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An evaluation of the performance and relative accuracy of a Cavity Attenuated Phase-Shift Single Scattering Albedo Monitor (CAPS PMSSA; Aerodyne Research, Inc.) was conducted in an optical-closure study with proven technologies: Cavity Attenuated Phase-Shift Particle Extinction Monitor (CAPS PMex; Aerodyne Research, Inc.), three-wavelength integrating nephelometer (TSI Model 3563) and three-wavelength filter-based Particle Soot Absorption Photometer (PSAP; Radiance Research Inc.). The evaluation was conducted by connecting the instruments to a controlled aerosol generation system and comparing the measured scattering, extinction and absorption coefficients measured by the CAPS PMSSA with the independent measurements. Three different particle types were used to generate aerosol samples with single-scattering albedos (SSAs) ranging from 0.4 to 1.0 at 630 nm wavelength. The CAPS PMSSA measurements compared well with the proven technologies. Extinction measurement comparisons exhibited a slope of the linear regression line for the full dataset between 1.05 and 1.01, an intercept below ±1.5×10-6 m−1 (±1.5 Mm−1), and a regression coefficient R2>0.99, whereas scattering measurements had a slope between 0.90 and 1.04, an intercept of less than ±2.0×10-6 m−1 (2.0 Mm−1), and a coefficient R2>0.96. The derived CAPS PMSSA absorption compared well to the PSAP measurements for the small particle sizes and modest (0.4 to 0.6) SSA values tested, with a linear regression slope between 0.90 and 1.07, an intercept of ±3.0×10-6 m−1 (3.0 Mm−1), and a coefficient R2>0.99. For the SSA measurements, agreement was highest (regression slopes within 1 %) for SSA =1.0 particles at extinction levels of per tens of inverse megameters and above; however, as extinctions approach 0, small uncertainties in the baseline can introduce larger errors. SSA measurements for absorbing particles exhibited absolute differences up to 18 %, though it is not clear which measurement had the best relative accuracy. For a given particle type, the CAPS PMSSA instrument exhibited the lowest scatter around the average. This study demonstrates that the CAPS PMSSA is a robust and reliable instrument for the direct measurement of the scattering and extinction coefficients and thus SSA. This conclusion also holds for the indirect measurement of the absorption coefficient with the constraint that the relative accuracy of this particular determination degrades as the SSA and particle size increases.

The mass concentration of black carbon (BC) particles in the atmosphere has traditionally been quantified with two methods: as elemental carbon (EC) concentrations measured by thermal–optical analysis and as equivalent black carbon (eBC) concentrations when BC mass is derived from particle light absorption coefficient measurements. Over the last decade, ambient measurements of refractory black carbon (rBC) mass concentrations based on laser-induced incandescence (LII) have become more common, mostly due to the development of the Single Particle Soot Photometer (SP2) instrument. In this work, EC and rBC mass concentration measurements from field campaigns across several background European sites (Palaiseau, Bologna, Cabauw and Melpitz) have been collated and examined to identify the similarities and differences between BC mass concentrations measured by the two techniques. All EC concentration measurements in PM2.5 were performed with the EUSAAR-2 thermal–optical protocol. All rBC concentration measurements were performed with SP2 instruments calibrated with the same calibration material as recommended in the literature. The observed values of median rBC-to-EC mass concentration ratios on the single-campaign level were 0.53, 0.65, 0.97, 1.20 and 1.29, respectively, and the geometric standard deviation (GSD) was 1.5 when considering all data points from all five campaigns. This shows that substantial systematic bias between these two quantities occurred during some campaigns, which also contributes to the large overall GSD. Despite considerable variability in BC properties and sources across the whole dataset, it was not possible to clearly assign reasons for discrepancies to one or the other method, both known to have their own specific limitations and uncertainties. However, differences in the particle size range covered by these two methods were identified as one likely reason for discrepancies. Overall, the observed correlation between rBC and EC mass reveals a linear relationship with a constant ratio, thus providing clear evidence that both methods essentially quantify the same property of atmospheric aerosols, whereas systematic differences in measured absolute values by up to a factor of 2 can occur. This finding for the level of agreement between two current state-of-the-art techniques has important implications for studies based on BC mass concentration measurements, for example for the interpretation of uncertainties in inferred BC mass absorption coefficient values, which are required for modeling the radiative forcing of BC. Homogeneity between BC mass determination techniques is also very important for moving towards a routine BC mass measurement for air quality regulations.

An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals at the parts per trillion level in the CSA simulation chamber (at LISA). The technique couples an incoherent broadband light source centered at 662 nm with a high-finesse optical cavity made of two highly reflecting mirrors. The optical cavity which has an effective length of 82 cm allows for up to 3 km of effective absorption and a high sensitivity for NO3 detection (up to 6 ppt for an integration time of 10 s). This technique also allows for NO2 monitoring (up to 9 ppb for an integration time of 10 s). Here, we present the experimental setup as well as tests for its characterization and validation. The validation tests include an intercomparison with another independent technique (Fourier-transform infrared, FTIR) and the absolute rate determination for the reaction trans-2-butene + NO3, which is already well documented in the literature. The value of (4.13 ± 0.45) × 10−13 cm3 molecule−1 s−1 has been found, which is in good agreement with previous determinations. From these experiments, optimal operation conditions are proposed. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (VOCs; with rate constants up to 10−10 cm3 molecule−1 s−1).

The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (the Netherlands) in September 2016 with the aim of assessing the consistency of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, long-path DOAS, direct-sun DOAS, Sun photometer and meteorological instruments). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations, with the focus on aerosol optical thicknesses (AOTs), trace gas vertical column densities (VCDs) and trace gas surface concentrations. The algorithms are based on three different techniques: six use the optimal estimation method, two use a parameterized approach and one algorithm relies on simplified radiative transport assumptions and analytical calculations. To assess the agreement among the inversion algorithms independent of inconsistencies in the trace gas slant column density acquisition, participants applied their inversion to a common set of slant columns. Further, important settings like the retrieval grid, profiles of O3, temperature and pressure as well as aerosol optical properties and a priori assumptions (for optimal estimation algorithms) have been prescribed to reduce possible sources of discrepancies. The profiling results were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions; however, these are sometimes at different altitudes and of different magnitudes. Under clear-sky conditions, the root-mean-square differences (RMSDs) among the results of individual participants are in the range of 0.01–0.1 for AOTs, (1.5–15) ×1014molec.cm-2 for trace gas (NO2, HCHO) VCDs and (0.3–8)×1010molec.cm-3 for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of 90×1014molec.cm-2 and trace gas surface concentrations of 11×1010molec.cm-3 observed over the campaign period. The discrepancies originate from differences in the applied techniques, the exact implementation of the algorithms and the user-defined settings that were not prescribed. For the comparison against supporting observations, the RMSDs increase to a range of 0.02–0.2 against AOTs from the Sun photometer, (11–55)×1014molec.cm-2 against trace gas VCDs from direct-sun DOAS observations and (0.8–9)×1010molec.cm-3 against surface concentrations from the long-path DOAS instrument. This increase in RMSDs is most likely caused by uncertainties in the supporting data, spatiotemporal mismatch among the observations and simplified assumptions particularly on aerosol optical properties made for the MAX-DOAS retrieval. As a side investigation, the comparison was repeated with the participants retrieving profiles from their own differential slant column densities (dSCDs) acquired during the campaign. In this case, the consistency among the participants degrades by about 30 % for AOTs, by 180 % (40 %) for HCHO (NO2) VCDs and by 90 % (20 %) for HCHO (NO2) surface concentrations. In former publications and also during this comparison study, it was found that MAX-DOAS vertically integrated aerosol extinction coefficient profiles systematically underestimate the AOT observed by the Sun photometer. For the first time, it is quantitatively shown that for optimal estimation algorithms this can be largely explained and compensated by considering biases arising from the reduced sensitivity of MAX-DOAS observations to higher altitudes and associated a priori assumptions.

A shipborne Sun–sky–lunar photometer of type CE318-T was tested during two trans-Atlantic cruises aboard the German research vessel Polarstern from 54∘ N to 54∘ S in May/June and December 2018. The continuous observations of the motion-stabilized shipborne CE318-T enabled the first-time observation of a full diurnal cycle of aerosol optical depth (AOD) and column-mean Ångström coefficient of a mixed dust–smoke episode. The latitudinal distribution of the AOD from the shipborne CE318-T, Raman lidar and MICROTOPS II shows the same trend with highest values in the dust belt from 0 to 20∘ N and overall low values in the Southern Hemisphere. The linear-regression coefficients of determination between MICROTOPS II and the CE318-T were 0.988, 0.987, 0.994 and 0.994 for AODs at 380, 440, 500 and 870 nm and 0.896 for the Ångström exponent at 440–870 nm. The root-mean-squared differences of AOD at 380, 440, 500 and 870 nm were 0.015, 0.013, 0.010 and 0.009, respectively.

We developed an optimal-estimation algorithm to simultaneously retrieve, for the first time, coexisting volcanic gaseous SO2 and sulfate aerosols (SA) from ground-based Fourier transform infrared (FTIR) observations. These effluents, both linked to magmatic degassing process and subsequent atmospheric evolution processes, have overlapping spectral signatures leading to mutual potential interferences when retrieving one species without considering the other. We show that significant overestimations may be introduced in SO2 retrievals if the radiative impact of coexistent SA is not accounted for, which may have impacted existing SO2 long-term series, e.g. from satellite platforms. The method was applied to proximal observations at Masaya volcano, where SO2 and SA concentrations, and SA acidity, were retrieved. A gas-to-particle sulfur partitioning of 400 and a strong SA acidity (sulfuric acid concentration: 65 %) were found, consistent with past in situ observations at this volcano. This method is easily exportable to other volcanoes to monitor magma extraction processes and the atmospheric sulfur cycle in the case of ash-free plumes.

Simultaneous measurement of C2H6 and CH4 concentrations, and of the δ13C-CH4 isotope ratio is demonstrated using a cavity-enhanced absorption spectroscopy technique in the mid-IR region. The spectrometer is compact and has been designed for field operation. It relies on optical-feedback-assisted injection of 3.3 µm radiation from an interband cascade laser (ICL) into a V-shaped high-finesse optical cavity. A minimum absorption coefficient of 2.8×10-9 cm−1 is obtained in a single scan (0.1 s) over 0.7 cm−1. Precisions of 3 ppbv, 11 ppbv, and 0.08 ‰ for C2H6, CH4, and δ13C-CH4, respectively, are achieved after 400 s of integration time. Laboratory calibrations and tests of performance are reported here. They show the potential for the spectrometer to be embedded in a sensor probe for in situ measurements in ocean waters, which could have important applications for the understanding of the source and fate of hydrocarbons from the seabed and in the water column.

Smog chamber experiments using ambient air as a starting point can improve our understanding of the evolution of atmospheric particulate matter at timescales longer than those achieved by traditional laboratory experiments. These types of studies can take place under more realistic environmental conditions addressing the interactions among multiple pollutants. The use of two identical smog chambers, with the first serving as the baseline chamber and the second as the perturbation chamber (in which addition or removal of pollutants, addition of oxidants, change in the relative humidity, etc.), can facilitate the interpretation of the results in such inherently complex experiments. The differences of the measurements in the two chambers can be used as the basis for the analysis of the corresponding chemical or physical processes of ambient air. A portable dual-smog-chamber system was developed using two identical pillow-shaped smog chambers (1.5 m3 each). The two chambers are surrounded by UV lamps in a hexagonal arrangement yielding a total JNO2 of 0.1 min−1. The system can be easily disassembled and transported, enabling the study of various atmospheric environments. Moreover, it can be used with natural sunlight. The results of test experiments using ambient air as the starting point are discussed as examples of applications of this system.

Measurements of dry air mole fractions of atmospheric greenhouse gases are used in inverse models of atmospheric tracer transport to quantify their sources and sinks. The measurements have to be calibrated to a common scale to avoid bias in the inferred fluxes. For this purpose, the World Meteorological Organization (WMO) has set requirements for the interlaboratory compatibility of atmospheric greenhouse gas (GHG) measurements. A widely used series of devices for these measurements are the GHG analyzers manufactured by Picarro, Inc. These are often operated in humid air, and the effects of water vapor are corrected for in post-processing. Here, we report on rarely detected and previously unexplained biases of the water correction method for CO2 and CH4 in the literature. They are largest at water vapor mole fractions below 0.5 % H2O, which were undersampled in previous studies, and can therefore affect measurements obtained in humid air. Setups that dry sample air using Nafion membranes may be affected as well if there are differences in residual water vapor levels between sample and calibration air. The biases are caused by a sensitivity of the pressure in the measurement cavity to water vapor. We correct these biases by modifying the water correction method from the literature. Our method relies on experiments that maintain stable water vapor levels to allow equilibration of cavity pressure. In our experiments with the commonly used droplet method, this requirement was not fulfilled. Correcting CO2 measurements proved challenging, presumably because of our humidification method. Open questions pertain to differences among analyzers and variability over time. In our experiments, the biases amounted to considerable fractions of the WMO interlaboratory compatibility goals. Since measurements of dry air mole fractions of CO2 and CH4 are also subject to other uncertainties, correcting the cavity pressure-related biases helps keep the overall accuracy of measurements obtained with Picarro GHG analyzers in humid and potentially in Nafion-dried air within the WMO goals.

In situ measurements using unmanned aerial vehicles (UAVs) and remote sensing observations can independently provide dense vertically resolved measurements of atmospheric aerosols, information which is strongly required in climate models. In both cases, inverting the recorded signals to useful information requires assumptions and constraints, and this can make the comparison of the results difficult. Here we compare, for the first time, vertical profiles of the aerosol mass concentration derived from light detection and ranging (lidar) observations and in situ measurements using an optical particle counter on board a UAV during moderate and weak Saharan dust episodes. Agreement between the two measurement methods was within experimental uncertainty for the coarse mode (i.e. particles having radii >0.5 µm), where the properties of dust particles can be assumed with good accuracy. This result proves that the two techniques can be used interchangeably for determining the vertical profiles of aerosol concentrations, bringing them a step closer towards their systematic exploitation in climate models.