologically determined Precambrian-Cambrian boundary. The upper Windermere profile as a whole compares closely with curves determined for other terminal Proterozoic successions. The lowermost diverse Ediacaran assemblages in the Sheepbed Formation correlate chemostratigraphically with the oldest fauna in Namibia, but the two assemblages differ in taxonomic composition. Blueflower assemblages correlate both chemostratigraphically and taxonomically with faunas from Australia, China, Siberia, and elsewhere. Increasing data support the hypothesis that paleontological and geochemical data together provide a reliable means of correlating terminal Proterozoic sedimentary rocks throughout the world.     

Impacts of a bottom trawling exclusion zone on Snow Crab abundance and fish harvester behavior in the Labrador Sea, Canada

The Hawke Box trawling exclusion zone off southern Labrador is a 8610 km² closed area implemented in 2003 to protect soft-shelled pre-recruit Snow Crab and juvenile cod from mortality imposed by shrimp trawling and other bottom-impact fisheries. This study utilizes survey, logbook, and observer data from the Snow Crab and Northern Shrimp fisheries to assess the effectiveness of the Hawke Box in protecting and possibly enhancing the Snow Crab resource off southern Labrador. The results indicate that the exclusion zone has failed to protect pre-recruit crabs largely due to a redistribution and intensification of directed Snow Crab effort inside the Box in the years following closure. This unexpected outcome resulted in a high level of fishery-induced mortality to pre-recruit crabs and masked any potential positive outcomes from the cessation of trawling. The shortcomings that contributed to the failure of this exclusion area are discussed in relation to the current state of knowledge on the effectiveness of marine protected areas in general as management tools for conserving aquatic resources.     

Temporal association of arc–continent collision,progressive magma contamination in arc volcanism and formation of gold-rich massive sulphide deposits on Wetar Island (Banda arc)

Whole-rock ⁸⁷Sr/⁸⁶Sr and δ¹⁸O analyses of volcanic rocks and ³He/⁴He analyses of sulphides and sulphates from mineralized rocks on Wetar, Indonesia indicate a variable contribution of assimilated crustal material or sediment sourced from the subducted Australian craton to the south. These new data support the idea of progressive source contamination with precisely dated events showing that Wetar Island hosts the most extreme examples of crustal assimilation in the region. The increased continental contamination occurs during the Pliocene (Zanclian to Piacenzian) during distinct magmatic events between 5 and 4 Ma, and at 2.4 Ma when ⁸⁷Sr/⁸⁶Sr ratios in unaltered lavas, with whole-rock δ¹⁸O values between 5.7 and 9.6‰, increase from 0.707484 to extreme radiogenic values of 0.711656.The earlier of these magmatic events is important in the generation of the hydrothermal systems responsible for the mineralization recorded on Wetar. Samples from this yield radiogenic ³He/⁴He ratios between 0.5 and 1.4 R/R_A, similar to the data from volcanic rocks on nearby Romang. The later magmatic event coincides with the arrival of the Australian Continental Margin at the subduction zone along the Banda arc. Progressive incorporation of continental-sourced components into the source region below the Wetar Island edifice coincides with the formation of gold-rich volcanogenic massive sulphide deposits hosted within the contaminated volcanic pile.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Paleolimnological evidence of the response of the central Canadian treeline zone to radiative forcing and hemispheric patterns of temperature change over the past 2000 years

Instrumental climate records from the central Canadian treeline zone display a pattern of variation similar to general Northern Hemisphere temperature trends. To examine whether this general correspondence extends back beyond the instrumental record, we obtained a sediment core from Lake S41, a small lake in the Northwest Territories of Canada at 63°43.11′ N, 109°19.07′ W. A radiocarbon-based chronology was developed for the core. The sediments were analyzed for organic-matter content by loss-on-ignition (LOI), biogenic-silica content (BSi), and chironomid community composition to reconstruct July air temperature and summer water temperature. The paleolimnological records were compared with records of atmospheric CO₂ concentration, solar variability, and hemispheric temperature variations over the past 2000 years. The results of the analyses suggest that widely-documented long-term variations in Northern Hemisphere temperature associated with radiative forcing, namely the cooling following the medieval period during the Little Ice Age (LIA), and twentieth century warming, are represented in the central Canadian treeline zone. There is also evidence of a brief episode of warming during the eighteenth century. As evidenced by LOI and BSi, the twentieth century warming is typified by increased lake productivity relative to the LIA. Depending upon the measure, the increased productivity of the twentieth century nearly equals or exceeds that of any other period in the past 2000 years. In contrast, the rate of chironomid head capsule accumulation decreased and remained low during the twentieth century. Although the chironomid-inferred temperature reconstructions indicate cooling during the LIA, they present no evidence of greatly increased temperatures during the twentieth century. Warming during the twentieth century might have enhanced lake stratification, and the response of the chironomid fauna to warming was attenuated by decreased oxygen and lower temperatures in the hypolimnion of the more stratification-prone lake.

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.