Spatiotemporal variations of tropospheric ozone in Spain (2008-2019).

This study aims to support the development of Spain's Ozone Mitigation Plan by evaluating the present-day spatial variation (2015-2019) and trends (2008-2019) for seven ground-level ozone (O3) metrics relevant for human/ecosystems exposure and regulatory purposes. Results indicate that the spatial variation of O3 depends on the part of the O3 distribution being analyzed. Metrics associated with moderate O3 concentrations depict an increasing O3 gradient between the northern and Mediterranean coasts due to climatic factors, while for metrics considering the upper end of the O3 distribution, this climatic gradient tends to attenuate in favor of hotspot regions pointing to relevant local/regional O3 formation. A classification of atmospheric regions in Spain is proposed based on their O3 pollution patterns, to identify priority areas (or O3 hotspots) where local/regional precursor abatement might significantly reduce O3 during pollution episodes. The trends assessment reveals a narrowing of the O3 distribution at the national level, with metrics influenced by lower concentrations tending to increase over time, and those reflecting the higher end of the O3 distribution tending to decrease. While most stations show no statistically significant variations, contrasting O3 trends are evident among the O3 hotspots. The Madrid area exhibits the majority of upward trends across all metrics, frequently with the highest increasing rates, implying increasing O3 associated with both chronic and episodic exposure. The Valencian Community area exhibits a mixed variation pattern, with moderate to high O3 metrics increasing and peak metrics decreasing, while O3 in areas downwind of Barcelona, the Guadalquivir Valley and Puertollano shows no variations. Sevilla is the only large Spanish city with generalized O3 decreasing trends. The different O3 trends among hotspots highlight the need for mitigation measures to be designed at a local/regional scale to be effective. This approach may offer valuable insights for other countries developing O3 mitigation plans.

Impact of the COVID-19 Lockdown in a European Regional Monitoring Network (Spain): Are We Free from Pollution Episodes?

The impact of the lockdown, during the period from March to June in 2020, upon the air quality of the Basque Country in northern Spain is analyzed. The evaluation accounts for the meteorology of the period. Daily and sub-daily analysis of aerosol and ozone records show that the territory was repeatedly affected by episodes of pollutants from outer regions. Three episodes of PM10 and ten of PM2.5 were caused by transported anthropogenic European sulfates, African dust, and wildland fires. The region, with a varied orographic climatology, shows high and diverse industrial activity. Urban and interurban road traffic of the region decreased by 49% and 53%, respectively, whereas industrial activity showed a lower reduction of 20%. Consequently, the average concentrations of NO2 in the cities during the period fell to 12.4 µg·m-3 (-45%). Ozone showed up to five exceedances of the WHOAQG for the daily maximum 8-h average in both rural and urban sites, associated with transport through France and the Bay of Biscay, under periods of European blocking anticyclones. However, averages showed a moderate decrease (-11%) in rural environments, in line with the precursor reductions, and disparate changes in the cities, which reproduced the weekend effect of their historical records. The PM10 decreased less than expected (-10% and -21%, in the urban and rural environments, respectively), probably caused by the modest decrease of industrial activity around urban sites and favorable meteorology for secondary aerosol formation, which could also influence the lower changes observed in the PM2.5 (-1% and +3% at the urban and rural sites, respectively). Consequently, in a future low NOx traffic emission scenario, the inter-regional PM and ozone control will require actions across various sectors, including the industry and common pollution control strategies.

Lessons from the COVID-19 air pollution decrease in Spain: Now what?

We offer an overview of the COVID-19 -driven air quality changes across 11 metropolises in Spain with the focus on lessons learned on how continuing abating pollution. Traffic flow decreased by up to 80% during the lockdown and remained relatively low during the full relaxation (June and July). After the lockdown a significant shift from public transport to private vehicles (+21% in Barcelona) persisted due to the pervasive fear that using public transport might increase the risk of SARS-CoV-2 infection, which need to be reverted as soon as possible. NO2 levels fell below 50% of the WHO annual air quality guidelines (WHOAQGs), but those of PM2.5 were reduced less than expected due to the lower contributions from traffic, increased contributions from agricultural and domestic biomass burning, or meteorological conditions favoring high secondary aerosol formation yields. Even during the lockdown, the annual PM2.5 WHOAQG was exceeded in cities within the NE and E regions with high NH3 emissions from farming and agriculture. Decreases in PM10 levels were greater than in PM2.5 due to reduced emissions from road dust, vehicle wear, and construction/demolition. Averaged O3 daily maximum 8-h (8hDM) experienced a generalized decrease in the rural receptor sites in the relaxation (June-July) with -20% reduced mobility. For urban areas O3 8hDM responses were heterogeneous, with increases or decreases depending on the period and location. Thus, after canceling out the effect of meteorology, 5 out of 11 cities experienced O3 decreases during the lockdown, while the remaining 6 either did not experience relevant reductions or increased. During the relaxation period and coinciding with the growing O3 season (June-July), most cities experienced decreases. However, the O3 WHOAQG was still exceeded during the lockdown and full relaxation periods in several cities. For secondary pollutants, such as O3 and PM2.5, further chemical and dispersion modeling along with source apportionment techniques to identify major precursor reduction targets are required to evaluate their abatement potential.

Ozone source apportionment during peak summer events over southwestern Europe.

It is well established that in Europe, high O3 concentrations are most pronounced in southern/Mediterranean countries due to the more favourable climatological conditions for its formation. However, the contribution of the different sources of precursors to O3 formation within each country relative to the imported (regional and hemispheric) O3 is poorly quantified. This lack of quantitative knowledge prevents local authorities from effectively designing plans that reduce the exceedances of the O3 target value set by the European air quality directive. O3 source attribution is a challenge because the concentration at each location and time results not only from local biogenic and anthropogenic precursors, but also from the transport of O3 and precursors from neighbouring regions, O3 regional and hemispheric transport and stratospheric O3 injections. The main goal of this study is to provide a first quantitative estimation of the contribution of the main anthropogenic activity sectors to peak O3 events in Spain relative to the contribution of imported (regional and hemispheric) O3. We also assess the potential of our source apportionment method to improve O3 modelling. Our study applies and thoroughly evaluates a countrywide O3 source apportionment method implemented in the CALIOPE air quality forecast system for Spain at high resolution (4 × 4 km2) over a 10-day period characterized by typical summer conditions in the Iberian Peninsula (IP). The method tags both O3 and its gas precursor emissions from source sectors within one simulation, and each tagged species is subject to the typical physico-chemical processes (advection, vertical mixing, deposition, emission and chemistry) as the actual conditions remain unperturbed. We quantify the individual contributions of the largest NO x local sources to high O3 concentrations compared with the contribution of imported O3. We show, for the first time, that imported O3 is the largest input to the ground-level O3 concentration in the IP, accounting for 46 %-68 % of the daily mean O3 concentration during exceedances of the European target value. The hourly imported O3 increases during typical northwestern advections (70 %-90 %, 60-80 µg m-3), and decreases during typical stagnant conditions (30 %-40 %, 30-60 µg m-3) due to the local NO titration. During stagnant conditions, the local anthropogenic precursors control the O3 peaks in areas downwind of the main urban and industrial regions (up to 40 % in hourly peaks). We also show that ground-level O3 concentrations are strongly affected by vertical mixing of O3-rich layers present in the free troposphere, which result from local/regional layering and accumulation, and continental/hemispheric transport. Indeed, vertical mixing largely explains the presence of imported O3 at ground level in the IP. Our results demonstrate the need for detailed quantification of the local and remote contributions to high O3 concentrations for local O3 management, and show O3 source apportionment to be an essential analysis prior to the design of O3 mitigation plans in any non-attainment area. Achieving the European O3 objectives in southern Europe requires not only ad hoc local actions but also decided national and European-wide strategies.

Summertime high resolution variability of atmospheric formaldehyde and non-methane volatile organic compounds in a rural background area.

On rural background areas atmospheric formaldehyde (HCHO) is important for its abundance and chemical reactivity, directly linked to the tropospheric ozone formation processes. HCHO is also toxic and carcinogenic to humans. Atmospheric HCHO was continuously measured in summer 2016 during 81 days (N = 6722, average: 1.42 ppbv) in a rural background area in Northern Spain, Valderejo Natural Park (VNP) using a Hantzsch fluorimetric system. To better characterize the photochemical processes the database was completed with hourly measurements of 63 Non-Methane Hydrocarbons (NMHC) performed by gas chromatography and other common atmospheric pollutants and meteorological parameters. HCHO mixing ratios were highly correlated with ozone and isoprene. Cloudy and rainy days, with low temperature and radiation, led to low HCHO mixing ratios, with maxima (<2 ppbv) registered around 14 UTC. On days with increased radiation and temperature HCHO maxima occurred slightly later (<6 ppbv, ≈16:00 UTC). During clear summer days with high temperature and radiation, two HCHO peaks were registered daily, one synchronized with the radiation maximum (≈3-4 ppbv, ≈13:00 UTC) and an absolute maximum (<10 ppbv, ≈18:00 UTC), associated with the addition of HCHO coming into VNP due to inbound transport of old polluted air masses. In the ozone episode studied, the processes of accumulation and recharge of ozone and of HCHO ran in parallel, leading to similar daily patterns of variation. Finally, HCHO mixing ratios measured in VNP were compared with other measurements at rural, forested, and remote sites all over the world, obtaining similar values.

Continuous measurement of atmospheric reduced sulphur compounds as key tracers between odour complaints and source apportionment.

Odour complaints are frequent nowadays, particularly nearby industrial facilities emitting odorous compounds. Among all compounds susceptible of causing odour annoyance, reduced sulphur compounds (RSC) were studied, due to their unpleasant odour and low odour threshold. RSC ambient air mixing ratios, meteorological conditions and population complaints were analysed in an area of complex topography in order to identify their potential sources. Mixing ratios of three compounds, dimethyl sulphide (DMS), carbon disulphide (CDS) and dimethyl disulphide (DMDS), were continuously monitored using an online gas chromatograph coupled with a mass spectrometer detector (GC-MSD), which was placed in a mobile air quality monitoring unit. Measurement campaigns were performed during 2012 and 2013 for periods of 7-25 days in an urban area (four campaigns, N = 1368) and an urban area surrounded by industrial activities (three campaigns, N = 564). During such campaigns, RSC mixing ratios were frequently above their odour thresholds, which did not always involve citizen complaints. Average RSC ambient air mixing ratios tended to be lower in the urban area (DMS 0.06-0.33, CDS 0.05-0.10, DMDS 0.07-0.30 µg m-3) than in the industry surrounded one (DMS 0.30-2.39, 0.05-0.18, DMDS 0.09-0.62 µg m-3). The DMS/DMDS mixing ratio was frequently above 1, being a paper mill one of the main sources of RSC in the area. DMS/DMDS ratios below 1 were also recorded, suggesting a waste treatment plant as the RSC source or older air masses coming from the paper mill.

Online hourly determination of 62 VOCs in ambient air: system evaluation and comparison with another two analytical techniques.

This paper presents results of the processing and validation of data collected by an automatic gas chromatograph (AGC). This system was used to monitor 62 volatile organic compounds (VOCs) in urban air in the Basque Country, Spain. The nonpolar compounds (C2-C10) identified-paraffins, olefins, aromatics, and chlorinated compounds-accounted for 88% of the mass of total non-methane hydrocarbons (TNMHCs) in ambient air. The evaluation of linearity, precision, detection limits (DLs), and stability of retention times (RTs) indicates that the equipment is suitable for measuring ambient air automatically for prolonged periods (6 months). The calibration of the equipment using response factors calculated on the basis of the effective carbon number (ECN) showed variations of over 10% for acetylene, isoprene, and n-hexane. The results provided by the automatic chromatograph correlated significantly with simultaneous results from other widely used techniques for determining VOCs in ambient air: (1) portable GC, equipped with photoionization detector (PID), and (2) active adsorption on Tenax-TA followed by thermal desorption and chromatographic analysis.