Photocatalytic fixation of NOx in soils

Nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants that are directly harmful to human health. Recently in urban and industrial areas, synthetic materials have been developed and deployed to photocatalytically oxidize NOx to nitrate (NO3−) in order to improve air quality. We show that the natural presence of small amounts (≤5%) of titanium oxides, such as anatase and rutile, can also drive NOx oxidation to nitrate in soils under UV–visible irradiation. The NO uptake coefficients ranged between 0.1 × 10−6 for sandy soils to 6.4 × 10−5 in the case of tropical clay soils; the latter comparable in efficiency to current industrial man-made catalysts. This photocatalytic N-fixation mechanism offers a new strategy for NOx mitigation from the atmosphere by transforming it into nitrate, and simultaneously provides an energy efficient source of essential fertilizer to agriculture

Assessing chemistry schemes and constraints in air quality models used to predict ozone in London against the detailed Master Chemical Mechanism

Air pollution is the environmental factor with the greatest impact on human health in Europe. Understanding the key processes driving air quality across the relevant spatial scales, especially during pollution exceedances and episodes, is essential to provide effective predictions for both policymakers and the public. It is particularly important for policy regulators to understand the drivers of local air quality that can be regulated by national policies versus the contribution from regional pollution transported from mainland Europe or elsewhere. One of the main objectives of the Coupled Urban and Regional processes: Effects on AIR quality (CUREAIR) project is to determine local and regional contributions to ozone events. A detailed zero-dimensional (0-D) box model run with the Master Chemical Mechanism (MCMv3.2) is used as the benchmark model against which the less explicit chemistry mechanisms of the Generic Reaction Set (GRS) and the Common Representative Intermediates (CRIv2-R5) schemes are evaluated. GRS and CRI are used by the Atmospheric Dispersion Modelling System (ADMS-Urban) and the regional chemistry transport model EMEP4UK, respectively. The MCM model uses a near-explicit chemical scheme for the oxidation of volatile organic compounds (VOCs) and is constrained to observations of VOCs, NOx, CO, HONO (nitrous acid), photolysis frequencies and meteorological parameters measured during the ClearfLo (Clean Air for London) campaign. The sensitivity of the less explicit chemistry schemes to different model inputs has been investigated: Constraining GRS to the total VOC observed during ClearfLo as opposed to VOC derived from ADMS-Urban dispersion calculations, including emissions and background concentrations, led to a significant increase (674% during winter) in modelled ozone. The inclusion of HONO chemistry in this mechanism, particularly during wintertime when other radical sources are limited, led to substantial increases in the ozone levels predicted (223%). When the GRS and CRIv2-R5 schemes are run with the equivalent model constraints to the MCM, they are able to reproduce the level of ozone predicted by the near-explicit MCM to within 40% and 20% respectively for the majority of the time. An exception to this trend was observed during pollution episodes experienced in the summer, when anticyclonic conditions favoured increased temperatures and elevated O3. The in situ O3 predicted by the MCM was heavily influenced by biogenic VOCs during these conditions and the low GRS [O3] : MCM [O3] ratio (and low CRIv2-R5 [O3] : MCM [O3] ratio) demonstrates that these less explicit schemes under-represent the full O3 creation potential of these VOCs. To fully assess the influence of the in situ O3 generated from local emissions versus O3 generated upwind of London and advected in, the time since emission (and, hence, how far the real atmosphere is from steady state) must be determined. From estimates of the mean transport time determined from the NOx : NOy ratio observed at North Kensington during the summer and comparison of the O3 predicted by the MCM model after this time, ∼60% of the median observed [O3] could be generated from local emissions. During the warmer conditions experienced during the easterly flows, however, the observed [O3] may be even more heavily influenced by London's emissions

Dead Sea evaporation by eddy covariance measurements vs. aerodynamic, energy budget, Priestley–Taylor, and Penman estimates

The Dead Sea is a terminal lake, located in an arid environment. Evaporation is the key component of the Dead Sea water budget and accounts for the main loss of water. So far, lake evaporation has been determined by indirect methods only and not measured directly. Consequently, the governing factors of evaporation are unknown. For the first time, long-term eddy covariance measurements were performed at the western Dead Sea shore for a period of 1 year by implementing a new concept for onshore lake evaporation measurements. To account for lake evaporation during offshore wind conditions, a robust and reliable multiple regression model was developed using the identified governing factors wind velocity and water vapour pressure deficit. An overall regression coefficient of 0.8 is achieved. The measurements show that the diurnal evaporation cycle is governed by three local wind systems: a lake breeze during daytime, strong downslope winds in the evening, and strong northerly along-valley flows during the night. After sunset, the strong winds cause half-hourly evaporation rates which are up to 100 % higher than during daytime. The median daily evaporation is 4.3 mm d−1 in July and 1.1 mm d−1 in December. The annual evaporation of the water surface at the measurement location was 994±88 mm a−1 from March 2014 until March 2015. Furthermore, the performance of indirect evaporation approaches was tested and compared to the measurements. The aerodynamic approach is applicable for sub-daily and multi-day calculations and attains correlation coefficients between 0.85 and 0.99. For the application of the Bowen ratio energy budget method and the Priestley–Taylor method, measurements of the heat storage term are inevitable on timescales up to 1 month. Otherwise strong seasonal biases occur. The Penman equation was adapted to calculate realistic evaporation, by using an empirically gained linear function for the heat storage term, achieving correlation coefficients between 0.92 and 0.97. In summary, this study introduces a new approach to measure lake evaporation with a station located at the shoreline, which is also transferable to other lakes. It provides the first directly measured Dead Sea evaporation rates as well as applicable methods for evaporation calculation. The first one enables us to further close the Dead Sea water budget, and the latter one enables us to facilitate water management in the region

HONO measurements with a chemical ionization mass spectrometer during FIONA

Nitrous acid (HONO) is an important source of the OH radical, the primary oxidant in the atmosphere. The chemistry of HONO and its possible sources in the atmosphere are not well understood. The aims of the FIONA (Formal Intercomparisons of Observations of Nitrous Acid) campaign are to establish a better understanding of HONO chemistry and to intercompare different measurement techniques. Data from 19 instruments from 9 countries including spectroscopy (DOAS, BBCEAS, LIF), wet chemistry, denuders and mass spectrometry were intercompared at typical urban and semi-rural conditions at the simulation chamber Euphore. During the FIONA campaign we deployed an Atmospheric chemical Ionization Mass Spectrometer (AIMS). The AIMS has extensively been calibrated to a gas-phase HONO source and interferences with other gases (particularly water) have been tested. We show first results of our mass spectrometric measurements. For specific observation conditions, the chemical ionization mass spectrometry can be used as a fast and sensitive method for the detection of HONO in the atmosphere

Snowpack nitrate photolysis drives the summertime atmospheric nitrous acid (HONO) budget in coastal Antarctica

Measurements of atmospheric nitrous acid (HONO) amount fraction and flux density above snow were carried out using a long path absorption photometer at Halley station in coastal Antarctica between 22 January and 3 February 2022. The mean±1σ HONO amount fraction was (2.1 ± 1.5) pmol mol−1 and showed a diurnal cycle (range 1.0−3.2 pmol mol−1) with a maximum at solar noon. These HONO amount fractions are generally lower than have been observed at other Antarctic locations. The flux density of HONO from the snow, measured between 31 January and 1 February 2022, was between 0.5 and 3.4 ×1012 m−2 s−1, and showed a decrease during the night. The measured flux density is at the upper limit of the calculated HONO production rate from photolysis of nitrate present in the snow. A simple box model of HONO sources and sinks showed that the flux of HONO from the snow makes a > 10 times larger contribution to the HONO budget than its formation through the reaction of OH and NO. Ratios of these HONO amount fractions to NOx measurements made in summer 2005 are low (0.15−0.35), which we take as an indication of our measurements being comparatively free from interferences. Further calculations suggest that HONO photolysis could produce up to 12 pmol mol−1 h−1 of OH, approximately half that produced by ozone photolysis, which highlights the importance of HONO snow emissions as an OH source in the atmospheric boundary layer above Antarctic snowpacks