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  1. North Atlantic cooling during Heinrich Stadial 1 triggered an east-west precipitation dipole over the tropical Indian Ocean. 
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  2. Abstract

    Sources of dissolved and particulate carbon to the Fraser River system vary significantly in space and time. Tributaries in the northern interior of the basin consistently deliver higher concentrations of dissolved organic carbon (DOC) to the main stem than other tributaries. Based on samples collected near the Fraser River mouth throughout 2013, the radiocarbon age of DOC exported from the Fraser River does not change significantly across seasons despite a spike in DOC concentration during the freshet, suggesting modulation of heterogeneous upstream chemical and isotopic signals during transit through the river basin. Dissolved inorganic carbon (DIC) concentrations are highest in the Rocky Mountain headwater region where carbonate weathering is evident, but also in tributaries with high DOC concentrations, suggesting that DOC respiration may be responsible for a significant portion of DIC in this basin. Using an isotope and major ion mass balance approach to constrain the contributions of carbonate and silicate weathering and DOC respiration, we estimate that up to 33 ± 11% of DIC is derived from DOC respiration in some parts of the Fraser River basin. Overall, these results indicate close coupling between the cycling of DOC and DIC, and that carbon is actively processed and transformed during transport through the river network.

     
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  3. Fly ash—the residuum of coal burning—contains a considerable amount of fossilized particulate organic carbon (FOC ash ) that remains after high-temperature combustion. Fly ash leaks into natural environments and participates in the contemporary carbon cycle, but its reactivity and flux remained poorly understood. We characterized FOC ash in the Chang Jiang (Yangtze River) basin, China, and quantified the riverine FOC ash fluxes. Using Raman spectral analysis, ramped pyrolysis oxidation, and chemical oxidation, we found that FOC ash is highly recalcitrant and unreactive, whereas shale-derived FOC (FOC rock ) was much more labile and easily oxidized. By combining mass balance calculations and other estimates of fly ash input to rivers, we estimated that the flux of FOC ash carried by the Chang Jiang was 0.21 to 0.42 Mt C⋅y −1 in 2007 to 2008—an amount equivalent to 37 to 72% of the total riverine FOC export. We attributed such high flux to the combination of increasing coal combustion that enhances FOC ash production and the massive construction of dams in the basin that reduces the flux of FOC rock eroded from upstream mountainous areas. Using global ash data, a first-order estimate suggests that FOC ash makes up to 16% of the present-day global riverine FOC flux to the oceans. This reflects a substantial impact of anthropogenic activities on the fluxes and burial of fossil organic carbon that has been made less reactive than the rocks from which it was derived. 
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  6. Radiocarbon ages and thermal stability measurements can be used to estimate the stability of soil organic carbon (OC). Soil OC is a complex reservoir that contains a range of compounds with different sources, reactivities, and residence times. This heterogeneity can shift bulk radiocarbon values and impact assessment of OC stability and turnover in soils. Four soil horizons (Oa, Bhs, Bs, Bg) were sampled from highly weathered 350 ka Pololu basaltic volcanics on the Island of Hawaii and analyzed by Ramped PyrOX (RPO) in both the pyrolysis (PY) and oxidation (OX) modes to separate a complex mixture of OC into thermally defined fractions. Fractions were characterized for carbon stable isotope and radiocarbon composition. PY and OX modes yielded similar results. Bulk radiocarbon measurements were modern in the Oa horizon (Fm = 1.013) and got progressively older with depth: the Bg horizon had an Fm value of 0.73. Activation energy distributions (p(E)) calculated using the ‘rampedpyrox’ model yielded consistent mean E values of 140 kJ mol-1 below the Oa horizon. The ‘rampedpyrox’ model outputs showed a mostly bimodal distribution in the p(E) below the Oa, with a primary peak at 135 kJ mol-1 and a secondary peak at 148 kJ mol-1, while the Oa was dominated by a single, higher E peak at 157 kJ mol-1. We suggest that mineral-carbon interaction, either through mineral surface-OC or metal-OC interactions, is the stabilization mechanism contributing to the observed mean E of 140 kJ mol-1 below the Oa horizon. In the Oa horizon, within individual RPO analyses, radiocarbon ages in the individual thermal fractions were indistinguishable (p[0.1). The flat age distributions indicate there is no relationship between age and thermal stability (E) in the upper horizon ([25 cm). Deeper in the soil profile higher lEf values were associated with older radiocarbon ages, with slopes progressively steepening with depth. In the deepest (Bg) horizon, there was the largest, yet modest change in Fm of 0.06 (626 radiocarbon years), indicating that older OC is slightly more thermally stable. 
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  7. Abstract Constraining radiocarbon ( 14 C) reservoir age offsets is critical to deriving accurate calendar-age chronologies from 14 C dating of materials which did not draw carbon directly from the atmosphere. The application of 14 C dating to such materials is severely limited in hydrologically sensitive environments like the Black Sea because of the difficulty to quantify reservoir age offsets, which can vary quickly and significantly through time, due to the dynamics of the biogeochemical cycling of carbon. Here we reconstruct 14 C reservoir age offsets (R shell-atm ) of Holocene bivalve shells from the coastal Black Sea relatively to their contemporaneous atmosphere. We show that the 14 C reservoir age offset and the stable carbon isotope composition of bivalve shells are linearly correlated in this region. From a biogeochemical standpoint, this suggests that inorganic stable carbon isotope and 14 C compositions of Black Sea coastal waters are controlled by the balance between autochthonous primary productivity and heterotrophic respiration of allochthonous pre-aged terrestrial organic matter supplied by rivers. This provided an important implication for Black Sea geochronology as the reservoir age offset of 14 C-dated bivalve shell can be inferred from its stable carbon isotope composition. Our results provide a fundamental and inexpensive geochemical tool which will considerably improve the accuracy of Holocene calendar age chronologies in the Black Sea. 
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