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Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS–MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.
Daytime formation of nitrous acid at a coastal remote site in Cyprus indicating a common ground source of atmospheric HONO and NO

Characterization of daytime sources of nitrous acid (HONO) is crucial to understand atmospheric oxidation and radical cycling in the planetary boundary layer. HONO and numerous other atmospheric trace constituents were measured on the Mediterranean island of Cyprus during the CYPHEX (CYprus PHotochemical EXperiment) campaign in summer 2014. Average volume mixing ratios of HONO were 35 pptv (±25 pptv) with a HONO ∕ NOx ratio of 0.33, which was considerably higher than reported for most other rural and urban regions. Diel profiles of HONO showed peak values in the late morning (60 ± 28 pptv around 09:00 local time) and persistently high mixing ratios during daytime (45 ± 18 pptv), indicating that the photolytic loss of HONO is compensated by a strong daytime source. Budget analyses revealed unidentified sources producing up to 3.4  ×  106 molecules cm−3 s−1 of HONO and up to 2.0  ×  107 molecules cm−3 s−1 NO. Under humid conditions (relative humidity  >  70 %), the source strengths of HONO and NO exhibited a close linear correlation (R2 = 0.72), suggesting a common source that may be attributable to emissions from microbial communities on soil surfaces.
Ozone production and its sensitivity to NOx and VOCs: results from the DISCOVER-AQ field experiment, Houston 2013

An observation-constrained box model based on the Carbon Bond mechanism, version 5 (CB05), was used to study photochemical processes along the NASA P-3B flight track and spirals over eight surface sites during the September 2013 Houston, Texas deployment of the NASA Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. Data from this campaign provided an opportunity to examine and improve our understanding of atmospheric photochemical oxidation processes related to the formation of secondary air pollutants such as ozone (O3). O3 production and its sensitivity to NOx and volatile organic compounds (VOCs) were calculated at different locations and times of day. Ozone production efficiency (OPE), defined as the ratio of the ozone production rate to the NOx oxidation rate, was calculated using the observations and the simulation results of the box and Community Multiscale Air Quality (CMAQ) models. Correlations of these results with other parameters, such as radical sources and NOx mixing ratio, were also evaluated. It was generally found that O3 production tends to be more VOC-sensitive in the morning along with high ozone production rates, suggesting that control of VOCs may be an effective way to control O3 in Houston. In the afternoon, O3 production was found to be mainly NOx-sensitive with some exceptions. O3 production near major emissions sources such as Deer Park was mostly VOC-sensitive for the entire day, other urban areas near Moody Tower and Channelview were VOC-sensitive or in the transition regime, and areas farther from downtown Houston such as Smith Point and Conroe were mostly NOx-sensitive for the entire day. It was also found that the control of NOx emissions has reduced O3 concentrations over Houston but has led to larger OPE values. The results from this work strengthen our understanding of O3 production; they indicate that controlling NOx emissions will provide air quality benefits over the greater Houston metropolitan area in the long run, but in selected areas controlling VOC emissions will also be beneficial.
Pan-Eurasian Experiment (PEEX): towards a holistic understanding of the feedbacks and interactions in the land–atmosphere–ocean–society continuum in the northern Eurasian region

The northern Eurasian regions and Arctic Ocean will very likely undergo substantial changes during the next decades. The Arctic–boreal natural environments play a crucial role in the global climate via albedo change, carbon sources and sinks as well as atmospheric aerosol production from biogenic volatile organic compounds. Furthermore, it is expected that global trade activities, demographic movement, and use of natural resources will be increasing in the Arctic regions. There is a need for a novel research approach, which not only identifies and tackles the relevant multi-disciplinary research questions, but also is able to make a holistic system analysis of the expected feedbacks. In this paper, we introduce the research agenda of the Pan-Eurasian Experiment (PEEX), a multi-scale, multi-disciplinary and international program started in 2012 (<a href="https://www.atm.helsinki.fi/peex/" target="_blank">https://www.atm.helsinki.fi/peex/</a>). PEEX sets a research approach by which large-scale research topics are investigated from a system perspective and which aims to fill the key gaps in our understanding of the feedbacks and interactions between the land–atmosphere–aquatic–society continuum in the northern Eurasian region. We introduce here the state of the art for the key topics in the PEEX research agenda and present the future prospects of the research, which we see relevant in this context.
Assessing the sensitivity of the hydroxyl radical to model biases in composition and temperature using a single-column photochemical model for Lauder, New Zealand

We assess the major factors contributing to local biases in the hydroxyl radical (OH) as simulated by a global chemistry–climate model, using a single-column photochemical model (SCM) analysis. The SCM has been constructed to represent atmospheric chemistry at Lauder, New Zealand, which is representative of the background atmosphere of the Southern Hemisphere (SH) mid-latitudes. We use long-term observations of variables essential to tropospheric OH chemistry, i.e. ozone (O3), water vapour (H2O), methane (CH4), carbon monoxide (CO), and temperature, and assess how using these measurements affect OH calculated in the SCM, relative to a reference simulation only using modelled fields. The analysis spans 1994 to 2010. Results show that OH responds approximately linearly to correcting biases in O3, H2O, CO, CH4, and temperature. The biggest impact on OH is due to correcting an overestimation by approximately 20 to 60 % of H2O, using radiosonde observations. Correcting this moist bias leads to a reduction of OH by around 5 to 35 %. This is followed by correcting predominantly overestimated O3. In the troposphere, the model biases are mostly in the range of −10 to 30 %. The impact of changing O3 on OH is due to two pathways; the OH responses to both are of similar magnitude but different seasonality: correcting in situ tropospheric ozone leads to changes in OH in the range −14 to 4 %, whereas correcting the photolysis rate of O3 in accordance with overhead column ozone changes leads to increases of OH of 8 to 16 %. The OH sensitivities to correcting CH4, CO, and temperature biases are all minor effects. The work demonstrates the feasibility of quantitatively assessing OH sensitivity to biases in longer-lived species, which can help explain differences in simulated OH between global chemistry models and relative to observations. In addition to clear-sky simulations, we have performed idealized sensitivity simulations to assess the impact of clouds (ice and liquid) on OH. The results indicate that the impacts on the ozone photolysis rate and OH are substantial, with a general decrease of OH below the clouds of up to 30 % relative to the clear-skies situation, and an increase of up to 15 % above. Using the SCM simulation we calculate recent OH trends at Lauder. For the period of 1994 to 2010, all trends are insignificant, in agreement with previous studies. For example, the trend in total-column OH is 0.5 ± 1.3 % over this period.
Direct inversion of circulation and mixing from tracer measurements – Part 1: Method

From a series of zonal mean global stratospheric tracer measurements sampled in altitude vs. latitude, circulation and mixing patterns are inferred by the inverse solution of the continuity equation. As a first step, the continuity equation is written as a tendency equation, which is numerically integrated over time to predict a later atmospheric state, i.e., mixing ratio and air density. The integration is formally performed by the multiplication of the initially measured atmospheric state vector by a linear prediction operator. Further, the derivative of the predicted atmospheric state with respect to the wind vector components and mixing coefficients is used to find the most likely wind vector components and mixing coefficients which minimize the residual between the predicted atmospheric state and the later measurement of the atmospheric state. Unless multiple tracers are used, this inversion problem is under-determined, and dispersive behavior of the prediction further destabilizes the inversion. Both these problems are addressed by regularization. For this purpose, a first-order smoothness constraint has been chosen. The usefulness of this method is demonstrated by application to various tracer measurements recorded with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). This method aims at a diagnosis of the Brewer–Dobson circulation without involving the concept of the mean age of stratospheric air, and related problems like the stratospheric tape recorder, or intrusions of mesospheric air into the stratosphere.
A Monte Carlo approach for determining cluster evaporation rates from concentration measurements

Evaporation rates of small negatively charged sulfuric acid–ammonia clusters are determined by combining detailed cluster formation simulations with cluster distributions measured in the CLOUD experiment at CERN. The analysis is performed by varying the evaporation rates with Markov chain Monte Carlo (MCMC), running cluster formation simulations with each new set of evaporation rates and comparing the obtained cluster distributions to the measurements. In a second set of simulations, the fragmentation of clusters in the mass spectrometer due to energetic collisions is studied by treating also the fragmentation probabilities as unknown parameters and varying them with MCMC. This second set of simulations results in a better fit to the experimental data, suggesting that a large fraction of the observed HSO4− and HSO4− ⋅ H2SO4 signals may result from fragmentation of larger clusters, most importantly the HSO4− ⋅ (H2SO4)2 trimer.
Inventory of anthropogenic methane emissions in mainland China from 1980 to 2010

Methane (CH4) has a 28-fold greater global warming potential than CO2 over 100 years. Atmospheric CH4 concentration has tripled since 1750. Anthropogenic CH4 emissions from China have been growing rapidly in the past decades and contribute more than 10 % of global anthropogenic CH4 emissions with large uncertainties in existing global inventories, generally limited to country-scale statistics. To date, a long-term CH4 emission inventory including the major sources sectors and based on province-level emission factors is still lacking. In this study, we produced a detailed annual bottom-up inventory of anthropogenic CH4 emissions from the eight major source sectors in China for the period 1980–2010. In the past 3 decades, the total CH4 emissions increased from 24.4 [18.6–30.5] Tg CH4 yr−1 in 1980 (mean [minimum–maximum of 95 % confidence interval]) to 44.9 [36.6–56.4] Tg CH4 yr−1 in 2010. Most of this increase took place in the 2000s decade with averaged yearly emissions of 38.5 [30.6–48.3] Tg CH4 yr−1. This fast increase of the total CH4 emissions after 2000 is mainly driven by CH4 emissions from coal exploitation. The largest contribution to total CH4 emissions also shifted from rice cultivation in 1980 to coal exploitation in 2010. The total emissions inferred in this work compare well with the EPA inventory but appear to be 36 and 18 % lower than the EDGAR4.2 inventory and the estimates using the same method but IPCC default emission factors, respectively. The uncertainty of our inventory is investigated using emission factors collected from state-of-the-art published literatures. We also distributed province-scale emissions into 0.1°  ×  0.1° maps using socioeconomic activity data. This new inventory could help understanding CH4 budgets at regional scale and guiding CH4 mitigation policies in China.
Detection of atmospheric gaseous amines and amides by a high-resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6) and amides (C1 to C6). This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of ∼  0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb) were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.
Implications on atmospheric dynamics and the effect on black carbon transport into the Eurasian Arctic based on the choice of land surface model schemes and reanalysis data in model simulations with WRF

A realistic simulation of physical and dynamical processes in the Arctic atmosphere and its feedbacks with the surface conditions is still a challenge for state-of-the-art Arctic climate models. This is of critical importance because studies of, for example, transport of pollutants from middle latitudes into the Arctic rely on the skill of the model in correctly representing atmospheric circulation including the key mechanisms and pathways of pollutant transport. In this work the performance of the Weather Research and Forecast model (WRF) with two land surface model schemes (Noah and NoahMP) and two reanalysis data sets for creation of lateral boundary conditions (ERA-interim and ASR) is evaluated focusing on meteorological surface properties and atmospheric dynamics. This includes the position and displacement of the polar dome and other features characterizing atmospheric circulation associated to sea ice maxima/minima extent within the Eurasian Arctic. The model simulations analyzed are carried out at 15-km horizontal resolution over a period of five years (2008 to 2012). The WRF model simulations are evaluated against surface meteorological data from automated weather stations and vertical profiles from radiosondes. Results show that the model is able to reproduce the main features of the atmospheric dynamics and vertical structure of the Arctic atmosphere reasonably well. The influence of the choice of the reanalyses used as initial and lateral boundary condition and of the LSM on the model results is complex and no combination is found to be clearly superior in all variables analyzed. The model results show that a more sophisticated formulation of land surface processes does not necessarily lead to significant improvements in the model results. This suggests that other factors such as the decline of the Arctic sea ice, stratosphere-troposphere interactions, atmosphere-ocean interaction, and boundary layer processes are also highly important and can have a significant influence on the model results. The “best” configuration for simulating Arctic meteorology and processes most relevant for pollutant transport (ASR + NoahMP) is then used in a simulation with WRF including aerosols and chemistry (WRF-Chem) to simulate black carbon (BC) concentrations in and around the Arctic and to assess the role of the modeled atmospheric circulation in the simulated BC concentrations inside the Arctic domain. Results from simulations with chemistry are evaluated against aerosol optical depth from several Aeronet stations and BC concentrations and particle number concentrations from several stations from the EBAS database. The results with WRF-Chem show a strong dependency of the simulated BC concentration on the modeled meteorology and the transport of the pollutants around our domain. The results also show that biases in the modeled BC concentrations can also be related to the emission data. Significant improvements of the models and of our understanding of the impact of anthropogenic BC emissions on the Arctic strongly depends on the availability of suitable, long-term observational data of concentrations of BC and particulate matter, vertical profiles of temperature and humidity and wind.