[1] Stable isotope ratios of various ecosystem components and net ecosystem exchange (NEE) CO 2 fluxes were measured in a C 3 -C 4 mixture tallgrass prairie near Manhattan, Kansas. The July 2002 study period was chosen because of contrasting soil moisture contents, which allowed us to address the effects of drought on photosynthetic CO 2 uptake and isotopic discrimination. Significantly higher NEE fluxes were observed for both daytime uptake and nighttime respiration during well-watered conditions when compared to a drought period. Given these differences, we investigated two carbon-flux partitioning questions: (1) What proportions of NEE were contributed by C 3 versus C 4 species? (2) What proportions of NEE fluxes resulted from canopy assimilation versus ecosystem respiration? To evaluate these questions, air samples were collected every 2 hours during daytime for 3 consecutive days at the same height as the eddy covariance system. These air samples were analyzed for both carbon isotope ratios and CO 2 concentrations to establish an empirical relationship for isoflux calculations. An automated air sampling system was used to collect nighttime air samples to estimate the carbon isotope ratios of ecosystem respiration (d R ) at weekly intervals for the entire growing season. Models of C 3 and C 4 photosynthesis were employed to estimate bulk canopy intercellular CO 2 concentration in order to calculate photosynthetic discrimination against 13 C. Our isotope/NEE results showed that for this grassland, C 4 vegetation contributed $80% of the NEE fluxes during the drought period and later $100% of the NEE fluxes in response to an impulse of intense precipitation. For the entire growing season, the C 4 contribution ranged from $68% early in the spring to nearly 100% in the late summer. Using an isotopic approach, the calculated partitioned respiratory fluxes were slightly greater than chamber-measured estimates during midday under well-watered conditions. In addition, time series analyses of our d R measurements revealed that occasionally during periods of high wind speed (increasing the sampling footprint) the C 3 cropland and forests surrounding the C 4 prairie could be detected and had an impact on the carbon isotopic signal. The implication is that isotopic air sampling of CO 2 can be useful as a tracer for evaluating the fetch of upwind airflow in a heterogeneous ecosystem.INDEX TERMS: 0315 Atmospheric Composition and Structure: Biosphere/atmosphere interactions; 1615 Global Change: Biogeochemical processes (4805); 1812 Hydrology: Drought; 3337 Meteorology and Atmospheric Dynamics: Numerical modeling and data assimilation; KEYWORDS: net ecosystem exchange, carbon isotopes, discrimination, isoflux, C 3 -C 4 composition, photosynthesis model, canopy carbon modeling Citation: Lai, C.-T., A. J. Schauer, C. Owensby, J. M. Ham, and J. R. Ehleringer, Isotopic air sampling in a tallgrass prairie to partition net ecosystem CO 2 exchange,

The δD and δ18O values of water are key measurements in polar ice-core research, owing to their strong and well-understood relationship with local temperature. Deuterium excess, d, the deviation from the average linear relationship between δD and δ18O, is also commonly used to provide information about the oceanic moisture sources where polar precipitation originates. Measurements of δ17O and “17O excess” (Δ17O) are also of interest because of their potential to provide information complementary to d. Such measurements are challenging because of the greater precision required, particularly for Δ17O. Here, high-precision measurements are reported for δ17O, δ18O, and δD on a new ice core from the South Pole, using a continuous-flow measurement system coupled to two cavity ring-down laser spectroscopy instruments. Replicate measurements show that at 0.5 cm resolution, external precision is ∼0.2‰ for δ17O and δ18O, and ∼1‰ for δD. For Δ17O, achieving external precision of <0.01‰ requires depth averages of ∼50 cm. The resulting ∼54,000-year record of the complete oxygen and hydrogen isotope ratios from the South Pole ice core is discussed. The time series of Δ17O variations from the South Pole shows significant millennial-scale variability, and is correlated with the logarithmic formulation of deuterium excess (dln), but not the traditional linear formulation (d).

Data from the South Pole ice core (SPC14) are used to constrain climate conditions and ice‐flow‐induced layer thinning for the last 54,000 years. Empirical constraints are obtained from the SPC14 ice and gas timescales, used to calculate annual‐layer thickness and the gas‐ice age difference (Δage), and from high‐resolution measurements of water isotopes, used to calculate the water‐isotope diffusion length. Both Δage and diffusion length depend on firn properties and therefore contain information about past temperature and snow‐accumulation rate. A statistical inverse approach is used to obtain an ensemble of reconstructions of temperature, accumulation‐rate, and thinning of annual layers in the ice sheet at the SPC14 site. The traditional water‐isotope/temperature relationship is not used as a constraint; the results therefore provide an independent calibration of that relationship. The temperature reconstruction yields a glacial‐interglacial temperature change of 6.7 ± 1.0°C at the South Pole. The sensitivity of δ18O to temperature is 0.99 ± 0.03 ‰°C−1, significantly greater than the spatial slope of 0.8‰°C−1 that has been used previously to determine temperature changes from East Antarctic ice core records. The reconstructions of accumulation rate and ice thinning show millennial‐scale variations in the thinning function as well as decreased thinning at depth compared to the results of a 1‐D ice flow model, suggesting influence of bedrock topography on ice flow.

Abstract. The South Pole Ice Core (SPICEcore), which spans the past 54 300 years, was drilled far from an ice divide such that ice recovered at depth originated upstream of the core site. If the climate is different upstream, the climate history recovered from the core will be a combination of the upstream conditions advected to the core site and temporal changes. Here, we evaluate the impact of ice advection on two fundamental records from SPICEcore: accumulation rate and water isotopes. We determined past locations of ice deposition based on GPS measurements of the modern velocity field spanning 100 km upstream, where ice of ∼20 ka age would likely have originated. Beyond 100 km, there are no velocity measurements, but ice likely originates from Titan Dome, an additional 90 km distant. Shallow radar measurements extending 100 km upstream from the core site reveal large (∼20 %) variations in accumulation but no significant trend. Water isotope ratios, measured at 12.5 km intervals for the first 100 km of the flowline, show a decrease with elevation of −0.008 ‰ m−1 for δ18O. Advection adds approximately 1 ‰ for δ18O to the Last Glacial Maximum (LGM)-to-modern change. We also use an existing ensemble of continental ice-sheet model runs to assess the ice-sheet elevation change through time. The magnitude of elevation change is likely small and the sign uncertain. Assuming a lapse rate of 10 ∘C km−1 of elevation, the inference of LGM-to-modern temperature change is ∼1.4 ∘C smaller than if the flow from upstream is not considered.

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Paleoenvironmental reconstructions are commonly based on isotopic signatures of a variety of carbonate types, including rhizoliths and land-snail shells, present in paleosol-loess sequences. However, various carbonate types are formed through distinct biotic and abiotic processes over various periods, and therefore may record diverging environmental information in the same sedimentological layer. Here, we investigate the effects of carbonate type on δ13C, δ18O, and clumped isotope-derived paleotemperature [T(Δ47)] from the Quaternary Nussloch paleosol-loess sequence (Rhine Valley, SW Germany). δ13C, δ18O, and T(Δ47) values of co-occurring rhizoliths (-8.2‰ to -5.8‰, -6.1‰ to -5.9‰, 12–32°C, respectively), loess dolls (-7.0‰, -5.6‰, 23°C), land-snail shells (-8.1‰ to -3.2‰, -4.0‰ to -2.2‰, 12–38°C), earthworm biospheroliths (-11‰, -4.7‰, 8°C), and “bulk” carbonates (-1.9‰ to -0.5‰, -5.6‰ to -5.3‰, 78–120°C) from three sediment layers depend systematically on the carbonate type, admixture from geogenic carbonate, and the duration of formation periods. Based on these findings, we provide a comprehensive summary for the application of the three isotopic proxies of δ13C, δ18O, and Δ47 in biogenic and pedogenic carbonates present in the same sediment layer to reconstruct paleoenvironments (e.g., local vegetation, evaporative conditions, and temperature). We conclude that bulk carbonates in Nussloch loess should be excluded from paleoenvironmental reconstructions. Instead, pedogenic and biogenic carbonates should be used to provide context for interpreting the isotopic signature for detailed site- and time-specific paleoenvironmental information.

Anthropogenic sulfate aerosols are estimated to have offset sixty percent of greenhouse-gas-induced warming in the Arctic, a region warming four times faster than the rest of the world. However, sulfate radiative forcing estimates remain uncertain because the relative contributions from anthropogenic versus natural sources to total sulfate aerosols are unknown. Here we measure sulfur isotopes of sulfate in a Summit, Greenland ice core from 1850 to 2006 CE to quantify the contribution of anthropogenic sulfur emissions to ice core sulfate. We use a Keeling Plot to determine the anthropogenic sulfur isotopic signature (δ34Santhro = +2.9 ± 0.3 ‰), and compare this result to a compilation of sulfur isotope measurements of oil and coal. Using δ34Santhro, we quantify anthropogenic sulfate concentration separated from natural sulfate. Anthropogenic sulfate concentration increases to 68 ± 7% of non-sea-salt sulfate (65.1 ± 20.2 µg kg-1) during peak anthropogenic emissions from 1960 to 1990 and decreases to 45 ± 11% of non-sea-salt sulfate (25.4 ± 12.8 µg kg-1) from 1996 to 2006. These observations provide the first long-term record of anthropogenic sulfate distinguished from natural sources (e.g., volcanoes, dimethyl sulfide), and can be used to evaluate model characterization of anthropogenic sulfate aerosol fraction and radiative forcing over the industrial era.

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