Soil HONO emissions at high moisture content are driven by microbial nitrate reduction to nitrite: tackling the HONO puzzle.

Nitrous acid (HONO) is a precursor of the hydroxyl radical (OH), a key oxidant in the degradation of most air pollutants. Field measurements indicate a large unknown source of HONO during the day time. Release of nitrous acid (HONO) from soil has been suggested as a major source of atmospheric HONO. We hypothesize that nitrite produced by biological nitrate reduction in oxygen-limited microzones in wet soils is a source of such HONO. Indeed, we found that various contrasting soil samples emitted HONO at high water-holding capacity (75-140%), demonstrating this to be a widespread phenomenon. Supplemental nitrate stimulated HONO emissions, whereas ethanol (70% v/v) treatment to minimize microbial activities reduced HONO emissions by 80%, suggesting that nitrate-dependent biotic processes are the sources of HONO. High-throughput Illumina sequencing of 16S rRNA as well as functional gene transcripts associated with nitrate and nitrite reduction indicated that HONO emissions from soil samples were associated with nitrate reduction activities of diverse Proteobacteria. Incubation of pure cultures of bacterial nitrate reducers and gene-expression analyses, as well as the analyses of mutant strains deficient in nitrite reductases, showed positive correlations of HONO emissions with the capability of microbes to reduce nitrate to nitrite. Thus, we suggest biological nitrate reduction in oxygen-limited microzones as a hitherto unknown source of atmospheric HONO, affecting biogeochemical nitrogen cycling, atmospheric chemistry, and global modeling.

Eyes on the future - evidence for trade-offs between growth, storage and defense in Norway spruce.

Carbon (C) allocation plays a central role in tree responses to environmental changes. Yet, fundamental questions remain about how trees allocate C to different sinks, for example, growth vs storage and defense. In order to elucidate allocation priorities, we manipulated the whole-tree C balance by modifying atmospheric CO2 concentrations [CO2 ] to create two distinct gradients of declining C availability, and compared how C was allocated among fluxes (respiration and volatile monoterpenes) and biomass C pools (total biomass, nonstructural carbohydrates (NSC) and secondary metabolites (SM)) in well-watered Norway spruce (Picea abies) saplings. Continuous isotope labelling was used to trace the fate of newly-assimilated C. Reducing [CO2 ] to 120 ppm caused an aboveground C compensation point (i.e. net C balance was zero) and resulted in decreases in growth and respiration. By contrast, soluble sugars and SM remained relatively constant in aboveground young organs and were partially maintained with a constant allocation of newly-assimilated C, even at expense of root death from C exhaustion. We conclude that spruce trees have a conservative allocation strategy under source limitation: growth and respiration can be downregulated to maintain 'operational' concentrations of NSC while investing newly-assimilated C into future survival by producing SM.

Nitrous oxide effluxes from plants as a potentially important source to the atmosphere.

The global budget for nitrous oxide (N2 O), an important greenhouse gas and probably dominant ozone-depleting substance emitted in the 21st century, is far from being fully understood. Cycling of N2 O in terrestrial ecosystems has traditionally exclusively focused on gas exchange between the soil surface (nitrification-denitrification processes) and the atmosphere. Terrestrial vegetation has not been considered in the global budget so far, even though plants are known to release N2 O. Here, we report the N2 O emission rates of 32 plant species from 22 different families measured under controlled laboratory conditions. Furthermore, the first isotopocule values (δ15 N, δ18 O and δ15 Nsp ) of N2 O emitted from plants were determined. A robust relationship established between N2 O emission and CO2 respiration rates, which did not alter significantly over a broad range of changing environmental conditions, was used to quantify plant-derived emissions on an ecosystem scale. Stable isotope measurements (δ15 N, δ18 O and δ15 Nsp ) of N2 O emitted by plants clearly show that the dual isotopocule fingerprint of plant-derived N2 O differs from that of currently known microbial or chemical processes. Our work suggests that vegetation is a natural source of N2 O in the environment with a large fraction released by a hitherto unrecognized process.

New Perspectives on CO2, Temperature, and Light Effects on BVOC Emissions Using Online Measurements by PTR-MS and Cavity Ring-Down Spectroscopy.

Volatile organic compounds (VOC) play important roles in atmospheric chemistry, plant ecology, and physiology, and biogenic VOC (BVOC) emitted by plants is the largest VOC source. Our knowledge about how environmental drivers (e.g., carbon, light, and temperature) may regulate BVOC emissions is limited because they are often not controlled. We combined a greenhouse facility to manipulate atmospheric CO2 ([CO2]) with proton-transfer-reaction mass spectrometry (PTR-MS) and cavity ring-down spectroscopy to investigate the regulation of BVOC in Norway spruce. Our results indicate a direct relationship between [CO2] and methanol and acetone emissions, and their temperature and light dependencies, possibly related to substrate availability. The composition of monoterpenes stored in needles remained constant, but emissions of mono-(linalool) and sesquiterpenes (ß-farnesene) increased at lower [CO2], with the effects being most pronounced at the highest air temperature. Pulse-labeling suggested an immediate incorporation of recently assimilated carbon into acetone, mono- and sesquiterpene emissions even under 50 ppm [CO2]. Our results provide new perspectives on CO2, temperature and light effects on BVOC emissions, in particular how they depend on stored pools and recent photosynthetic products. Future studies using smaller but more seedlings may allow sufficient replication to examine the physiological mechanisms behind the BVOC responses.

Biological soil crusts accelerate the nitrogen cycle through large NO and HONO emissions in drylands.

Reactive nitrogen species have a strong influence on atmospheric chemistry and climate, tightly coupling the Earth's nitrogen cycle with microbial activity in the biosphere. Their sources, however, are not well constrained, especially in dryland regions accounting for a major fraction of the global land surface. Here, we show that biological soil crusts (biocrusts) are emitters of nitric oxide (NO) and nitrous acid (HONO). Largest fluxes are obtained by dark cyanobacteria-dominated biocrusts, being ∼20 times higher than those of neighboring uncrusted soils. Based on laboratory, field, and satellite measurement data, we obtain a best estimate of ∼1.7 Tg per year for the global emission of reactive nitrogen from biocrusts (1.1 Tg a(-1) of NO-N and 0.6 Tg a(-1) of HONO-N), corresponding to ∼20% of global nitrogen oxide emissions from soils under natural vegetation. On continental scales, emissions are highest in Africa and South America and lowest in Europe. Our results suggest that dryland emissions of reactive nitrogen are largely driven by biocrusts rather than the underlying soil. They help to explain enigmatic discrepancies between measurement and modeling approaches of global reactive nitrogen emissions. As the emissions of biocrusts strongly depend on precipitation events, climate change affecting the distribution and frequency of precipitation may have a strong impact on terrestrial emissions of reactive nitrogen and related climate feedback effects. Because biocrusts also account for a large fraction of global terrestrial biological nitrogen fixation, their impacts should be further quantified and included in regional and global models of air chemistry, biogeochemistry, and climate.

Soil nitrite as a source of atmospheric HONO and OH radicals.

Hydroxyl radicals (OH) are a key species in atmospheric photochemistry. In the lower atmosphere, up to ~30% of the primary OH radical production is attributed to the photolysis of nitrous acid (HONO), and field observations suggest a large missing source of HONO. We show that soil nitrite can release HONO and explain the reported strength and diurnal variation of the missing source. Fertilized soils with low pH appear to be particularly strong sources of HONO and OH. Thus, agricultural activities and land-use changes may strongly influence the oxidizing capacity of the atmosphere. Because of the widespread occurrence of nitrite-producing microbes, the release of HONO from soil may also be important in natural environments, including forests and boreal regions.