Low cost sensors for measuring atmospheric pollutants are experiencing an increase in popularity worldwide among practitioners, academia and environmental agencies, and a large amount of data by these devices are being delivered to the public. Notwithstanding their behaviour, performance and reliability are not yet fully investigated and understood. In the present study we investigate the medium term performance of a set of NO and NO₂ electrochemical sensors in Switzerland using three different regression algorithms within a field calibration approach. In order to mimic a realistic application of these devices, the sensors were initially co-located at a rural regulatory monitoring site for a 4-month calibration period, and subsequently deployed for 4 months at two distant regulatory urban sites in traffic and urban background conditions, where the performance of the calibration algorithms was explored. The applied algorithms were Multivariate Linear Regression, Support Vector Regression and Random Forest; these were tested, along with the sensors, in terms of generalisability, selectivity, drift, uncertainty, bias, noise and suitability for spatial mapping intra-urban pollution gradients with hourly resolution. Results from the deployment at the urban sites show a better performance of the non-linear algorithms (Support Vector Regression and Random Forest) achieving RMSE < 5 ppb, R² between 0.74 and 0.95 and MAE between 2 and 4 ppb. The combined use of both NO and NO₂ sensor output in the estimate of each pollutant showed some contribution by NO sensor to NO₂ estimate and vice-versa. All algorithms exhibited a drift ranging between 5 and 10 ppb for Random Forest and 15 ppb for Multivariate Linear Regression at the end of the deployment. The lowest concentration correctly estimated, with a 25 % relative expanded uncertainty, resulted in ca. 15–20 ppb and was provided by the non-linear algorithms. As an assessment for the suitability of the tested sensors for a targeted application, the probability of resolving hourly concentration difference in cities was investigated. It was found that NO concentration differences of 5–10 ppb (8–10 for NO₂) can reliably be detected (90 % confidence), depending on the air pollution level. The findings of this study, although derived from a specific sensor type and sensor model, are based on a flexible methodology and have extensive potential for exploring the performance of other low cost sensors, that are different in their target pollutant and sensing technology.

The Mann–Kendall test associated with the Sen's slope is a very widely used non-parametric method for trend analysis. It requires serially uncorrelated time series, yet most of the atmospheric processes exhibit positive autocorrelation. Several prewhitening methods have therefore been designed to overcome the presence of lag-1 autocorrelation. These include a prewhitening, a detrending and/or a correction of the detrended slope and the original variance of the time series. The choice of which prewhitening method and temporal segmentation to apply has consequences for the statistical significance, the value of the slope and of the confidence limits. Here, the effects of various prewhitening methods are analyzed for seven time series comprising in situ aerosol measurements (scattering coefficient, absorption coefficient, number concentration and aerosol optical depth), Raman lidar water vapor mixing ratio, as well as tropopause and zero-degree temperature levels measured by radio-sounding. These time series are characterized by a broad variety of distributions, ranges and lag-1 autocorrelation values and vary in length between 10 and 60 years. A common way to work around the autocorrelation problem is to decrease it by averaging the data over longer time intervals than in the original time series. Thus, the second focus of this study evaluates the effect of time granularity on long-term trend analysis. Finally, a new algorithm involving three prewhitening methods is proposed in order to maximize the power of the test, to minimize the number of erroneous detected trends in the absence of a real trend and to ensure the best slope estimate for the considered length of the time series.

Aerosol particles are essential constituents of the Earth's atmosphere, impacting the earth radiation balance directly by scattering and absorbing solar radiation, and indirectly by acting as cloud condensation nuclei. In contrast to most greenhouse gases, aerosol particles have short atmospheric residence times, resulting in a highly heterogeneous distribution in space and time. There is a clear need to document this variability at regional scale through observations involving, in particular, the in situ near-surface segment of the atmospheric observation system. This paper will provide the widest effort so far to document variability of climate-relevant in situ aerosol properties (namely wavelength dependent particle light scattering and absorption coefficients, particle number concentration and particle number size distribution) from all sites connected to the Global Atmosphere Watch network. High-quality data from almost 90 stations worldwide have been collected and controlled for quality and are reported for a reference year in 2017, providing a very extended and robust view of the variability of these variables worldwide. The range of variability observed worldwide for light scattering and absorption coefficients, single-scattering albedo, and particle number concentration are presented together with preliminary information on their long-term trends and comparison with model simulation for the different stations. The scope of the present paper is also to provide the necessary suite of information, including data provision procedures, quality control and analysis, data policy, and usage of the ground-based aerosol measurement network. It delivers to users of the World Data Centre on Aerosol, the required confidence in data products in the form of a fully characterized value chain, including uncertainty estimation and requirements for contributing to the global climate monitoring system.

The Po valley in northern Italy is renowned for its high air pollutant concentrations. Measurements of air pollutants from a background site in Modena, a town of 200 thousand inhabitants within the Po valley, are analysed. These comprise hourly data for CO, NO, NO₂ , NO_x , and O₃, and daily gravimetric equivalent data for PM₁₀ from 1998–2010. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and auto-correlation and cross-correlation functions. CO, NO and NO₂ exhibit a strongly traffic-related pattern, with daily peaks at morning and evening rush hour and lower concentrations over the weekend. Ozone shows an annual cycle with a peak in July due to local production; notwithstanding the diurnal cycle dominated by titration by nitrogen oxide, the decreasing long term trend in NO concentration did not affect the long term trend in O₃, whose mean concentration remained steady over the sampling period. PM₁₀ shows a strong seasonality with higher concentration in winter and lower concentration in summer and spring. Both PM₁₀ and ozone show a marked weekly cycle in summer and winter respectively. Regressions of PM₁₀ upon NO_x show a consistently greater intercept in winter, representing higher secondary PM₁₀ in the cooler months of the year. There is a seasonal pattern in primary PM₁₀ to NO_x ratios, with lower values in winter and higher values in summer, but the reasons are unclear.

The limits to atmospheric pollutant concentration set by the European Commission provide a challenging target for the municipalities in the Po Valley, because of the characteristic climatic conditions and high population density of this region. In order to assess climatology and trends in the concentration of atmospheric particles in the Po Valley, a data set of PM10 data from 41 sites across the Po Valley have been analysed, including both traffic and background sites (either urban, suburban or rural). Of these 41 sites, 18 with 10 yr or longer record have been analysed for long-term trend in deseasonalized monthly means, in annual quantiles and in monthly frequency distribution. A widespread significant decreasing trend has been observed at most sites, up to a few percent per year, by a generalized least squares and Theil–Sen method. All 41 sites have been tested for significant weekly periodicity by Kruskal–Wallis test for mean anomalies and by Wilcoxon test for weekend effect magnitude. A significant weekly periodicity has been observed for most PM10 series, particularly in summer and ascribed mainly to anthropic particulate emissions. A cluster analysis has been applied in order to highlight stations sharing similar pollution conditions over the reference period. Five clusters have been found, two encompassing the metropolitan areas of Turin and Milan and their respective nearby sites and the other three clusters gathering northeast, northwest and central Po Valley sites respectively. Finally, the observed trends in atmospheric PM10 have been compared to trends in provincial emissions of particulates and PM precursors, and analysed along with data on vehicular fleet age, composition and fuel sales. A significant basin-wide drop in emissions occurred for gaseous pollutants, contrarily to emissions of PM10 and PM2.5, whose drop was low and restricted to a few provinces. It is not clear whether the decrease for only gaseous emissions is sufficient to explain the observed drop in atmospheric PM10, or if the low drop in particulate emissions is indeed due to the uncertainty in the emission inventory data for this species.

The Po Valley is one of the largest European regions with a remarkably high concentration level of atmospheric pollutants, both for particulate and gaseous compounds. In the last decade stringent regulations on air quality standards and on anthropogenic emissions have been set by the European Commission, including also for PM_2.5 and its main components since 2008. These regulations have led to an overall improvement in air quality across Europe, including the Po Valley and specifically PM₁₀, as shown in a previous study by Bigi and Ghermandi (2014). In order to assess the trend and variability in PM_2.5 in the Po Valley and its role in the decrease in PM₁₀, we analysed daily gravimetric equivalent concentration of PM_2.5 and of PM_10–2.5 at 44 and 15 sites respectively across the Po Valley. The duration of the times series investigated in this work ranges from 7 to 10 years. For both PM sizes, the trend in deseasonalized monthly means, annual quantiles and in monthly frequency distribution was estimated: this showed a significant decreasing trend at several sites for both size fractions and mostly occurring in winter. All series were tested for a significant weekly periodicity (a proxy to estimate the impact of primary anthropogenic emissions), yielding positive results for summer PM_2.5 and for summer and winter PM_10–2.5. Hierarchical cluster analysis showed moderate variability in PM_2.5 across the valley, with two to three main clusters, dividing the area in western, eastern and southern/Apennines foothill sectors. The trend in atmospheric concentration was compared with the time series of local emissions, vehicular fleet details and fuel sales, suggesting that the decrease in PM_2.5 and in PM₁₀ originates from a drop both in primary and in precursors of secondary inorganic aerosol emissions, largely ascribed to vehicular traffic. Potentially, the increase in biomass burning emissions in winter and the modest decrease in NH₃ weaken an otherwise even larger drop in atmospheric concentrations.