Early exposure to UV radiation overshadowed by precipitation and litter quality as drivers of decomposition in the northern Chihuahuan Desert.

Dryland ecosystems cover nearly 45% of the Earth's land area and account for large proportions of terrestrial net primary production and carbon pools. However, predicting rates of plant litter decomposition in these vast ecosystems has proven challenging due to their distinctly dry and often hot climate regimes, and potentially unique physical drivers of decomposition. In this study, we elucidated the role of photopriming, i.e. exposure of standing dead leaf litter to solar radiation prior to litter drop that would chemically change litter and enhance biotic decay of fallen litter. We exposed litter substrates to three different UV radiation treatments simulating three-months of UV radiation exposure in southern New Mexico: no light, UVA+UVB+Visible, and UVA+Visible. There were three litter types: mesquite leaflets (Prosopis glandulosa, litter with high nitrogen (N) concentration), filter paper (pure cellulose), and basswood (Tilia spp, high lignin concentration). We deployed the photoprimed litter in the field within a large scale precipitation manipulation experiment: ∼50% precipitation reduction, ∼150% precipitation addition, and ambient control. Our results revealed the importance of litter substrate, particularly N content, for overall decomposition in drylands, as neither filter paper nor basswood exhibited measurable mass loss over the course of the year-long study, while high N-containing mesquite litter exhibited potential mass loss. We saw no effect of photopriming on subsequent microbial decay. We did observe a precipitation effect on mesquite where the rate of decay was more rapid in ambient and precipitation addition treatments than in the drought treatment. Overall, we found that precipitation and N played a critical role in litter mass loss. In contrast, photopriming had no detected effects on mass loss over the course of our year-long study. These results underpin the importance of biotic-driven decomposition, even in the presence of photopriming, for understanding litter decomposition and biogeochemical cycles in drylands.

NOx instrument intercomparison for laboratory biomass burning source studies and urban ambient measurements in Albuquerque, New Mexico.

Understanding nitrogen oxides (NOx = NO + NO2) measurement techniques is important as air-quality standards become more stringent, important sources change, and instrumentation develops. NOx observations are compared in two environments: source testing from the combustion of Southwestern biomass fuels, and urban, ambient NOx. The latter occurred in the urban core of Albuquerque, NM, at an EPA NCORE site during February-March 2017, a relatively clean photochemical environment with ozone (O3) <60 ppb for all but 6 hr. We compare two techniques used to measure NOx in biomass smoke during biomass burning source testing: light absorption at 405 nm and a traditional chemiluminescence monitor. Two additional oxides of nitrogen techniques were added in urban measurements: a cavity attenuated phase shift instrument for direct NO2, and the NOy chemiluminescence instrument (conversion of NOy to NO by molybdenum catalyst). We find agreement similar to laboratory standards for NOx, NO2, and NO comparing all four instruments (R2 > 0.97, slopes between 0.95 and 1.01, intercepts < 2 ppb for 1-hr averages) in the slowly varying ambient setting. Little evidence for significant interferences in NO2 measurements was observed in comparing techniques in late-winter urban Albuquerque. This was also confirmed by negligible NOz contributions as measured with an NOy instrument. For the rapidly varying (1-min) higher NOx concentrations in biomass smoke source testing, larger variability characterized chemiluminescence and absorption instruments. Differences between the two instruments were both positive and negative and occurred for total NOx, NO, and NO2. Nonetheless, integrating the NOx signals over an entire burn experiment and comparing 95 combustion experiments, showed little evidence for large systematic influences of possible interfering species biasing the methods. For concentrations of <2 ppm, a comparison of burn integrated NOx, NO2, and NO yielded slopes of 0.94 to 0.96, R2 of 0.83 to 0.93, and intercepts of 8 to 25 ppb. We attribute the latter, at least in part, to significant noise particularly at low NOx concentrations, resulting from short averaging times during highly dynamic lab burns. Discrepancies between instruments as indicated by the intercepts urge caution with oxides of nitrogen measurements at concentrations <50 ppb for rapidly changing conditions. Implications: Multiple NOx measurement methods were employed to measure NOx concentrations at an EPA NCORE site in Albuquerque, NM, and in smoke produced by the combustion of Southwestern biomass fuels. Agreement shown during intercomparison of these NOx techniques indicated little evidence of significant interfering species biasing the methods in these two environments. Instrument agreement is important to understand for accurately characterizing ambient NOx conditions in a range of environments.

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.

Methane Isotope Instrument Validation and Source Identification at Four Corners, New Mexico, United States.

Measurements of δ(13)CH4 and CH4 concentration were made at a field site in Four Corners, New Mexico (FC), where we observed large sustained CH4 enhancements (2-8 ppm peaks for hours) during nocturnal inversions. Potential sources of this large CH4 signal at FC include (1) fugitive emissions from coal mining and gas processing that are thermogenic and isotopically (13)C enriched relative to background atmosphere and (2) emissions from agriculture, ruminants, landfills, and coalbed biogenic methane that are(13)C depleted relative to background atmosphere. We analyze our measurements of methane concentration and δ(13)C during spring and summer of 2012 to identify fugitive methane sources. We find CH4 plumes that are both enriched and depleted in (13)C relative to CH4 in background air. Keeling plots show a continuum of δ(13)C source compositions between -40‰ and -60‰ that are consistent with thermogenic and biogenic sources. The Picarro Mobile Methane Investigator (PMMI), a mobile δ(13)CH4 instrument platform, was deployed in the spring of 2013 and used to verify the isotopic enrichment of coal bed methane in the region. We combine our results with meteorological data to spatially separate these sources in the Four Corners regions. Using CO and CO2 data, along with meteorological data, we propose that the high methane concentration events ([CH4] > 3.5 ppm) are from both thermogenic and biogenic methane released from coal beds.

Multiscale observations of CO2, 13CO2, and pollutants at Four Corners for emission verification and attribution.

There is a pressing need to verify air pollutant and greenhouse gas emissions from anthropogenic fossil energy sources to enforce current and future regulations. We demonstrate the feasibility of using simultaneous remote sensing observations of column abundances of CO2, CO, and NO2 to inform and verify emission inventories. We report, to our knowledge, the first ever simultaneous column enhancements in CO2 (3-10 ppm) and NO2 (1-3 Dobson Units), and evidence of δ(13)CO2 depletion in an urban region with two large coal-fired power plants with distinct scrubbing technologies that have resulted in ∆NOx/∆CO2 emission ratios that differ by a factor of two. Ground-based total atmospheric column trace gas abundances change synchronously and correlate well with simultaneous in situ point measurements during plume interceptions. Emission ratios of ∆NOx/∆CO2 and ∆SO2/∆CO2 derived from in situ atmospheric observations agree with those reported by in-stack monitors. Forward simulations using in-stack emissions agree with remote column CO2 and NO2 plume observations after fine scale adjustments. Both observed and simulated column ∆NO2/∆CO2 ratios indicate that a large fraction (70-75%) of the region is polluted. We demonstrate that the column emission ratios of ∆NO2/∆CO2 can resolve changes from day-to-day variation in sources with distinct emission factors (clean and dirty power plants, urban, and fires). We apportion these sources by using NO2, SO2, and CO as signatures. Our high-frequency remote sensing observations of CO2 and coemitted pollutants offer promise for the verification of power plant emission factors and abatement technologies from ground and space.

Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2.

Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120 per thousand relative to the world's oceans. This cannot be explained by the sources of H2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H2 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 per thousand, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H2 produced from CH4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H2 from CH4 concentrates D in the product H2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H2.