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.     

Integrated chronostratigraphy of Proterozoic-Cambrian boundary beds in the western Anabar region, northern Siberia

Carbonate-rich sedimentary rocks of the western Anabar region, northern Siberia, preserve an exceptional record of evolutionary and biogeochemical events near the Proterozoic/Cambrian boundary. Sedimentologically, the boundary succession can be divided into three sequences representing successive episodes of late transgressive to early highstand deposition; four parasequences are recognized in the sequence corresponding lithostratigraphically to the Manykal Formation. Small shelly fossils are abundant and include many taxa that also occur in standard sections of southeastern Siberia. Despite this coincidence of faunal elements, biostratigraphic correlations between the two regions have been controversial because numerous species that first appear at or immediately above the basal Tommotian boundary in southeastern sections have first appearances scattered through more than thirty metres of section in the western Anabar. Carbon- and Sr-isotopic data on petrographically and geochemically screened samples collected at one- to two-metre intervals in a section along the Kotuikan River, favour correlation of the Staraya Reckha Formation and most of the overlying Manykai Formation with sub-Tommotian carbonates in southeastern Siberia. In contrast, isotopic data suggest that the uppermost Manykai Formation and the basal 26 m of the unconformably overlying Medvezhya Formation may have no equivalent in the southeast; they appear to provide a sedimentary and palaeontological record of an evolutionarily significant time interval represented in southeastern Siberia only by the sub-Tommotian unconformity. Correlations with radiometrically dated horizons in the Olenek and Kharaulakh regions of northern Siberia suggest that this interval lasted approximately three to six million years, during which essentially all 'basal Tommotian' small shelly fossils evolved.     

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.     

Late Quaternary Spring-Fed Deposits of the Grand Canyon and Their Implication for Deep Lava-Dammed Lakes

One of the most intriguing episodes in the Quaternary evolution of the Grand Canyon of the Colorado River, Arizona, was the development of vast lakes that are thought to have backed up behind lava erupted into the gorge. Stratigraphic evidence for these deep lava-dammed lakes is expectedly sparse. Possible lacustrine deposits at six areas in the eastern canyon yielded no compelling evidence for sediment deposited in a deep lake. At two of the sites the sediment was associated with late Quaternary spring-fed pools and marshes. Water-lain silt and sand at lower Havasu Creek was deposited 3000 cal yr ago. The deposit contains an ostracode assemblage similar to that living in the modern travertine-dammed pools adjacent to the outcrop. The second deposit, at Lees Ferry, formed in a spring-fed marsh 43,000 cal yr ago, as determined by ¹⁴C and amino acid geochronology. It contains abundant ostracode and mollusk fossils, the richest assemblages reported from the Grand Canyon to date. Our interpretation of these sediments as spring-fed deposits, and their relative youth, provides an alternative to the conventional view that deposits like these were formed in deep lava-dammed lakes that filled the Grand Canyon.     

Paleoclimate reconstruction based on the timing of speleothem growth and oxygen and carbon isotope composition in a cave located in the rain shadow in Israel

High-resolution ²³⁰Th/²³⁴U ages and δ¹⁸O and δ¹³C compositions of speleothems in Ma’ale Efrayim Cave located to the east of the central mountain ridge of Israel enable us to examine the nature of the rain shadow aridity during glacial and interglacial intervals. Speleothem growth occurred during marine glacial isotopic periods, with no growth during the two last marine isotope interglacial intervals and during the peak of the Last Glacial Maximum. This contrasts with speleothem growth in caves located on the western flank of the central mountain ridge, in the Eastern Mediterranean semiarid climatic zone, which continued throughout the last 240,000 yr. Thus, during glacial periods water reached both sides of the central mountain ridge. A comparison of the present-day rain and cave water isotopic compositions and amounts at the Ma’ale Efrayim Cave site with those on the western flank shows that evaporation and higher temperatures on the eastern flank are major influences on isotopic composition and the lack of rainfall. The δ¹⁸O and δ¹³C profiles of the speleothems deposited between 67,000 and 25,000 yr B.P. match the general trends of the isotopic profiles of Soreq Cave speleothems, suggesting a similar source (eastern Mediterranean Sea) and similar climatic conditions. Thus, during glacial periods the desert boundary effectively migrated further south or east from its present-day location on the eastern flank, whereas interglacial periods appear to have been similar to the present, with the desert boundary at the same position. The decrease in overall temperature and a consequent reduction in the evaporation to precipitation ratios on the eastern flank are viewed as the major factors controlling the decay of the rain shadow effect during glacial periods.     

Deducing the spatial variability of exchange within a longitudinal channel water balance

Developing an appropriate data collection scheme to infer stream–subsurface interactions is not trivial due to the spatial and temporal variability of exchange flowpaths. Within the context of a case study, this paper presents the results from a number of common data collection techniques ranging from point to reach scales used in combination to better understand the spatial complexity of subsurface exchanges, infer the hydrologic conditions where individual influences of hyporheic and groundwater exchange components on stream water can be characterized, and determine where gaps in information arise. We start with a tracer‐based, longitudinal channel water balance to quantify hydrologic gains and losses at a sub‐reach scale nested within two consecutive reaches. Next, we look at groundwater and stream water surface levels, shallow streambed vertical head gradients, streambed and aquifer hydraulic conductivities, water chemistry, and vertical flux rates estimated from streambed temperatures to provide more spatially explicit information. As a result, a clearer spatial understanding of gains and losses was provided, but some limitations in interpreting results were identified even when combining information collected over various scales. Due to spatial variability of exchanges and areas of mixing, each technique frequently captured a combination of groundwater and hyporheic exchange components. Ultimately, this study provides information regarding technique selection, emphasizes that care must be taken when interpreting results, and identifies the need to apply or develop more advanced methods for understanding subsurface exchanges. Copyright © 2013 John Wiley & Sons, Ltd.     

What is the source of baseflow in agriculturally fragmented catchments? Complex groundwater/surface‐water interactions in three tributary catchments of the Wabash River,Indiana, USA

Some conceptual models suggest that baseflow in agriculturally fragmented watersheds may contain little, if any, groundwater. This has critical implications for stream quality and ecosystem functioning. Here, we (a) identify the sources and flowpaths contributing to baseflow using ²²²Rn and ⁸⁷Sr/⁸⁶Sr and (b) quantify mean apparent ages of groundwater and baseflow using multiple isotopic tracers (CFC, SF₆, ³⁶Cl, and ³H) in 4 small (0.08 to 0.64 km²) tributary catchments to the Wabash River in Indiana, USA. ²²²Rn activities and ⁸⁷Sr/⁸⁶Sr ratios indicate that baseflow in 3 catchments is sourced primarily from groundwater; baseflow in the fourth is dominated by a source similar to agricultural run‐off. CFC‐12 data indicate that springs in 1 catchment are discharging significant proportions of water that recharged between 1974 (42 ± 2 years) and 1961 (55 ± 2 years). Those same springs have ³⁶Cl/Cl ratios between 1,381.08 ± 29.37 (×10^?15) and 1,530.64 ± 27.65 (×10^?15) indicating that a substantial proportion of the discharge likely recharged between 1975 (41 years) and 1950 (66 years). Groundwater samples collected from streambed mini‐piezometers in a separate catchment have CFC‐12 concentrations indicating that a large proportion of the recharge occurred between 1948 (68 ± 2 years) and 1950 (66 ± 2 years). Repeat sampling conducted in September 2015 after above‐average summer rainfall did not show significant decreases in mean apparent age. The relatively old ages observed in 3 of the catchments can be explained by geological complexities that are likely present in all 4 catchments, but overwhelmed by flow from the shallow phreatic aquifer in the fourth catchment.     

The impact of biofuel-induced food-price inflation on dietary energy demand and dietary greenhouse gas emissions

Dramatic increases in liquid biofuel production have led to concerns about associated impacts on food prices, with many modeling studies showing significant biofuel-related price inflation. In turn, by changing patterns of food demand, biofuel production may indirectly influence greenhouse gas emissions. We estimated changes to dietary energy (calorie) demand and greenhouse gas emissions embodied in average diets under different biofuel-related food-price scenarios for Brazil, China and the United States, using food-price projections and food-price elasticities. Average energy demand decreased in all countries, from about 40 kcal per person per day in Brazil under a moderate price inflation scenario – a reduction of 1% relative to the (2009) reference scenario – to nearly 300 per day in the United States with high price inflation – almost 8% of reference levels. However, emissions per calorie increased slightly in all three countries. In terms of total greenhouse gas emissions, the results are suggestive of overall reductions only in the United States, where average reductions ranged from about 40 to 110 kg of carbon dioxide equivalent emissions per person per year. In China, the direction of impact is unclear, but the net change is likely to be small. Brazilian results were sensitive to parameter values and the direction and magnitude of impact is therefore uncertain. Despite the uncertainty, even small changes (positive or negative) in individual dietary emissions can produce large changes at the population level, arguing for the inclusion of the dietary pathway in greenhouse gas accounting of liquid biofuels.     

Community‐Derived Standards for LA‐ICP‐MS U‐(Th‐)Pb Geochronology – Uncertainty Propagation,Age Interpretation and Data Reporting

The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess ²³⁰Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.