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Laboratory evidence of organic peroxide and peroxyhemiacetal formation in the aqueous phase and implications for aqueous OH

Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is considered a potentially important atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2–C3) are precursors for SOAaq; products include organic acids, organic sulfates, and high-molecular-weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra-high-resolution Fourier transform ion cyclotron resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals and epoxides (i.e., IEPOX), and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.
Impact of particle shape on the morphology of noctilucent clouds

Noctilucent clouds (NLCs) occur during summer in the polar region at altitudes around 83 km. They consist of ice particles with a typical size around 50 nm. The shape of NLC particles is less well known but is important both for interpreting optical measurements and modeling ice cloud characteristics. In this paper, NLC modeling of microphysics and optics is adapted to use cylindrical instead of spherical particle shape. The optical properties of the resulting ice clouds are compared directly to NLC three-color measurements by the Arctic Lidar Observatory for Middle Atmosphere Research (ALOMAR) Rayleigh/Mie/Raman (RMR) lidar between 1998 and 2014. Shape distributions including both needle- and disc-shaped particles are consistent with lidar measurements. The best agreement occurs if disc shapes are 60 % more common than needles, with a mean axis ratio of 2.8. Cylindrical particles cause stronger ice clouds on average than spherical shapes with an increase of backscatter at 532 nm by ≈ 30 % and about 20 % in ice mass density. This difference is less pronounced for bright than for weak ice clouds. Cylindrical shapes also cause NLCs to have larger but a smaller number of ice particles than for spherical shapes.
Characteristics and sources of submicron aerosols above the urban canopy (260 m) in Beijing, China, during the 2014 APEC summit

The megacity of Beijing has experienced frequent severe fine particle pollution during the last decade. Although the sources and formation mechanisms of aerosol particles have been extensively investigated on the basis of ground measurements, real-time characterization of aerosol particle composition and sources above the urban canopy in Beijing is rare. In this study, we conducted real-time measurements of non-refractory submicron aerosol (NR-PM1) composition at 260 m at the Beijing 325 m meteorological tower (BMT) from 10 October to 12 November 2014, by using an aerosol chemical speciation monitor (ACSM) along with synchronous measurements of size-resolved NR-PM1 composition near ground level using a high-resolution time-of-flight aerosol mass spectrometer (HR–ToF–AMS). The NR-PM1 composition above the urban canopy was dominated by organics (46 %), followed by nitrate (27 %) and sulfate (13 %). The high contribution of nitrate and high NO3− / SO42− mass ratios illustrates an important role of nitrate in particulate matter (PM) pollution during the study period. The organic aerosol (OA) was mainly composed of secondary OA (SOA), accounting for 61 % on an average. Different from that measured at the ground site, primary OA (POA) correlated moderately with SOA, likely suggesting a high contribution from regional transport above the urban canopy. The Asia–Pacific Economic Cooperation (APEC) summit with strict emission controls provides a unique opportunity to study the impacts of emission controls on aerosol chemistry. All aerosol species were shown to have significant decreases of 40–80 % during APEC from those measured before APEC, suggesting that emission controls over regional scales substantially reduced PM levels. However, the bulk aerosol composition was relatively similar before and during APEC as a result of synergetic controls of aerosol precursors. In addition to emission controls, the routine circulations of mountain–valley breezes were also found to play an important role in alleviating PM levels and achieving the "APEC blue" effect. The evolution of vertical differences between 260 m and the ground level was also investigated. Our results show complex vertical differences during the formation and evolution of severe haze episodes that are closely related to aerosol sources and boundary-layer dynamics.
Feedbacks of dust and boundary layer meteorology during a dust storm in the eastern Mediterranean

Aerosols affect the atmosphere through direct interaction with short-wave and long-wave radiation and the microphysical properties of clouds. In this paper we report in detail on several mechanisms by which the short-term impact of dust on surface radiative fluxes can affect the dust loading of the atmosphere via modification of boundary-layer meteorology. This in turn affects the aerosol radiative forcing itself. Examples of these feedbacks between dust and boundary layer meteorology were observed during a series of dust storms in the Sahara and the eastern Mediterranean in April 2012. These case studies have been analysed using the Monitoring Atmospheric Composition and Climate – Interim Implementation (MACC-II) system. The radiative fluxes in the short-wave and long-wave spectra were both significantly affected by the prognostic aerosol–radiation interaction, which in turn impacted the meteorological simulation. Reduced incoming solar radiation below the aerosol layers led to a decrease in maximum surface temperatures and to a more stable thermal stratification of the lower atmosphere. This in turn forced weaker surface wind speeds and eventually smaller dust emissions. Moreover, we also observed a secondary impact of the aerosol radiative forcing, whereby horizontal gradients of surface temperature were increased at the edge of the dust plume, which led to local increases of surface wind speeds due to the thermal wind effect. The differentiated impact of the aerosol layer on surface pressure also contributed to the increase in surface wind speed and dust production in the same area. Enhanced long-wave radiative fluxes by the dust mass were associated with opposite processes. Less stable thermal stratification at night, brought mainly by higher minimum temperatures at the surface, caused stronger surface winds. At the edge of the dust storm, weaker horizontal temperature and pressure gradients forced lower winds and reduced dust production. Regarding dust emissions, short-wave radiative forcing had a larger impact than long-wave radiative forcing, corroborating several previous studies. For surface temperature, short-wave and long-wave contribution were close in intensity. These feedbacks were amplified when using data assimilation to build the aerosol analysis of the MACC-II global system. This led to an improvement in the short-term forecasts of thermal radiative fluxes and surface temperatures.
Changes in chemical components of aerosol particles in different haze regions in China from 2006 to 2013 and contribution of meteorological factors

Since there have been individual reports of persistent haze–fog events in January 2013 in central-eastern China, questions on factors causing the drastic differences in changes in 2013 from changes in adjacent years have been raised. Changes in major chemical components of aerosol particles over the years also remain unclear. The extent of meteorological factors contributing to such changes is yet to be determined. The study intends to present the changes in daily based major water-soluble constituents, carbonaceous species, and mineral aerosol in PM10 at 13 stations within different haze regions in China from 2006 to 2013, which are associated with specific meteorological conditions that are highly related to aerosol pollution (parameterized as an index called Parameter Linking Aerosol Pollution and Meteorological Elements – PLAM). No obvious changes were found in annual mean concentrations of these various chemical components and PM10 in 2013, relative to 2012. By contrast, wintertime mass of these components was quite different. In Hua Bei Plain (HBP), sulfate, organic carbon (OC), nitrate, ammonium, element carbon (EC), and mineral dust concentrations in winter were approximately 43, 55, 28, 23, 21, and 130 μg m−3, respectively; these masses were approximately 2 to 4 times higher than those in background mass, which also exhibited a decline during 2006 to 2010 and then a rise till 2013. The mass of these concentrations and PM10, except minerals, respectively, increased by approximately 28 to 117 % and 25 % in January 2013 compared with that in January 2012. Thus, persistent haze–fog events occurred in January 2013, and approximately 60 % of this increase in component concentrations from 2012 to 2013 can be attributed to severe meteorological conditions in the winter of 2013. In the Yangtze River Delta (YRD) area, winter masses of these components, unlike HBP, have not significantly increase since 2010; PLAM were also maintained at a similar level without significant changes. In the Pearl River Delta (PRD) area, the regional background concentrations of the major chemical components were similar to those in the YRD, accounting for approximately 60–80 % of those in HBP. Since 2010, a decline has been found for winter concentrations, which can be partially attributable to persistently improving meteorological conditions and emission cutting with an emphasis on coal combustion in this area. In addition to the scattered and centralized coal combustion for heating, burning biomass fuels contributed to the large increase in concentrations of carbonaceous aerosol in major haze regions in winter, except in the PRD. No obvious changes were found for the proportions of each chemical components of PM10 from 2006 to 2013. Among all of the emissions recorded in chemical compositions in 2013, coal combustion was still the largest anthropogenic source of aerosol pollution in various areas in China, with a higher sulfate proportion of PM10 in most areas of China, and OC was normally ranked third. PM10 concentrations increased by approximately 25 % in January of 2013 relative to 2012, which caused persistent haze–fog events in HBP; emissions also reduced by approximately 35 % in Beijing and its vicinity (BIV) in late autumn of 2014, thereby producing the Asia Pacific Economic Cooperation (APEC) blue (extremely good air quality); thus, one can expect that the persistent haze–fog events would be reduced significantly in the BIV, if approx. one-third of the 2013 winter emissions were reduced, which can also be viewed as the upper limit of atmospheric aerosol pollution capacity in this area.
The origins of ice crystals measured in mixed-phase clouds at the high-alpine site Jungfraujoch

During the winter of 2013 and 2014 measurements of cloud microphysical properties over a 5-week period at the high-alpine site Jungfraujoch, Switzerland, were carried out as part of the Cloud Aerosol Characterisation Experiments (CLACE) and the Ice Nucleation Process Investigation and Quantification project (INUPIAQ). Measurements of aerosol properties at a second, lower site, Schilthorn, Switzerland, were used as input for a primary ice nucleation scheme to predict ice nuclei concentrations at Jungfraujoch. Frequent, rapid transitions in the ice and liquid properties of the clouds at Jungfraujoch were identified that led to large fluctuations in ice mass fractions over temporal scales of seconds to hours. During the measurement period we observed high concentrations of ice particles that exceeded 1000 L−1 at temperatures around −15 °C, verified by multiple instruments. These concentrations could not be explained using the usual primary ice nucleation schemes, which predicted ice nucleus concentrations several orders of magnitude smaller than the peak ice crystal number concentrations. Secondary ice production through the Hallett–Mossop process as a possible explanation was ruled out, as the cloud was rarely within the active temperature range for this process. It is shown that other mechanisms of secondary ice particle production cannot explain the highest ice particle concentrations. We describe four possible mechanisms that could lead to high cloud ice concentrations generated from the snow-covered surfaces surrounding the measurement site. Of these we show that hoar frost crystals generated at the cloud enveloped snow surface could be the most important source of cloud ice concentrations. Blowing snow was also observed to make significant contributions at higher wind speeds when ice crystal concentrations were < 100 L−1.
North Atlantic Oscillation model projections and influence on tracer transport

The North Atlantic Oscillation (NAO) plays an important role in the climate variability of the Northern Hemisphere with significant consequences on pollutant transport. We study the influence of the NAO on the atmospheric dispersion of pollutants in the near past and in the future by considering simulations performed by the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model. We analyze two model runs: a simulation with circulation dynamics nudged towards ERA-Interim reanalysis data over a period of 35 years (1979–2013) and a simulation with prescribed Sea Surface Temperature (SST) boundary conditions over 150 years (1950–2099). The model is shown to reproduce the NAO spatial and temporal variability and to be comparable with observations. We find that the decadal variability in the NAO, which has been pronounced since 1950s until 1990, will continue to dominate in the future considering decadal periods, although no significant trends are present in the long term projection (100–150 years horizon). We do not find in the model projections any significant temporal trend of the NAO for the future, meaning that neither positive or negative phases will dominate. Tracers with idealised decay and emissions are considered to investigate the NAO effects on transport; it is shown that during the positive phase of the NAO, the transport from North America towards northern Europe is stronger and pollutants are shifted northwards over the Arctic and southwards over the Mediterranean and North Africa, with two distinct areas of removal and stagnation of pollutants.
Isotopic signatures of production and uptake of H2 by soil

Molecular hydrogen (H2) is the second most abundant reduced trace gas (after methane) in the atmosphere, but its biogeochemical cycle is not well understood. Our study focuses on the soil production and uptake of H2 and the associated isotope effects. Air samples from a grass field and a forest site in the Netherlands were collected using soil chambers. The results show that uptake and emission of H2 occurred simultaneously at all sampling sites, with strongest emission at the grassland sites where clover (N2 fixing legume) was present. The H2 mole fraction and deuterium content were measured in the laboratory to determine the isotopic fractionation factor during H2 soil uptake (αsoil) and the isotopic signature of H2 that is simultaneously emitted from the soil (δDsoil). By considering all net-uptake experiments, an overall fractionation factor for deposition of αsoil = kHD / kHH = 0.945 ± 0.004 (95 % CI) was obtained. The difference in mean αsoil between the forest soil 0.937 ± 0.008 and the grassland 0.951 ± 0.026 is not statistically significant. For two experiments, the removal of soil cover increased the deposition velocity (vd) and αsoil simultaneously, but a general positive correlation between vd and αsoil was not found in this study. When the data are evaluated with a model of simultaneous production and uptake, the isotopic composition of H2 that is emitted at the grassland site is calculated as δDsoil = (−530 ± 40) &permil;. This is less deuterium depleted than what is expected from isotope equilibrium between H2O and H2.
Instantaneous longwave radiative impact of ozone: an application on IASI/MetOp observations

Ozone is an important greenhouse gas in terms of anthropogenic radiative forcing (RF). RF calculations for ozone were until recently entirely model based, and significant discrepancies were reported due to different model characteristics. However, new instantaneous radiative kernels (IRKs) calculated from hyperspectral thermal IR satellites have been able to help adjudicate between different climate model RF calculations. IRKs are defined as the sensitivity of the outgoing longwave radiation (OLR) flux with respect to the ozone vertical distribution in the full 9.6 μm band. Previous methods applied to measurements from the Tropospheric Emission Spectrometer (TES) on Aura rely on an anisotropy approximation for the angular integration. In this paper, we present a more accurate but more computationally expensive method to calculate these kernels. The method of direct integration is based on similar principles to the anisotropy approximation, but it deals more precisely with the integration of the Jacobians. We describe both methods and highlight their differences with respect to the IRKs and the ozone longwave radiative effect (LWRE), i.e., the radiative impact in OLR due to absorption by ozone, for both tropospheric and total columns, from measurements of the Infrared Atmospheric Sounding Interferometer (IASI) onboard MetOp-A. Biases between the two methods vary from −25 to +20 % for the LWRE, depending on the viewing angle. These biases point to the inadequacy of the anisotropy method, especially at nadir, suggesting that the TES-derived LWREs are biased low by around 25 % and that chemistry–climate model OLR biases with respect to TES are underestimated. In this paper we also exploit the sampling performance of IASI to obtain first daily global distributions of the LWRE, for 12 days (the 15th of each month) in 2011, calculated with the direct integration method. We show that the temporal variation of global and latitudinal averages of the LWRE shows patterns which are controlled by changes in the surface temperature and ozone variation due to specific processes, such as the ozone hole in the polar regions and stratospheric intrusions into the troposphere.
Black carbon aerosol in winter northeastern Qinghai–Tibetan Plateau, China: the source, mixing state and optical property

Black carbon (BC) aerosol at high altitudes of the Qinghai–Tibetan Plateau has potential effects on the regional climate and hydrological cycle. An intensive measurement campaign was conducted at Qinghai Lake (~ 3200 m above sea level) at the edge of the northeastern Qinghai–Tibetan Plateau during winter using a ground-based single particle soot photometer (SP2) and a photoacoustic extinctiometer (PAX). The average concentration of refractory BC (rBC) and number fraction of coated rBC were found to be 160 ± 190 ng m−3 and 59 % for the entire campaign, respectively. Significant enhancements of rBC loadings and number fraction of coated rBC were observed during a pollution episode, with an average value of 390 ng m−3 and 65 %, respectively. The mass size distribution of rBC particles showed log-normal distribution, with a peak diameter of ~ 187 nm regardless of the pollution level. Five-day backward trajectory analysis suggests that the air masses from north India contributed to the increased rBC loadings during the campaign. The potential source contribution function (PSCF) model combined with the fire counts map further proves that biomass burning from north India is an important potential source influencing the northeastern Qinghai–Tibetan Plateau during the pollution episode. The rBC mass absorption cross section (MACrBC) at λ = 532 nm was slightly larger in clean days (14.9 m2 g−1) than during the pollution episode (9.3 m2 g−1), likely due to the effects of brown carbon and the uncertainty of the MACrBC calculation. The MACrBC was positively correlated with number fraction of coated rBC during the pollution episode with an increasing rate of 0.18 (m2 g−1) %−1. The number fraction of coated rBC particles showed positive correlation with light absorption, suggesting that the increase of coated rBC particles will enhance the light absorption. Compared to rBC mass concentration, rBC mixing sate is more important in determining absorption during the pollution episode, estimated from the same percentage-wise increment of either rBC mass concentration or the number fraction of coated rBC. The estimated BC direct radiative forcing was +0.93 W m−2 for the pollution episode, which is 2 times larger than that in clean days. Our study provides insight into the potential climatic impacts of rBC aerosol transported to the Qinghai–Tibetan Plateau from south Asian regions, and is also useful for future modeling studies.