Yafang Cheng

Soil Nitrite as a Source of Atmospheric HONO and OH Radicals

Biogenic nitrite in soils is an important source of atmospheric HONO and OH. 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.

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China.

Multiphase chemistry of NO2 and alkaline matter in aerosol water explains rapid sulfate formation and severe haze in China. Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to ~300 μg m−3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution.

An Improved Model for the Turbulent PBL

Abstract Second-order turbulence models of the Mellor and Yamada type have been widely used to simulate the planetary boundary layer (PBL). It is, however, known that these models have several deficiencies. For example, assuming the production of the turbulent kinetic energy equals its dissipation, they all predict a critical Richardson number that is about four times smaller than the large eddy simulation (LES) data in stably stratified flows and are unable to distinguish the vertical and lateral components of the turbulent kinetic energy in neutral PBLs, and they predict a boundary layer height lower than expected. In the present model, three new ingredients are employed: 1) an updated expression for the pressure–velocity correlation, 2) an updated expression for the pressure–temperature correlation, and 3) recent renormalization group (RNG) expressions for the different turbulence timescales, which yield 1) a critical Richardson number of order unity in the stably stratified PBL (at level 2 of the mode...

HONO Emissions from Soil Bacteria as a Major Source of Atmospheric Reactive Nitrogen

From Soil to Sky Trace gases emitted either through the activity of microbial communities or from abiotic reactions in the soil influence atmospheric chemistry. In laboratory column experiments using several soil types, Oswald et al. (p. 1233) showed that soils from arid regions and farmlands can produce substantial quantities of nitric oxide (NO) and nitrous acid (HONO). Ammonia-oxidizing bacteria are the primary source of HONO at comparable levels to NO, thus serving as an important source of reactive nitrogen to the atmosphere. HONO emissions from soil are comparable to those of NO in arid and arable regions. Abiotic release of nitrous acid (HONO) in equilibrium with soil nitrite (NO2–) was suggested as an important contributor to the missing source of atmospheric HONO and hydroxyl radicals (OH). The role of total soil-derived HONO in the biogeochemical and atmospheric nitrogen cycles, however, has remained unknown. In laboratory experiments, we found that for nonacidic soils from arid and arable areas, reactive nitrogen emitted as HONO is comparable with emissions of nitric oxide (NO). We show that ammonia-oxidizing bacteria can directly release HONO in quantities larger than expected from the acid-base and Henry’s law equilibria of the aqueous phase in soil. This component of the nitrogen cycle constitutes an additional loss term for fixed nitrogen in soils and a source for reactive nitrogen in the atmosphere.

Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon

Salty Origins of Fresh Water Cloud droplets above the Amazonian rain forest form mostly around organic aerosols, but the source of the aerosols has been a mystery. Pöhlker et al. (p. 1075) report that particles rich in potassium salts emitted by Amazonian vegetation can act as the seeds for the growth of organic aerosol particles that function as condensation nuclei for water droplets. These specks of biogenic salts provide a surface for the condensation of low- or semi-volatile organic compounds formed by the atmospheric oxidation of isoprene and terpenes, molecules produced in great abundance by many kinds of Amazonian plants. Potassium salt particles account for the previously mysterious initiation sites of aerosol growth above the Amazonian rainforest. The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt–rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.

Stably Stratified Flows: A Model with No Ri(cr)*

A large set of laboratory, direct numerical simulation (DNS), and large eddy simulation (LES) data indicates that in stably stratified flows turbulent mixing exists up to Ri O(100), meaning that there is practically no Ri(cr). On the other hand, traditional local second-order closure (SOC) models entail a critical Ri(cr) O(1) above which turbulence ceases to exist and are therefore unable to explain the above data. The authors suggest how to modify the recent SOC model of Cheng et al. to reproduce the above data for arbitrary Ri.

Size dependence of phase transitions in aerosol nanoparticles

Phase transitions of nanoparticles are of fundamental importance in atmospheric sciences, but current understanding is insufficient to explain observations at the nano-scale. In particular, discrepancies exist between observations and model predictions of deliquescence and efflorescence transitions and the hygroscopic growth of salt nanoparticles. Here we show that these discrepancies can be resolved by consideration of particle size effects with consistent thermodynamic data. We present a new method for the determination of water and solute activities and interfacial energies in highly supersaturated aqueous solution droplets (Differential Köhler Analysis). Our analysis reveals that particle size can strongly alter the characteristic concentration of phase separation in mixed systems, resembling the influence of temperature. Owing to similar effects, atmospheric secondary organic aerosol particles at room temperature are expected to be always liquid at diameters below ~20 nm. We thus propose and demonstrate that particle size should be included as an additional dimension in the equilibrium phase diagram of aerosol nanoparticles.

New Third-Order Moments for the Convective Boundary Layer

Abstract Turbulent convection is inherently a nonlocal phenomenon and a primary condition for a successful treatment of the convective boundary layer is a reliable model of nonlocality. In the dynamic equations governing the convective flux, the turbulent kinetic energy, etc., nonlocality is represented by the third-order moments (TOMs). Since the simplest form, the so-called down gradient approximation (DGA), severely underestimates the TOMs (up to an order of magnitude), a more physical model is needed. In 1994, an analytical model was presented that was derived directly from the dynamical equations for the TOMs. It considerably improved the DGA but was a bit cumbersome to use and, more importantly, it was based on the quasi-normal (QN) approximation for the fourth-order moments. Here, we present a new analytic expression for the TOMs that is structurally simpler than the 1994 expression and avoids the QN approximation. The resulting fit to the LES data is superior to that of the 1994 model.

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

Significance Biological soil crusts (biocrusts), occurring on ground surfaces in drylands throughout the world, are among the oldest life forms consisting of cyanobacteria, lichens, mosses, and algae plus heterotrophic organisms in varying proportions. They prevent soil erosion and nurture ecosystems by fixing carbon and nitrogen from the atmosphere. Here, we show that the fixed nitrogen is processed within the biocrusts, and during this metabolic activity, nitrogen oxide and nitrous acid are released to the atmosphere. Both of these gases are highly relevant, as they influence the radical formation and oxidizing capacity of the lower atmosphere, also interacting with climate change. In drylands, biocrusts appear to play a key role both in nitrogen fixation and the release of atmospheric reactive nitrogen. 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.

Nonlocal Convective PBL Model Based on New Third- and Fourth-Order Moments

The standard approach to studying the planetary boundary layer (PBL) via turbulence models begins with the first-moment equations for temperature, moisture, and mean velocity. These equations entail second-order moments that are solutions of dynamic equations, which in turn entail third-order moments, and so on. How and where to terminate (close) the moments equations has not been a generally agreed upon procedure and a variety of models differ precisely in the way they terminate the sequence. This can be viewed as a bottom-up approach. In this paper, a top-down procedure is suggested, worked out, and justified, in which a new closure model is proposed for the fourth-order moments (FOMs). The key reason for this consideration is the availability of new aircraft data that provide for the first time the z profile of several FOMs. The new FOM expressions have nonzero cumulants that the model relates to the z integrals of the third-order moments (TOMs), giving rise to a nonlocal model for the FOMs. The new FOM model is based on an analysis of the TOM equations with the aid of large-eddy simulation (LES) data, and is verified by comparison with the aircraft data. Use of the new FOMs in the equations for the TOMs yields a new TOM model, in which the TOMs are damped more realistically than in previous models. Surprisingly, the new FOMs with nonzero cumulants simplify, rather than complicate, the TOM model as compared with the quasi-normal (QN) approximation, since the resulting analytic expressions for the TOMs are considerably simpler than those of previous models and are free of algebraic singularities. The new TOMs are employed in a second-order moment (SOM) model, a numerical simulation of a convective PBL is run, and the resulting mean potential temperature T, the SOMs, and the TOMs are compared with several LES data. As a final consistency check, T, SOMs, and TOMs are substituted from the PBL run back into the FOMs, which are again compared with the aircraft data.