Stable isotope fractionation during ultraviolet photolysis of N_2O

The biogeochemical cycling of nitrous oxide plays an important role in greenhouse forcing and ozone regulation. Laboratory studies of N_2O:N_2 mixtures irradiated between 193–207 nm reveal a significant enrichment of the residual heavy nitrous oxide isotopomers. The isotopic signatures resulting from photolysis are well modeled by an irreversible Rayleigh distillation process, with large enrichment factors of ε_(15,18)(193 nm) = −18.4,‐14.5 per mil and ε_(15,18)(207 nm) = −48.7,‐46.0 per mil. These results, when combined with diffusive mixing processes, have the potential to explain the stratospheric enrichments previously observed

High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW) SOA (m/z \u3c 300) are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10–15 carbon atoms in the first group (e.g. C11H18O6) provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (m/z \u3e 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels

Concentration and δD of molecular hydrogen in boreal forests: Ecosystem-scale systematics of atmospheric H_2

We examined the concentration and δD of atmospheric H2 in a boreal forest in interior Alaska to investigate the systematics of high latitude soil uptake at ecosystem scale. Samples collected during nighttime inversions exhibited vigorous H_2 uptake, with concentration negatively correlated with the concentration of CO_2 (−0.8 to −1.2 ppb H_2 per ppm CO_2) and negatively correlated with δD of H_2. We derived H_2 deposition rates of between 2 to 12 nmol m^(−2) s^(−1). These rates are comparable to those observed in lower latitude ecosystems. We also derive an average fractionation factor, α = D:H_(residual)/D:H_(consumed) = 0.94 ± 0.01 and suggestive evidence that α depends on forest maturity. Our results show that high northern latitude soils are a significant sink of molecular hydrogen indicating that the record of atmospheric H_2 may be sensitive to changes in climate and land use

Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H_2

Molecular hydrogen (H_2) is the second most abundant trace gas in the atmosphere after methane (CH_4). In the troposphere, the D/H ratio of H_2 is enriched by 120‰ relative to the world's oceans. This cannot be explained by the sources of H_2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H_2 from its single largest source—the photochemical oxidation of methane—has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440‰, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H_2 produced from CH_4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H_2 from CH_4 concentrates D in the product H_2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H_2

Unsaturation of vapour pressure inside leaves of two conifer species

Stomatal conductance (gs) impacts both photosynthesis and transpiration, and is therefore fundamental to the global carbon and water cycles, food production, and ecosystem services. Mathematical models provide the primary means of analysing this important leaf gas exchange parameter. A nearly universal assumption in such models is that the vapour pressure inside leaves (ei) remains saturated under all conditions. The validity of this assumption has not been well tested, because so far ei cannot be measured directly. Here, we test this assumption using a novel technique, based on coupled measurements of leaf gas exchange and the stable isotope compositions of CO2 and water vapour passing over the leaf. We applied this technique to mature individuals of two semiarid conifer species. In both species, ei routinely dropped below saturation when leaves were exposed to moderate to high air vapour pressure deficits. Typical values of relative humidity in the intercellular air spaces were as low 0.9 in Juniperus monosperma and 0.8 in Pinus edulis. These departures of ei from saturation caused significant biases in calculations of gs and the intercellular CO2 concentration. Our results refute the longstanding assumption of saturated vapour pressure in plant leaves under all conditions.We thank Meisha Holloway-Phillips, Alex Cheesman, Hilary Stuart-Williams, and Michael Roderick for helpful discussions and comments on the manuscript; and Lily Cohen, Adam Collins, and Turin Dickman for measurement and field assistance. This research was supported by Australian Research Council Discovery Grants DP1097276 and DP150100588

Causes and Implications of Extreme Atmospheric Moisture Demand during the Record-Breaking 2011 Wildfire Season in the Southwestern United States

In 2011, exceptionally low atmospheric moisture content combined with moderately high temperatures to produce a record-high vapor pressure deficit (VPD) in the southwestern United States (SW). These conditions combined with record-low cold-season precipitation to cause widespread drought and extreme wildfires. Although interannual VPD variability is generally dominated by temperature, high VPD in 2011 was also driven by a lack of atmospheric moisture. The May–July 2011 dewpoint in the SW was 4.5 standard deviations below the long-term mean. Lack of atmospheric moisture was promoted by already very dry soils and amplified by a strong ocean-to-continent sea level pressure gradient and upper-level convergence that drove dry northerly winds and subsidence upwind of and over the SW. Subsidence drove divergence of rapid and dry surface winds over the SW, suppressing southerly moisture imports and removing moisture from already dry soils. Model projections developed for the fifth phase of the Coupled Model Intercomparison Project (CMIP5) suggest that by the 2050s warming trends will cause mean warm-season VPD to be comparable to the record-high VPD observed in 2011. CMIP5 projections also suggest increased interannual variability of VPD, independent of trends in background mean levels, as a result of increased variability of dewpoint, temperature, vapor pressure, and saturation vapor pressure. Increased variability in VPD translates to increased probability of 2011-type VPD anomalies, which would be superimposed on ever-greater background VPD levels. Although temperature will continue to be the primary driver of interannual VPD variability, 2011 served as an important reminder that atmospheric moisture content can also drive impactful VPD anomalies

Correlations between components of the water balance and burned area reveal new insights for predicting forest fire area in the southwest United States

We related measurements of annual burned area in the southwest United States during 1984–2013 to records of climate variability. Within forests, annual burned area correlated at least as strongly with spring–summer vapour pressure deficit (VPD) as with 14 other drought-related metrics, including more complex metrics that explicitly represent fuel moisture. Particularly strong correlations with VPD arise partly because this term dictates the atmospheric moisture demand. Additionally, VPD responds to moisture supply, which is difficult to measure and model regionally due to complex micrometeorology, land cover and terrain. Thus, VPD appears to be a simple and holistic indicator of regional water balance. Coupled with the well-known positive influence of prior-year cold season precipitation on fuel availability and connectivity, VPD may be utilised for burned area forecasts and also to infer future trends, though these are subject to other complicating factors such as land cover change and management. Assuming an aggressive greenhouse gas emissions scenario, climate models predict mean spring–summer VPD will exceed the highest recorded values in the southwest in nearly 40% of years by the middle of this century. These results forewarn of continued increases in burned forest area in the southwest United States, and likely elsewhere, when fuels are not limiting

D/H ratios of atmospheric H_2 in urban air: Results using new methods for analysis of nano-molar H_2 samples

We present the results of a study of the concentration and D/H ratio of molecular hydrogen from air in the Los Angeles Basin and adjacent San Gabriel Mountains. These data define a mixing relationship in dimensions of D/H ratio vs. 1/(H_2) which constrains the δD_(VSMOW) of unpolluted winter air in this region to be ca. +100 to +125 ‰ and that of urban H2 sources to be ca. −270 ‰. This study makes use of a new method for measuring the deuterium content of molecular hydrogen in small samples (∼100 to 500 cc) of air, which we describe in detail. The method consists of an off-line separation of H_2 followed by introduction to the mass spectrometer in a continuous flow of He. Off-line, all components of an atmospheric gas sample, with the exception of He, H_2, and Ne are condensed by exposure to a cold-trap held at 30 Kelvin. This separation is followed by cryo-transfer of non-condensable gases to a small volume molecular sieve finger, with assist from a mercury piston pump. At the mass spectrometer, the sample is put in line with a continuous flow of He where it is focused on to an additional column of molecular sieve before subsequent introduction into the ion source. Analyses of DH/H_2 ratio have accuracy and precision of ±4 to 7 per mil. Comparison of sample peak area to peak areas of standards of known size allows for determination of H_2 concentration with accuracy and precision of ∼±5%, relative. The method reduces sample size and processing time by several orders of magnitude compared to previous methods, allowing for sampling at proportionately higher spatial and temporal resolution

Experimental constraints on the stable-isotope systematics of CO_2 ice/vapor systems and relevance to the study of Mars

Variations in the isotopic compositions of oxygen, hydrogen, and carbon in the near-surface environment of Mars are likely influenced by condensation, evaporation, and sublimation of major volatile species (H_2O, CO_2). We present here an experimental study of the fractionations of ^(18)O/^(16)O and ^(13)C/^(12)C ratios between CO_2 ice and vapor at conditions relevant to the present near-surface of Mars; these experiments constrain isotopic variations generated by the current Martian CO_2 condensation/sublimation cycle. Oxygen-isotope fractionation between ice and vapor (Δ_(ice-vapor) = 1000 · 1n ([^(18)O_(ice)/^(16)O_(ice)] / [^(18)O_(vapor)/^(16)O_(vapor)]) varies approximately linearly vs. 1/T between temperatures of 150 and 130 K (from 4.2 and 7.5 ‰, respectively). Carbon isotopes are unfractionated (Δ^(13)C_(ice-vapor) ≤ 0.2‰) at temperatures ≥ 135 K and only modestly fractionated (Δ^(13)C_(ice-vapor) ≤ 0.4‰) at temperatures between 135 and 130 K. Martian atmospheric volumes that are residual to high extents of condensation (i.e., at high latitudes during the winter) may vary in δ^(18)O by up to tens of per mil, depending on the scales and mechanisms of ice/vapor interaction and atmospheric mixing. Precise (i.e., per mil level) examination of the Martian atmosphere or ices could be used as a tool for examining the Martian climate; at present such precision is only likely to be had from laboratory study of returned samples or substantial advances in the performance of mass spectrometers on landers and/or orbital spacecraft. Oxygen-isotope fractionations accompanying the CO_2 condensation/sublimation cycle may play a significant role in the oxygen-isotope geochemistry of secondary phases formed in SNC meteorites, in particular as a means of generating ^(18)O-depleted volatile reservoirs