HELIOS/SICRIT/mass spectrometry for analysis of aerosols in engine exhaust

Current legislations typically characterize systems of aerosols, such as from vehicle exhaust, primarily by number concentration and size distributions. While potential health threats have a dependence on the particle size, the chemical composition of particles, including the volatile and semi-volatile components adsorbed onto nonvolatile particle cores present at roadside and urban settings, is important in understanding the impact of exhaust particles on health. To date, the only tools suitable for an online in-depth chemical aerosol characterization are aerosol mass spectrometers, which are typically composed of complex and cost intensive instrumentation. We present a new analytical system, which combines a novel inexpensive infrared-radiation-based evaporation system (HELIOS) with a commercially available highly efficient atmospheric ionization source (SICRIT) connected to a rather low-price ion-trap mass spectrometer. Our inexpensive, robust and mobile aerosol characterization HELIOS/SICRIT/Mass Spectrometry system enables highly sensitive chemical analysis of particle-associated volatile substances. We validate the HELIOS/SICRIT/Mass Spectrometry system in laboratory experiments with coated particles generated under controlled conditions, and show that the system is capable of identification of combustion-generated polycyclic aromatic hydrocarbons and relative quantification of individual chemical species adsorbed on particle surfaces. We then employ our system to analyze real-world vehicle engine exhaust aerosol and show through time-resolved measurements with high time resolution (<10 s) that the chemical composition of the particles changes during different parts of an engine test cycle.acceptedVersionPeer reviewe

Photoacoustics of single laser-trapped nanodroplets for the direct observation of nanofocusing in aerosol photokinetics

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.ISSN:2041-172

Photoacoustic Spectroscopy for the Quantification of N₂O in the Off-Gas of Wastewater Treatment Plants

Different configurations of photoacoustic (PA) setups for the online-measurement of gaseous N₂O, employing semiconductor lasers at 2.9 and 4.5 μm, were developed and tested. Their performance was assessed with respect to the analysis of N₂O emissions from wastewater treatment plants. For this purpose, the local N₂O emissions of a wastewater treatment bioreactor was sampled by a dedicated mobile sampling device, and the total N₂O 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 <i>V</i>–<i>T</i> 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 N₂O 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