• Energy Research

Spraying is a common way to distribute occupational products, but it puts worker's health at risk by exposing them to potentially harmful particles and gases. The objective of this study is to use time-resolved measurements to gain an understanding of spray applications at the process level and to compare them to predictions of exposure models. We used proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) at 1-s time resolution to monitor the gas phase concentration of the solvents acetone, ethanol, butyl acetate, xylene and 1-methoxy-2-propy acetate during outdoor spraying and indoor drying of metal plate under various conditions of outdoor air supply. We found that during spraying, gas-phase exposure was dominated by the more volatile solvents acetone and ethanol, which exhibited strong concentration variations due to the outdoor winds. During drying, exposure strongly depended on the strength of ventilation. Under conditions with high supply of outdoor air, our measurements show a near-exponential decay of the solvent concentrations during drying. Conversely, under conditions without outdoor air supply, the drying process required hours, during which the less volatile solvents passed through a concentration maximum in the gas phase, so that the exposure during drying exceeded the exposure during spraying. The concentrations measured during spraying were then compared for each of the substances individually with the predictions of the exposure models ECETOC TRA, Stoffenmanager, and ART using TREXMO. For these conditions, ECETOC TRA and Stoffenmanager predicted exposures in the measured concentration range, albeit not conservative for all solvents and each application. In contrast, ART largely overestimated the exposure for the more volatile solvents acetone and ethanol and slightly underestimated exposure to 1M2PA for one spraying. ECETOC TRA and ART do not have options to predict exposure during drying. Stoffenmanager has the option to predict drying together with spraying, but not to predict the drying phase independently. Our study demonstrates the importance of considering both the spray cloud and solvent evaporation during the drying process. To improve workplace safety, there is a critical need for enhanced exposure models and comprehensive datasets for calibration and validation covering a broader range of exposure situations.

The first excited state of molecular oxygen is singlet-state oxygen (1O2), formed by indirect photochemistry of chromophoric organic matter. To determine whether 1O2 can be a competitive atmospheric oxidant, we must first quantify its production in organic aerosols (OA). Here, we report the spatiotemporal distribution of 1O2 over a 1-year dataset of PM10 extracts at two locations in Switzerland, representing a rural and suburban site. Using a chemical probe technique, we measured 1O2 steady-state concentrations with a seasonality over an order of magnitude peaking in wintertime at 4.59 ± 0.01 × 10-13 M and with a quantum yield of up to 2%. Next, we identified biomass burning and anthropogenic secondary OA (SOA) as the drivers for 1O2 formation in the PM10 aqueous extracts using source apportionment data. Importantly, the quantity, the amount of brown carbon present in PM10, and the quality, the chemical composition of the brown carbon present, influence the concentration of 1O2 sensitized in each extract. Anthropogenic SOA in the extracts were 4 times more efficient in sensitizing 1O2 than primary biomass burning aerosols. Last, we developed an empirical fit to estimate 1O2 concentrations based on PM10 components, unlocking the ability to estimate 1O2 from existing source apportionment data. Overall, 1O2 is likely a competitive photo-oxidant in PM10 since 1O2 is sensitized by ubiquitous biomass burning OA and anthropogenic SOA.

AbstractA list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog1,2, but how it occurs in cities is often puzzling3. If the growth rates of urban particles are similar to those found in cleaner environments (1–10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below −15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid–base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms4,5.