Photochemistry taking place in atmospheric aerosol droplets has a significant impact on the Earth's climate. Nanofocusing of electromagnetic radiation inside aerosols plays a crucial role in their absorption behaviour, since the radiation flux inside the droplet strongly affects the activation rate of photochemically active species. However, size-dependent nanofocusing effects in the photokinetics of small aerosols have escaped direct observation due to the inability to measure absorption signatures from single droplets. Here we show that photoacoustic measurements on optically trapped single nanodroplets provide a direct, broadly applicable method to measure absorption with attolitre sensitivity. We demonstrate for a model aerosol that the photolysis is accelerated by an order of magnitude in the sub-micron to micron size range, compared with larger droplets. The versatility of our technique promises broad applicability to absorption studies of aerosol particles, such as atmospheric aerosols where quantitative photokinetic data are critical for climate predictions.

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Different configurations of photoacoustic (PA) setups for the online-measurement of gaseous NO, employing semiconductor lasers at 2.9 and 4.5 μm, were developed and tested. Their performance was assessed with respect to the analysis of NO emissions from wastewater treatment plants. For this purpose, the local NO emissions of a wastewater treatment bioreactor was sampled by a dedicated mobile sampling device, and the total NO emissions were analyzed in the gastight headspace of the bioreactor. We found that the use of a quantum-cascade laser emitting at about 4.53 μm, operated in a wavelength modulation mode, in combination with a conventional longitudinal PA cell yielded the highest sensitivity (<100 ppbv). However, we also observed a strong cross-sensitivity to humidity, which can be explained by increased V-T relaxation. This observation in combination with the limited dynamic range (max conc. ∼ 3000 ppmv) led us to the use of the less-sensitive but spectroscopically more robust 2.9 μm laser. A detection limit below 1 ppmv, a dynamic range of more than 4 orders of magnitude, no influence of humidity or any other substance relevant to the off-gas analysis, as well as a comparable low price of the laser source made it the ideal tool for NO analyses of the off-gas of a wastewater treatment plant. Such a system was implemented successfully in a full-scale wastewater treatment plant. The results regarding the comparison of different PA setups can be transferred to other systems, and the optimum performance can be selected according to the specific demands.

Nitrous oxide (NO) is a strong greenhouse gas, whose atmospheric concentration has been continuously increasing for more than 200 years. One major source is wastewater treatment plants (WWTPs), where NO emissions should either be minimized or pushed to levels where exploitation in biogas combustion engines becomes efficient. Both these strategies require online control of the NO concentrations in the liquid as well as in the gas phase. For this purpose, we propose a system for membrane extraction of the gas from the liquid phase, which then allows for a subsequent gas-phase analysis, which we perform by photoacoustic spectroscopy. We compare different theoretical calculations of the extraction efficiency, based either on a straightforward mathematical model or on a finite element simulation. The comparison of results with measurements produced on a well-defined model system shows good accordance. Based on the outcome, a field probe was developed and tested on a WWTP, yielding results comparable to the one achieved by GC reference analysis. Graphical abstract Gas extraction from liquids, e.g. from a wastewater treatment plant, for online gas monitoring.

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