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Evidence for an unidentified non-photochemical ground-level source of formaldehyde in the Po Valley with potential implications for ozone production

Ozone concentrations in the Po Valley of northern Italy often exceed international regulations. As both a source of radicals and an intermediate in the oxidation of most volatile organic compounds (VOCs), formaldehyde (HCHO) is a useful tracer for the oxidative processing of hydrocarbons that leads to ozone production. We investigate the sources of HCHO in the Po Valley using vertical profile measurements acquired from the airship Zeppelin NT over an agricultural region during the PEGASOS 2012 campaign. Using a 1-D model, the total VOC oxidation rate is examined and discussed in the context of formaldehyde and ozone production in the early morning. While model and measurement discrepancies in OH reactivity are small (on average 3.4 ± 13%), HCHO concentrations are underestimated by as much as 1.5 ppb (45%) in the convective mixed layer. A similar underestimate in HCHO was seen in the 2002–2003 FORMAT Po Valley measurements, though the additional source of HCHO was not identified. Oxidation of unmeasured VOC precursors cannot explain the missing HCHO source, as measured OH reactivity is explained by measured VOCs and their calculated oxidation products. We conclude that local direct emissions from agricultural land are the most likely source of missing HCHO. Model calculations demonstrate that radicals from degradation of this non-photochemical HCHO source increase model ozone production rates by as much as 0.6 ppb h−1 (12%) before noon.
WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7–0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg−1air, compared with measurements of 1.0–1.5 μg kg−1air). Two flights from the campaign were used as test cases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and comparable for dimethylsulfide (DMS). However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the night-time minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles and will negatively impact on regional air quality, requiring this process to be included in regional models.
Size-resolved observations of refractory black carbon particles in cloud droplets at a marine boundary layer site

Size-resolved observations of aerosol particles and cloud droplet residuals were studied at a marine boundary layer site (251 m a.m.s.l.) in La Jolla, San Diego, California, during 2012. A counterflow virtual impactor (CVI) was used as the inlet to sample cloud residuals while a total inlet was used to sample both cloud residuals and interstitial particles. Two cloud events totaling 10 h of in-cloud sampling were analyzed. Based on bulk aerosol particle concentrations, mass concentrations of refractory black carbon (rBC), and back trajectories, the two air masses sampled were classified as polluted marine air. Since the fraction of cloud droplets sampled by the CVI was less than 100%, the measured activated fractions of rBC should be considered as lower limits to the total fraction of rBC activated during the two cloud events. Size distributions of rBC and a coating analysis showed that sub-100 nm rBC cores with relatively thick coatings were incorporated into the cloud droplets (i.e., 95 nm rBC cores with median coating thicknesses of at least 65 nm were incorporated into the cloud droplets). Measurements also show that the coating volume fraction of rBC cores is relatively large for sub-100 nm rBC cores. For example, the median coating volume fraction of 95 nm rBC cores incorporated into cloud droplets was at least 0.9, a result that is consistent with κ-Köhler theory. Measurements of the total diameter of the rBC-containing particles (rBC core and coating) suggest that the total diameter of rBC-containing particles needed to be at least 165 nm to be incorporated into cloud droplets when the core rBC diameter is ≥ 85 nm. This result is consistent with previous work that has shown that particle diameter is important for activation of non-rBC particles. The activated fractions of rBC determined from the measurements ranged from 0.01 to 0.1 for core rBC diameters ranging from 70 to 220 nm. This type of data is useful for constraining models used for predicting rBC concentrations in the atmosphere.
Effects of molecular weight and temperature on liquid–liquid phase separation in particles containing organic species and inorganic salts

Atmospheric particles containing organic species and inorganic salts may undergo liquid–liquid phase separation when the relative humidity varies between high and low values. To better understand the parameters that affect liquid–liquid phase separation in atmospheric particles, we studied the effects of molecular weight and temperature on liquid–liquid phase separation in particles containing one organic species mixed with either ammonium sulfate or ammonium bisulfate. In the molecular-weight-dependent studies, we measured liquid–liquid phase separation relative humidity (SRH) in particles containing ammonium sulfate and organic species with large molecular weights (up to 1153 Da). These results were combined with recent studies of liquid–liquid phase separation in the literature to assess if molecular weight is a useful parameter for predicting SRH. The combined results, which include results from 33 different particle types, illustrate that SRH does not depend strongly on molecular weight (i.e., a clear relationship between molecular weight and SRH was not observed). In the temperature-dependent studies, we measured liquid–liquid phase separation in particles containing ammonium sulfate mixed with 20 different organic species at 244 ± 1 K, 263 ± 1 K, and 278 ± 1 K; a few particles were also studied at 290 ± 1 K. These new results were combined with previous measurements of the same particle types at 290 ± 1 K. The combined SRH data illustrate that for the organic–ammonium sulfate particles studied, the SRH does not depend strongly on temperature. At most the SRH varied by 9.7% as the temperature varied from 290 to 244 K. The high SRH values (> 65%) in these experiments may explain the lack of temperature dependence. Since water is a plasticizer, high relative humidities can lead to high water contents, low viscosities, and high diffusion rates in the particles. For these cases, unless the temperature is very low, liquid–liquid phase separation is not expected to be kinetically inhibited. The occurrence of liquid–liquid phase separation and SRH did depend strongly on temperature over the range of 290–244 K for particles containing α,4-dihydroxy-3-methoxybenzeneacetic acid mixed with ammonium bisulfate. For this particle type, a combination of low temperatures and low water content likely favored kinetic inhabitation of the liquid–liquid phase separation by slow diffusion rates in highly viscous particles. The combined results suggest that liquid–liquid phase separation is likely a common occurrence in atmospheric particles at temperatures from 244–290 K, although particles that do not undergo liquid–liquid phase separation are also likely common.
Ultraviolet and visible complex refractive indices of secondary organic material produced by photooxidation of the aromatic compounds toluene and m-xylene

Secondary organic material (SOM) produced by the oxidation of anthropogenic volatile organic compounds can be light-absorbing (i.e., brown carbon). Spectral data of the optical properties, however, are scarce. The present study obtained the continuous spectra of the real and imaginary refractive indices (m = n-i k) in the ultraviolet (UV)-to-visible region using spectroscopic ellipsometry for n and UV–visible spectrometry for k. Several different types of SOM were produced in an oxidation flow reactor by photooxidation of toluene and m-xylene for variable concentrations of nitrogen oxides (NOx). The results show that the k values of the anthropogenically derived material were at least 10 times greater than those of the biogenically derived material. The presence of NOx was associated with the production of organonitrogen compounds, such as nitro-aromatics and organonitrates, which enhanced light absorption. Compared with the SOM derived from m-xylene, the toluene-derived SOM had larger k values, as well as a greater NOx-induced enhancement, suggesting different brown-carbon-forming potentials of different aromatic precursor compounds. The results imply that anthropogenic SOM produced around urban environments can have an important influence on ultraviolet irradiance, which might consequently influence photochemical cycles of urban pollution.
Evaluation of black carbon emission inventories using a Lagrangian dispersion model – a case study over southern India

We evaluated three emission inventories of black carbon (BC) using Lagrangian particle dispersion model simulations and BC observations from a rural site in southern India (Gadanki; 13.48° N, 79.18° E) from 2008 to 2012. We found that 93 to 95% of the BC load at the observation site originated from emissions in India and the rest from the neighbouring countries and shipping. A substantial fraction (33 to 43%) of the BC was transported from northern India. Wet deposition is found to play a minor role in reducing BC mass at the site because of its proximity to BC sources during rainy season and relatively short rainy season over western and northern parts of India. Seasonally, the highest BC concentration (approx. 3.3 μg m−3) is observed during winter, followed by spring (approx. 2.8 μg m−3). While the model reproduced well the seasonal cycle, the modelled BC concentrations are significantly lower than observed values, especially in spring. The model bias is correlated to fire radiative power – a proxy of open biomass burning activity. Using potential emission sensitivity maps derived using the model, we suggest that underestimation of BC mass in the model during spring is due to the underestimation of BC fluxes over southern India (possibly from open-biomass-burning/forest-fires). The overall performance of the model simulations using three different emission inventories (SAFAR-India, ECLIPSE and RETRO) is similar, with ECLIPSE and SAFAR-India performing marginally better as both have about 30% higher emissions for India than RETRO. The ratio of observed to modelled annual mean BC concentration was estimated as 1.5 for SAFAR, 1.7 for ECLIPSE and 2.4 for RETRO.
Intercomparing different devices for the investigation of ice nucleating particles using Snomax® as test substance

Seven different instruments and measurement methods were used to examine the immersion freezing of bacterial ice nuclei from Snomax® (hereafter Snomax), a product containing ice-active protein complexes from non-viable Pseudomonas syringae bacteria. The experimental conditions were kept as similar as possible for the different measurements. Of the participating instruments, some examined droplets which had been made from suspensions directly, and the others examined droplets activated on previously generated Snomax particles, with particle diameters of mostly a few hundred nanometers and up to a few micrometers in some cases. Data were obtained in the temperature range from −2 to −38 °C, and it was found that all ice-active protein complexes were already activated above −12 °C. Droplets with different Snomax mass concentrations covering 10 orders of magnitude were examined. Some instruments had very short ice nucleation times down to below 1 s, while others had comparably slow cooling rates around 1 K min−1. Displaying data from the different instruments in terms of numbers of ice-active protein complexes per dry mass of Snomax, nm, showed that within their uncertainty, the data agree well with each other as well as to previously reported literature results. Two parameterizations were taken from literature for a direct comparison to our results, and these were a time-dependent approach based on a contact angle distribution (Niedermeier et al., 2014) and a modification of the parameterization presented in Hartmann et al. (2013) representing a time-independent approach. The agreement between these and the measured data were good; i.e., they agreed within a temperature range of 0.6 K or equivalently a range in nm of a factor of 2. From the results presented herein, we propose that Snomax, at least when carefully shared and prepared, is a suitable material to test and compare different instruments for their accuracy of measuring immersion freezing.
Sensitivity of top-down CO source estimates to the modeled vertical structure in atmospheric CO

We assessed the sensitivity of regional CO source estimates to the modeled vertical CO distribution by assimilating multi-spectral MOPITT (Measurements of Pollution In The Troposphere) V5J CO retrievals with the GEOS-Chem model. We compared the source estimates obtained by assimilating the CO profiles and the surface layer retrievals from June 2004 to May 2005. Because the surface layer retrievals are less sensitive to CO in the free troposphere, it is expected that they should provide constraints in the CO source estimates that are less sensitive to the vertical structure of CO in the free troposphere. The inferred source estimates all suggest a reduction in CO emissions in the tropics and subtropics, and an increase in the extratropics over the a priori estimates. The tropical decreases were particularly pronounced for regions where the biogenic source of CO was dominant, suggesting an overestimate of the a priori isoprene source of CO in the model. We found that the differences between the regional source estimates inferred from the profile and surface layer retrievals for 2004–2005 were small, generally less than 10% for the main continental regions, except for estimates for southern Asia, North America, and Europe. Because of discrepancies in convective transport in the model, the CO source estimates for India and southeastern Asia inferred from the CO profiles were significantly higher than those estimated from the surface layer retrievals during June–August 2004. On the other hand, the profile inversion underestimated the CO emissions from North America and Europe compared to the assimilation of the surface layer retrievals. We showed that vertical transport of air from the North American and European boundary layers is slower than from other continental regions, and thus air in the free troposphere from North America and Europe in the model is more chemically aged, which could explain the discrepancy between the source estimates inferred from the profile and surface layer retrievals. We also examined the impact of the OH distribution on the source estimates and found that the discrepancies between the source estimates obtained with two OH fields were larger when using the profile data, which is consistent with greater sensitivity to the more chemically aged air in the free troposphere. Our findings indicate that regional CO source estimates are sensitive to the vertical CO structure. They suggest that diagnostics to assess the age of air from the continental source regions should help interpret the results from CO source inversions. Our results also suggest that assimilating a broader range of composition measurements to provide better constraint on tropospheric OH and the biogenic sources of CO is essential for reliable quantification of the regional CO budget.
Trends of non-methane hydrocarbons (NMHC) emissions in Beijing during 2002–2013

Non-methane hydrocarbons (NMHCs) play a critical role in the photochemical production of ozone (O3) and organic aerosols. Obtaining an accurate understanding on temporal trends of NMHC emissions is essential for predicting air quality changes and evaluating the effectiveness of current control measures. In this study, we evaluated temporal trends of anthropogenic NMHC emissions during August in Beijing based on ambient measurements during selected summer periods at an urban site in Beijing from 2002 to 2013. In the contrast to the results from the most recent inventory (Multi-resolution Emission Inventory for China, MEIC), which reported that anthropogenic NMHC emissions during August increased by 28% from 2004 to 2012, whereas mixing ratios of NMHCs measured at this urban site decreased by 37% during the same time period. A positive matrix factorization (PMF) model was applied to these NMHC measurements for source apportionment. The results showed that the relative contributions of vehicular exhaust and gasoline evaporation to measured NMHC concentrations decreased by 66% during August from 2004 to 2012, comparable to the relative decline of 67% for transportation-related NMHC emissions reported by the MEIC inventory. This finding indicates that the implementation of stricter emissions standards for new vehicles and specific control measures for in-use vehicles has been effective for reducing transportation-related NMHC emissions. In addition, the PMF results suggested that there were no significant temporal changes in NMHC concentrations from solvent use and industry during August from 2004 to 2012, in contrast with the rapid rate of increase (8.8% yr−1) reported by the MEIC inventory. To re-evaluate the NMHC emissions trends for solvent use and industry, annual variations in NMHC / NOx ratios were compared between ambient measurements at the PKU site and the MEIC inventory. In contrast to the significant rise in NMHC / NOx ratios from the MEIC inventory, the measured NMHC / NOx ratios declined by 14% during August from 2005 to 2012. The inferred NMHC / NOx ratios based on PMF results exhibited a comparable decline of 11% to measured ratios. These results indicate that the increase rate for NMHC emissions from solvent use and industry in Beijing might be overestimated in the current inventory; therefore, additional research is necessary to verify the NMHC emission trends for this source.
Effects of pre-existing ice crystals on cirrus clouds and comparison between different ice nucleation parameterizations with the Community Atmosphere Model (CAM5)

In order to improve the treatment of ice nucleation in a more realistic manner in the Community Atmosphere Model version 5.3 (CAM5.3), the effects of pre-existing ice crystals on ice nucleation in cirrus clouds are considered. In addition, by considering the in-cloud variability in ice saturation ratio, homogeneous nucleation takes place spatially only in a portion of the cirrus cloud rather than in the whole area of the cirrus cloud. Compared to observations, the ice number concentrations and the probability distributions of ice number concentration are both improved with the updated treatment. The pre-existing ice crystals significantly reduce ice number concentrations in cirrus clouds, especially at mid- to high latitudes in the upper troposphere (by a factor of ~10). Furthermore, the contribution of heterogeneous ice nucleation to cirrus ice crystal number increases considerably. Besides the default ice nucleation parameterization of Liu and Penner (2005, hereafter LP) in CAM5.3, two other ice nucleation parameterizations of Barahona and Nenes (2009, hereafter BN) and Kärcher et al. (2006, hereafter KL) are implemented in CAM5.3 for the comparison. In-cloud ice crystal number concentration, percentage contribution from heterogeneous ice nucleation to total ice crystal number, and pre-existing ice effects simulated by the three ice nucleation parameterizations have similar patterns in the simulations with present-day aerosol emissions. However, the change (present-day minus pre-industrial times) in global annual mean column ice number concentration from the KL parameterization (3.24 × 106 m−2) is less than that from the LP (8.46 × 106 m−2) and BN (5.62 × 106 m−2) parameterizations. As a result, the experiment using the KL parameterization predicts a much smaller anthropogenic aerosol long-wave indirect forcing (0.24 W m−2) than that using the LP (0.46 W m−2) and BN (0.39 W m−2) parameterizations.