This study focused on the photoaging of atmospheric particulate matter smaller than 2.5 μm (PM2.5) in the aqueous phase. PM2.5 was collected during a winter, a spring, and a summer campaign in urban and rural settings in Colorado and extracted into water. The aqueous extracts were photoirradiated using simulated sunlight, and the production rate (r•OH) and the effects of hydroxyl radicals (•OH) were measured as well as the optical properties as a function of the photoaging of the extracts. r•OH was seen to have a strong seasonality with low mean values for the winter and spring extracts (4.8 and 14 fM s-1 mgC-1 L, respectively) and a higher mean value for the summer extracts (65.4 fM s-1 mgC-1 L). For the winter extracts, •OH was seen to mostly originate from nitrate photolysis while for the summer extracts, a correlation was seen between r•OH and iron concentration. The extent of photobleaching of the extracts was correlated with r•OH, and the correlation also indicated that non-•OH processes took place. Using the •OH measurements and singlet oxygen (1O2) measurements, the half-life of a selection of compounds was modeled in the atmospheric aqueous phase to be between 1.9 and 434 h.

Abstract Atmospheric iron solubility varies depending on whether the particles are collected in rural or urban areas, with urban areas showing increased iron solubility. In this study, we investigate if the iron species present in different environments affects its ultimate solubility. Field data are presented from the Platte River Air Pollution and Photochemistry Experiment (PRAPPE), aimed at understanding the interactions between organic carbon and trace elements in atmospheric particulate matter (PM). 24‐hr PM2.5 samples were collected during the summer and winter (2016–2017), at three different sites on the Eastern Colorado plains: an urban, agricultural, and a mixed site. Downtown Denver had an average total and water‐soluble iron air concentration of 181.2 and 7.7 ng m−3, respectively. Platteville, the mixed site, had an average of total iron of 76.1 ng m−3, with average water‐soluble iron concentration of 9.1 ng m−3. Jackson State Park (rural/agricultural) had the lowest total iron average of 31.5 ng m−3 and the lowest water‐soluble iron average, 1.3 ng m−3. The iron oxidation state and chemical speciation of 97 samples across all sites and seasons was probed by X‐ray absorption near edge structure (XANES) spectroscopy. The most common iron phases observed were almandine (Fe₃Al₂Si₃O₁₂) (Denver 21%, Platteville 16%, Jackson 24%), magnetite (Fe3O4) (Denver 9%, Platteville 4%, Jackson 5%) and Fe (III)dextran (Denver 5%, Platteville 13%, Jackson 5%), a surrogate for Fe‐organic complexes. Additionally, native iron [Fe(0)] was found in significant amounts at all sites. No correlation was observed between iron solubility and iron oxidation state or chemical speciation.

Household air pollution from the combustion of solid fuels is a leading global health and human rights concern, affecting billions every day. Instrumentation to assess potential solutions to this problem faces challenges—especially related to cost. A low-cost ($159) particulate matter tool called the Household Air Pollution Exposure (HAPEx) Nano was evaluated in the field as part of the Prices, Peers, and Perceptions cookstove study in northern Ghana. Measurements of temperature, relative humidity, absolute humidity, and carbon dioxide and carbon monoxide concentrations made at 1-min temporal resolution were integrated with 1-min particulate matter less than 2.5 microns in diameter (PM2.5) measurements from the HAPEx, within 62 kitchens, across urban and rural households and four seasons totaling 71 48-h deployments. Gravimetric filter sampling was undertaken to ground-truth and evaluate the low-cost measurements. HAPEx baseline drift and relative humidity corrections were investigated and evaluated using signals from paired HAPEx, finding significant improvements. Resulting particle coefficients and integrated gravimetric PM2.5 concentrations were modeled to explore drivers of variability; urban/rural, season, kitchen characteristics, and dust (a major PM2.5 mass constituent) were significant predictors. The high correlation (R2 = 0.79) between 48-h mean HAPEx readings and gravimetric PM2.5 mass (including other covariates) indicates that the HAPEx can be a useful tool in household energy studies.

Diffuse emission sources outside of kitchen areas are poorly understood, and measurements of their emission factors (EFs) are sparse for regions of sub-Saharan Africa. Thirty-one in-field emission measurements were taken in northern Ghana from combustion sources common to rural regions worldwide. Sources sampled included commercial cooking, trash burning, kerosene lanterns, and diesel generators. EFs were calculated for carbon monoxide (CO), carbon dioxide (CO2), as well as carbonaceous particulate matter, specifically elemental carbon (EC) and organic carbon (OC). EC and OC emissions were measured from kerosene lighting events (EFEC = 25.1 g/kg-fuel SD = 25.7, EFOC = 9.5 g/kg-fuel SD = 10.0). OC emissions from trash burning events were large and highly variable (EFOC = 38.9 g/kg-fuel SD = 30.5). Combining our results with other recent in-field emission factors for rural Ghana, we explored updated emission estimates for Ghana using a region specific emissions inventory. Large differences are calculated for all updated source emissions, showing a 96% increase in OC and 78% decrease in EC compared to prior estimates for Ghana's emissions. Differences for carbon monoxide were small when averaged across all updated source types (-1%), though the household wood use and trash burning categories individually show large differences.

The HITEMP2010 and HITRAN2012 databases are important tools for predicting molecular absorption under various environmental conditions. At room temperature, the databases can be quite accurate, owing to their development using room temperature absorption data. However, at elevated temperatures common to combustion and planetary research, their broadband accuracy is largely unexplored. We utilize a dual frequency comb spectrometer and a high temperature optical cell to assess the capability of these databases to accurately predict water vapor absorption for over 600 transitions at conditions up to 1300K from 6800cm−1 to 7200cm−1. We demonstrate that at 1300K, HITEMP2010 and HITRAN2012 accurately predict the existence and position (within 0.033cm−1) of >99% of transitions with an intensity greater than 1E−28 (cm−1/molecule cm−2), which is the approximate minimum detectable intensity for our absorption spectra. Of the slightly less than 1% of transitions that are misreported, all have linestrengths below 1E−23 (cm−1/molecule cm−2). HITEMP more often predicts transitions that are not observed in the absorption spectra, while HITRAN more often fails to predict an observed line. Updated temperature-scaling coefficients for air-broadening and updated line assignments improve the high temperature performance of HITRAN compared to HITEMP for lineshapes and positions. Our analysis also shows that adding simple temperature-scaling relationships for air-pressure shift and self-broadening half width increase the predictive accuracy of simulations using both databases, and should be employed whenever transition-specific information is unavailable.

We compare water-vapor absorption models generated with HITRAN Online and HITEMP2010 to measurements with a dual-comb spectrometer. For strong lines up to 1300K, HITRAN Online is a more accurate predictor of strengths, shapes, and positions.