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Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition

Emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uintah Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and for short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas well pads with collection and dehydration on the well pad were clearly associated with higher mixing ratios than other wells. The comparison of the VOC composition of the emissions from the oil and natural gas well pads showed that gas well pads without dehydration on the well pad compared well with the majority of the data at Horse Pool, and that oil well pads compared well with the rest of the ground site data. Oil well pads on average emit heavier compounds than gas well pads. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.
TNO-MACC_II emission inventory; a multi-year (2003–2009) consistent high-resolution European emission inventory for air quality modelling

Emissions to air are reported by countries to EMEP. The emissions data are used for country compliance checking with EU emission ceilings and associated emission reductions. The emissions data are also necessary as input for air quality modelling. The quality of these "official" emissions varies across Europe. As alternative to these official emissions, a spatially explicit high-resolution emission inventory (7 × 7 km) for UNECE-Europe for all years between 2003 and 2009 for the main air pollutants was made. The primary goal was to supply air quality modellers with the input they need. The inventory was constructed by using the reported emission national totals by sector where the quality is sufficient. The reported data were analysed by sector in detail, and completed with alternative emission estimates as needed. This resulted in a complete emission inventory for all countries. For particulate matter, for each source emissions have been split in coarse and fine particulate matter, and further disaggregated to EC, OC, SO4, Na and other minerals using fractions based on the literature. Doing this at the most detailed sectoral level in the database implies that a consistent set was obtained across Europe. This allows better comparisons with observational data which can, through feedback, help to further identify uncertain sources and/or support emission inventory improvements for this highly uncertain pollutant. The resulting emission data set was spatially distributed consistently across all countries by using proxy parameters. Point sources were spatially distributed using the specific location of the point source. The spatial distribution for the point sources was made year-specific. The TNO-MACC_II is an update of the TNO-MACC emission data set. Major updates included the time extension towards 2009, use of the latest available reported data (including updates and corrections made until early 2012) and updates in distribution maps.
Exploiting simultaneous observational constraints on mass and absorption to estimate the global direct radiative forcing of black carbon and brown carbon

Atmospheric black carbon (BC) is a leading climate warming agent, yet uncertainties on the global direct radiative forcing (DRF) remain large. Here we expand a global model simulation (GEOS-Chem) of BC to include the absorption enhancement associated with BC coating and separately treat both the aging and physical properties of fossil-fuel and biomass-burning BC. In addition we develop a global simulation of brown carbon (BrC) from both secondary (aromatic) and primary (biomass burning and biofuel) sources. The global mean lifetime of BC in this simulation (4.4 days) is substantially lower compared to the AeroCom I model means (7.3 days), and as a result, this model captures both the mass concentrations measured in near-source airborne field campaigns (ARCTAS, EUCAARI) and surface sites within 30%, and in remote regions (HIPPO) within a factor of 2. We show that the new BC optical properties together with the inclusion of BrC reduces the model bias in absorption aerosol optical depth (AAOD) at multiple wavelengths by more than 50% at AERONET sites worldwide. However our improved model still underestimates AAOD by a factor of 1.4 to 2.8 regionally, with the largest underestimates in regions influenced by fire. Using the RRTMG model integrated with GEOS-Chem we estimate that the all-sky top-of-atmosphere DRF of BC is +0.13 Wm−2 (0.08 Wm−2 from anthropogenic sources and 0.05 Wm−2 from biomass burning). If we scale our model to match AERONET AAOD observations we estimate the DRF of BC is +0.21 Wm−2, with an additional +0.11 Wm−2 of warming from BrC. Uncertainties in size, optical properties, observations, and emissions suggest an overall uncertainty in BC DRF of −80%/+140%. Our estimates are at the lower end of the 0.2–1.0 Wm−2 range from previous studies, and substantially less than the +0.6 Wm−2 DRF estimated in the IPCC 5th Assessment Report. We suggest that the DRF of BC has previously been overestimated due to the overestimation of the BC lifetime (including the effect on the vertical profile) and the incorrect attribution of BrC absorption to BC.
Modeling ultrafine particle growth at a pine forest site influenced by anthropogenic pollution during BEACHON-RoMBAS 2011

Formation and growth of ultrafine particles is crudely represented in chemistry-climate models, contributing to uncertainties in aerosol composition, size distribution, and aerosol effects on cloud condensation nuclei (CCN) concentrations. Measurements of ultrafine particles, their precursor gases, and meteorological parameters were performed in a ponderosa pine forest in the Colorado Front Range in July–August 2011, and were analyzed to study processes leading to small particle burst events (PBEs) which were characterized by an increase in the number concentrations of ultrafine 4–30 nm diameter size particles. These measurements suggest that PBEs were associated with the arrival at the site of anthropogenic pollution plumes midday to early afternoon. During PBEs, number concentrations of 4–30 nm diameter particles typically exceeded 104 cm−3, and these elevated concentrations coincided with increased SO2 and monoterpene concentrations, and led to a factor-of-2 increase in CCN concentrations at 0.5% supersaturation. The PBEs were simulated using the regional WRF-Chem model, which was extended to account for ultrafine particle sizes starting at 1 nm in diameter, to include an empirical activation nucleation scheme in the planetary boundary layer, and to explicitly simulate the subsequent growth of Aitken particles (10–100 nm) by condensation of organic and inorganic vapors. The updated model reasonably captured measured aerosol number concentrations and size distribution during PBEs, as well as ground-level CCN concentrations. Model results suggest that sulfuric acid originating from anthropogenic SO2 triggered PBEs, and that the condensation of monoterpene oxidation products onto freshly nucleated particles contributes to their growth. The simulated growth rate of ~ 3.4 nm h−1 for 4–40 nm diameter particles was comparable to the measured average value of 2.3 nm h−1. Results also suggest that the presence of PBEs tends to modify the composition of sub-20 nm diameter particles, leading to a higher mass fraction of sulfate aerosols. Sensitivity simulations suggest that the representation of nucleation processes in the model largely influences the predicted number concentrations and thus CCN concentrations. We estimate that nucleation contributes 67% of surface CCN at 0.5% supersaturation in this pine forest environment.
A global model simulation of present and future nitrate aerosols and their direct radiative forcing of climate

The ammonia cycle and nitrate particle formation are introduced into the LMDz-INCA (Laboratoire de Météorologie Dynamique, version 4 – INteraction with Chemistry and Aerosols, version 3) global model. An important aspect of this new model is that both fine nitrate particle formation in the accumulation mode and coarse nitrate forming on existing dust and sea-salt particles are considered. The model simulates distributions of nitrates and related species in agreement with previous studies and observations. The calculated present-day total nitrate direct radiative forcing since the pre-industrial is −0.056 W m−2. This forcing corresponds to 18% of the sulfate forcing. Fine particles largely dominate the nitrate forcing, representing close to 90% of this value. The model has been used to investigate the future changes in nitrates and direct radiative forcing of climate based on snapshot simulations for the four representative concentration pathway (RCP) scenarios and for the 2030, 2050, and 2100 time horizons. Due to a decrease in fossil fuel emissions in the future, the concentration of most of the species involved in the nitrate–ammonium–sulfate system drop by 2100 except for ammonia, which originates from agricultural practices and for which emissions significantly increase in the future. Despite the decrease of nitrate surface levels in Europe and North America, the global burden of accumulation mode nitrates increases by up to a factor of 2.6 in 2100. This increase in ammonium nitrate in the future arises despite decreasing NOx emissions due to increased availability of ammonia to form ammonium nitrate. The total aerosol direct forcing decreases from its present-day value of −0.234 W m−2 to a range of −0.070 to −0.130 W m−2 in 2100 based on the considered scenario. The direct forcing decreases for all aerosols except for nitrates, for which the direct negative forcing increases to a range of −0.060 to −0.115 W m−2 in 2100. Including nitrates in the radiative forcing calculations increases the total direct forcing of aerosols by a factor of 1.3 in 2000, by a factor of 1.7–2.6 in 2030, by 1.9–4.8 in 2050, and by 6.4–8.6 in 2100. These results show that the agricultural emissions of ammonia will play a key role in the future mitigation of climate change, with nitrates becoming the dominant contributor to the anthropogenic aerosol optical depth during the second half of the 21st century and significantly increasing the calculated aerosol direct forcing. This significant increase in the influence that nitrate exerts on climate in the future will at the same time affect regional air quality and nitrogen deposition to the ecosystem.
The decreasing albedo of the Zhadang glacier on western Nyainqentanglha and the role of light-absorbing impurities

A large change in albedo has a significant effect on glacier ablation. Atmospheric aerosols – e.g. black carbon (BC) and dust – can reduce the albedo of glaciers and thus contribute to their melting. In this study, two main themes were explored: (1) the decrease in albedo of the Zhadang glacier on Mt. Nyainqentanglha between 2001 and 2012, as observed by the Moderate Resolution Imaging Spectroradiometer (MODIS) on-board the Terra satellite, and the correlation of this albedo with mass balance; and (2) the concentrations of BC and dust in the glacier measured during 2012, and the associated impacts of these impurities on albedo and radiative forcings (RF). The average albedo of the Zhadang glacier from the MODIS increased with the altitude and fluctuated but had a decreasing trend (−0.003 a−1) during the period 2001–2012, with the highest (0.722) in 2003 and the lowest (0.597) in 2009 and 2010. The mass balance of the glacier has a positively significant correlation with its surface albedo derived from MODIS. Snow samples were collected on the Zhadang glacier to measure the BC and dust in the summer of 2012. The impacts of BC and dust on albedo reduction in different melting conditions were identified with the SNow ICe Aerosol Radiative (SNICAR) model initiated by in situ observation data. The sensitivity analysis showed that BC was a major factor in albedo reduction when the glacier was covered by newly fallen snow. Nevertheless, the contribution of dust to albedo reduction can reach as high as 56%, much exceeding that of BC (28%), when the glacier experiences strong surficial melting and its surface is almost bare ice. The average RF caused by dust could increase from 1.1 to 8.6 W m−2, exceeding the RF caused by BC after snow was deposited and surface melting occurred in the Zhadang glacier. This implies that it may be dust that primarily dominates the melting of some glaciers in the inner Tibetan Plateau during melting seasons, rather than BC.
Variability of the infrared complex refractive index of African mineral dust: experimental estimation and implications for radiative transfer and satellite remote sensing

Experimental estimations of the infrared refractive index of African mineral dust have been retrieved from laboratory measurements of particle transmission spectra in the wavelength range 2.5–25 μm. Five dust samples collected at Banizoumbou (Niger) and Tamanrasset (Algeria) during dust events originated from different Western Saharan and Sahelian areas have been investigated. The real (n) and imaginary (k) parts of the refractive index obtained for the different dust samples vary in the range 1.1–2.7 and 0.05–1.0, respectively, and are strongly sensitive to the mineralogical composition of the particles, especially in the 8–12 and 17–25 μm spectral intervals. Dust absorption is controlled mainly by clays (kaolinite, illite, smectite) and, to a lesser extent, by quartz and calcium-rich minerals (e.g. calcite, gypsum). Significant differences are obtained when comparing our results with existing experimental estimations available in the literature, and with the values of the OPAC (Optical Properties of Aerosols and Clouds) database. The different data sets appear comparable in magnitude, with our values of n and k falling within the range of variability of past studies. However, literature data fail in accurately reproducing the spectral signatures of the main minerals, in particular clays, and they significantly overestimate the contribution of quartz. Furthermore, the real and the imaginary parts of the refractive index from some literature studies are found not to verify the Kramers–Kronig relations, thus being theoretically incorrect. The comparison between our results, from western Africa, and literature data, from different locations in Europe, Africa, and the Caribbean, nonetheless, confirms the expected large variability of the dust infrared refractive index. This highlights the necessity for an extended systematic investigation of dust properties at infrared wavelengths. For the five analysed dust samples, aerosol intensive optical properties relevant to radiative transfer (mass extinction efficiency, kext, single scattering albedo, ω, and asymmetry factor, g) have been calculated, by using the Mie theory, based on the estimated refractive index and measured particle size distribution. The optical properties show a large sample-to-sample variability, with kext, ω, and g varying in the range 0.05–0.35, 0.25–1.0, and 0.05–0.75. This variability is expected to significantly impact satellite retrievals of atmospheric and surface parameters (e.g. from the Infrared Atmospheric Sounding Interferometer, IASI) and estimates of the dust radiative forcing.
Evaluation of tropospheric SO2 retrieved from MAX-DOAS measurements in Xianghe, China

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of sulfur dioxide (SO2) have been performed at the Xianghe station (39.8° N, 117.0° E) located at ~ 50 km southeast of Beijing from March 2010 to February 2013. Tropospheric SO2 vertical profiles and corresponding vertical column densities (VCDs), retrieved by applying the optimal estimation method to the MAX-DOAS observations, have been used to study the seasonal and diurnal cycles of SO2, in combination with correlative measurements from in situ instruments, as well as meteorological data. A marked seasonality was observed in both SO2 VCD and surface concentration, with a maximum in winter (February) and a minimum in summer (July). This can be explained by the larger emissions in winter due to the domestic heating and, in case of surface concentration, by more favorable meteorological conditions for the accumulation of SO2 close to the ground during this period. Wind speed and direction are also found to be two key factors in controlling the level of the SO2-related pollution at Xianghe. In the case of east or southwest wind, the SO2 concentration does not change significantly with the wind speed, since the city of Tangshan and heavy polluting industries are located to the east and southwest of the station, respectively. In contrast, when wind comes from other directions, the stronger the wind, the less SO2 is observed due to a more effective dispersion. Regarding the diurnal cycle, the SO2 amount is larger in the early morning and late evening and lower at noon, in line with the diurnal variation of pollutant emissions and atmospheric stability. A strong correlation with correlation coefficients between 0.6 and 0.9 is also found between SO2 and aerosols in winter, suggesting that anthropogenic SO2, through the formation of sulfate aerosols, contributes significantly to the total aerosol content during this season. The observed diurnal cycles of MAX-DOAS SO2 surface concentration are also in very good agreement (correlation coefficient close to 0.9) with those from collocated in situ data, indicating the good reliability and robustness of our retrieval.
Hygroscopicity of organic compounds from biomass burning and their influence on the water uptake of mixed organic ammonium sulfate aerosols

Hygroscopic behavior of organic compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, as well as their effects on the hygroscopic properties of ammonium sulfate (AS) in internally mixed particles are studied by a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds used represent pyrolysis products of wood that are emitted from biomass burning sources. It is found that humic acid aerosol particles only slightly take up water, starting at RH (relative humidity) above ~70%. This is contrasted by the continuous water absorption of levoglucosan aerosol particles in the range 5–90% RH. However, no hygroscopic growth is observed for 4-hydroxybenzoic acid aerosol particles. Predicted water uptake using the ideal solution theory, the AIOMFAC model and the E-AIM (with UNIFAC) model are consistent with measured hygroscopic growth factors of levoglucosan. However, the use of these models without consideration of crystalline organic phases is not appropriate to describe the hygroscopicity of organics that do not exhibit continuous water uptake, such as 4-hydroxybenzoic acid and humic acid. Mixed aerosol particles consisting of ammonium sulfate and levoglucosan, 4-hydroxybenzoic acid, or humic acid with different organic mass fractions, take up a reduced amount of water above 80% RH (above AS deliquescence) relative to pure ammonium sulfate aerosol particles of the same mass. Hygroscopic growth of mixtures of ammonium sulfate and levoglucosan with different organic mass fractions agree well with the predictions of the thermodynamic models. Use of the Zdanovskii–Stokes–Robinson (ZSR) relation and AIOMFAC model lead to good agreement with measured growth factors of mixtures of ammonium sulfate with 4-hydroxybenzoic acid assuming an insoluble organic phase. Deviations of model predictions from the HTDMA measurement are mainly due to the occurrence of a microscopical solid phase restructuring at increased humidity (morphology effects), which are not considered in the models. Hygroscopic growth factors of mixed particles containing humic acid are well reproduced by the ZSR relation. Lastly, the organic surrogate compounds represent a selection of some of the most abundant pyrolysis products of biomass burning. The hygroscopic growths of mixtures of the organic surrogate compounds with ammonium sulfate with increasing organics mass fraction representing ambient conditions from the wet to the dry seasonal period in the Amazon basin, exhibit significant water uptake prior to the deliquescence of ammonium sulfate. The measured water absorptions of mixtures of several organic surrogate compounds (including levoglucosan) with ammonium sulfate are close to those of binary mixtures of levoglucosan with ammonium sulfate, indicating that levoglucosan constitutes a major contribution to the aerosol water uptake prior to (and beyond) the deliquescence of ammonium sulfate. Hence, certain hygroscopic organic surrogate compounds can substantially affect the deliquescence point of ammonium sulfate and overall particle water uptake.
Re-evaluating the reactive uptake of HOBr in the troposphere with implications for the marine boundary layer and volcanic plumes

The reactive uptake of HOBr onto halogen-rich aerosols promotes conversion of Br−(aq) into gaseous reactive bromine (incl. BrO) with impacts on tropospheric oxidants and mercury deposition. However, experimental data quantifying HOBr reactive uptake on tropospheric aerosols is limited, and reported values vary in magnitude. This study introduces a new evaluation of HOBr reactive uptake coefficients in the context of the general acid-assisted mechanism. We emphasise that the termolecular kinetic approach assumed in numerical model studies of tropospheric reactive bromine chemistry to date is strictly only valid for a specific pH range and, according to the general acid-assisted mechanism for HOBr, the reaction kinetics becomes bimolecular and independent of pH at high acidity. This study reconciles for the first time the different reactive uptake coefficients reported from laboratory experiments. The re-evaluation confirms HOBr reactive uptake is rapid on moderately acidified sea-salt aerosol (and slow on alkaline aerosol), but predicts very low reactive uptake coefficients on highly acidified submicron particles. This is due to acid-saturated kinetics combined with low halide concentrations induced by both acid-displacement reactions and the dilution effects of H2SO4(aq). A mechanism is thereby proposed for reported Br enhancement (relative to Na) in H2SO4-rich submicron particles in the marine environment. Further, the fact that HOBr reactive uptake on H2SO4-acidified supra-micron particles is driven by HOBr+Br− (rather than HOBr+Cl−) indicates self-limitation via decreasing γHOBr once aerosol Br- is converted into reactive bromine. First predictions of HOBr reactive uptake on sulfate particles in halogen-rich volcanic plumes are also presented. High (accommodation limited) HOBr+Br- uptake coefficient in concentrated (> 1 μmol mol−1 SO2) plume environments supports potential for rapid BrO formation in plumes throughout the troposphere. However, reduced HOBr reactive uptake may reduce the rate of BrO cycling in dilute plumes in the lower troposphere. In summary, our re-evaluation of HOBr kinetics provides a new framework for the interpretation of experimental data and suggests that the reactive uptake of HOBr on H2SO4-acidified particles is substantially overestimated in current numerical models of BrO chemistry in the troposphere.