Hannah Meusel

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.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in the environment – A review

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are derivatives of PAHs with at least one nitro-functional group (-NO2) on the aromatic ring. The toxic effects of several nitro-PAHs are more pronounced than those of PAHs. Some nitro-PAHs are classified as possible or probable human carcinogens by the International Agency for Research on Cancer. Nitro-PAHs are released into the environment from combustion of carbonaceous materials (e.g. fossil fuels, biomass, waste) and post-emission transformation of PAHs. Most studies on nitro-PAHs are about air (gas-phase and particulate matter), therefore less is known about the occurrence, concentrations, transport and fate of nitro-PAHs in soils, aquatic environment and biota. Studies on partition and exchange of nitro-PAHs between adjacent environmental compartments are also sparse. The concentrations of nitro-PAHs cannot easily be predicted from the intensity of anthropogenic activity or easily related to those of PAHs. This is because anthropogenic source strengths of nitro-PAHs are different from those of PAHs, and also nitro-PAHs have additional sources (formed by photochemical conversion of PAHs). The fate and transport of nitro-PAHs could be considerably different from their related PAHs because of their higher molecular weights and considerably different sorption mechanisms. Hence, specific knowledge on nitro-PAHs is required. Regulations on nitro-PAHs are also lacking. We present an extensive review of published literature on the sources, formation, physico-chemical properties, methods of determination, occurrence, concentration, transport, fate, (eco)toxicological and adverse health effects of nitro-PAHs. We also make suggestions and recommendations about data needs, and future research directions on nitro-PAHs. It is expected that this review will stimulate scientific discussion and provide the basis for further research and regulations on nitro-PAHs.

Protein Cross-Linking and Oligomerization through Dityrosine Formation upon Exposure to Ozone

Air pollution is a potential driver for the increasing prevalence of allergic disease, and post-translational modification by air pollutants can enhance the allergenic potential of proteins. Here, the kinetics and mechanism of protein oligomerization upon ozone (O3) exposure were studied in coated-wall flow tube experiments at environmentally relevant O3 concentrations, relative humidities and protein phase states (amorphous solid, semisolid, and liquid). We observed the formation of protein dimers, trimers, and higher oligomers, and attribute the cross-linking to the formation of covalent intermolecular dityrosine species. The oligomerization proceeds fast on the surface of protein films. In the bulk material, reaction rates are limited by diffusion depending on phase state and humidity. From the experimental data, we derive a chemical mechanism and rate equations for a kinetic multilayer model of surface and bulk reaction enabling the prediction of oligomer formation. Increasing levels of tropospheric O3 in the Anthropocene may promote the formation of protein oligomers with enhanced allergenicity and may thus contribute to the increasing prevalence of allergies.

Oxidation processes in the Eastern Mediterranean atmosphere: Evidence from the Modelling of HOx Measurements over Cyprus

The Mediterranean is a climatically sensitive region located at the crossroads of air masses from three continents: Europe, Africa, and Asia. The chemical processing of air masses over this region has implications not only for the air quality but also for the long-range transport of air pollution. To obtain a comprehensive understanding of oxidation processes over the Mediterranean, atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2) were measured during an intensive field campaign (CYprus PHotochemistry EXperiment, CYPHEX2014) in the northwest of Cyprus in the summer of 2014. Very low local anthropogenic and biogenic emissions around the measurement location provided a vantage point to study the contrasts in atmospheric oxidation pathways under highly processed marine air masses and those influenced by relatively fresh emissions from mainland Europe. The CYPHEX measurements were used to evaluate OH and HO2 simulations using a photochemical box model (CAABA/MECCA) constrained with CYPHEX observations of O3, CO, NOx , hydrocarbons, peroxides, and other major HOx (OH+HO2) sources and sinks in a low-NOx environment (< 100 pptv of NO). The model simulations for OH agreed to within 10 % with in situ OH observations. Model simulations for HO2 agreed to within 17 % of the in situ observations. However, the model strongly under-predicted HO2 at high terpene concentrations, this under-prediction reaching up to 38 % at the highest terpene levels. Different schemes to improve the agreement between observed and modelled HO2, including changing the rate coefficients for the reactions of terpene-generated peroxy radicals (RO2) with NO and HO2 as well as the autoxidation of terpenegenerated RO2 species, are explored in this work. The main source of OH in Cyprus was its primary production from O3 photolysis during the day and HONO photolysis during early morning. Recycling contributed about one-third of the total OH production, and the maximum recycling efficiency was about 0.7. CO, which was the largest OH sink, was also the largest HO2 source. The lowest HOx production and losses occurred when the air masses had higher residence time over the oceans.

Physicochemical uptake and release of volatile organic compounds by soil in coated-wall flow tube experiments with ambient air

Overall Comments. The manuscript by Li et al. describes a novel field experiment used to study the uptake of ambient VOCs on soil surfaces. The study represents a test of a new system for measuring VOC uptake coefficients on soil under ambient conditions and in ambient air masses with all their complexity. It is comprised of two flow tubes (one is Teflon, the other is coated with sterilized soil) that are exposed to ambient air, the output of which is flowed into a proton-transfer mass spectrometer (PTR-MS). The main advantage of the technique is it allows simultaneous measurements of multiple reactants under ambient conditions. The potentially large data sets can allow calculation of uptake parameters of multiple species as a function of various ambient conditions (e.g., VOC concentration, T, RH, light intensity, etc.). Some of the