Foliar uptake of atmospheric nitrate by two dominant subalpine plants: insights from in situ triple-isotope analysis.

The significance of foliar uptake of nitrogen (N) compounds in natural conditions is not well understood, despite growing evidence of its importance to plant nutrition. In subalpine meadows, N-limitation fosters the dominance of specific subalpine plant species, which in turn ensures the provision of essential ecosystems services. Understanding how these plants absorb N and from which sources is important in predicting ecological consequences of increasing N deposition. Here, we investigate the sources of N to plants from subalpine meadows with distinct land-use history in the French Alps, using the triple isotopes (Δ17 O, δ18 O, and δ15 N) of plant tissue nitrate (NO3- ). We use this approach to evaluate the significance of foliar uptake of atmospheric NO3- (NO3-atm ). The foliar uptake of NO3-atm accounted for 4-16% of the leaf NO3- content, and contributed more to the leaf NO3- pool after peak biomass. Additionally, the gradual 15 N enrichment of NO3- from the soil to the leaves reflected the contribution of NO3-atm assimilation to plants' metabolism. The present study confirms that foliar uptake is a potentially important pathway for NO3-atm into subalpine plants. This is of major significance as N emissions (and deposition) are predicted to increase globally in the future.

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis.

RATIONALE: Precise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution. METHODS: One mL of reducing solution made of HI and NaH2 PO2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H2 S was purged with inert gas (He or N2 ) through gas-washing tubes and then collected by NaOH solution. The collected H2 S was converted into Ag2 S by adding AgNO3 solution and the co-precipitated Ag2 O was removed by adding a few drops of concentrated HNO3 . RESULTS: Within 2-3 h, a 100% yield was observed for samples with 0.2-2.5 µmol Na2 SO4 . The reduction rate was much slower for BaSO4 and a complete reduction was not observed. International sulfur reference materials, NBS-127, SO-5 and SO-6, were processed with this method, and the measured against accepted δ34 S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R2 value of 0.998. CONCLUSIONS: The new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H2 S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available.

Tracing the Fate of Atmospheric Nitrate in a Subalpine Watershed Using Δ17O.

Nitrogen is an essential nutrient for life on Earth, but in excess, it can lead to environmental issues (e.g., N saturation, loss of biodiversity, acidification of lakes, etc.). Understanding the nitrogen budget (i.e., inputs and outputs) is essential to evaluate the prospective decay of the ecosystem services (e.g., freshwater quality, erosion control, loss of high patrimonial-value plant species, etc.) that subalpine headwater catchments provide, especially as these ecosystems experience high atmospheric nitrogen deposition. Here, we use a multi-isotopic tracer (Δ17O, δ15N and δ18O) of nitrate in aerosols, snow, and streams to assess the fate of atmospherically deposited nitrate in the subalpine watershed of the Lautaret Pass (French Alps). We show that atmospheric N deposition contributes significantly to stream nitrate pool year-round, either by direct inputs (up to 35%) or by in situ nitrification of atmospheric ammonium (up to 35%). Snowmelt in particular leads to high exports of atmospheric nitrate, most likely fast enough to impede assimilation by surrounding ecosystems. Yet, in a context of climate change, with shorter snow seasons, and increasing nitrogen emissions, our results hint at possibly stronger ecological consequences of nitrogen atmospheric deposition in the close future.

Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

RATIONALE: Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. METHODS: The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N2 O separation by gas chromatography before N2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. RESULTS: The δ17 O, δ18 O, and Δ17 O values increased with increasing sample size, although the δ15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ18 O, Δ17 O, and δ15 N values, results that are not inferior to those from other systems using gold tube or gold wire. CONCLUSIONS: An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision and sample throughput (23 min per sample on average), and minimal manual treatment. Copyright © 2016 John Wiley & Sons, Ltd.

Sunlight-driven nitrate loss records Antarctic surface mass balance.

Standard proxies for reconstructing surface mass balance (SMB) in Antarctic ice cores are often inaccurate or coarsely resolved when applied to more complicated environments away from dome summits. Here, we propose an alternative SMB proxy based on photolytic fractionation of nitrogen isotopes in nitrate observed at 114 sites throughout East Antarctica. Applying this proxy approach to nitrate in a shallow core drilled at a moderate SMB site (Aurora Basin North), we reconstruct 700 years of SMB changes that agree well with changes estimated from ice core density and upstream surface topography. For the under-sampled transition zones between dome summits and the coast, we show that this proxy can provide past and present SMB values that reflect the immediate local environment and are derived independently from existing techniques.

Atmospheric nitrate export in streams along a montane to urban gradient.

Nitrogen (N) emissions associated with urbanization exacerbate the atmospheric N influx to remote ecosystems - like mountains -, leading to well-documented detrimental effects on ecosystems (e.g., soil acidification, pollution of freshwaters). Here, the importance and fate of N deposition in a watershed was evaluated along a montane to urban gradient, using a multi-isotopic tracers approach (Δ17O, δ15N, δ18O of nitrate, δ2H and δ18O of water). In this setting, the montane streams had higher proportions of atmospheric nitrate compared to urban streams, and exported more atmospheric nitrate on a yearly basis (0.35 vs 0.10 kg-Nha-1yr-1). In urban areas, nitrate exports were driven by groundwater, whereas in the catchment head nitrate exports were dominated by surface runoff. The main sources of nitrate to the montane streams were microbial nitrification and atmospheric deposition, whereas microbial nitrification and sewage leakage contributed most to urban streams. Based on the measurement of δ15N and δ18O-NO3-, biological processes such as denitrification or N assimilation were not predominant in any streams in this study. The observed low δ15N and δ18O range of terrestrial nitrate (i.e., nitrate not coming from atmospheric deposition) in surface water compared to literature suggests that atmospheric deposition may be underestimated as a direct source of N.

Timing of atmospheric CO2 and Antarctic temperature changes across termination III.

The analysis of air bubbles from ice cores has yielded a precise record of atmospheric greenhouse gas concentrations, but the timing of changes in these gases with respect to temperature is not accurately known because of uncertainty in the gas age-ice age difference. We have measured the isotopic composition of argon in air bubbles in the Vostok core during Termination III (approximately 240,000 years before the present). This record most likely reflects the temperature and accumulation change, although the mechanism remains unclear. The sequence of events during Termination III suggests that the CO2 increase lagged Antarctic deglacial warming by 800 +/- 200 years and preceded the Northern Hemisphere deglaciation.