A methodology to determine 212Pb, 212Bi, 214Pb and 214Bi in atmospheric aerosols; Application to precisely obtain aerosol residence times and Rn-daughters' equilibrium factors.

Progeny of 222Rn and 220Rn, (212Pb, 212Bi, 214Pb and 214Bi) are essential to assess radiological hazard, external and internal doses, residence times and equilibrium factors. Precise measurements of these nuclides are quite complex due to their very short half-lives. This study outlines a new and precise methodology to measure these nuclides. Radon-222 and 220Rn were measured using a radon monitoring system, while their respective progenies were collected in an atmospheric filter using an ASS-500 sampler and measured by gamma-ray spectrometry. The 212Pb concentrations were very similar to the thoron ones, where all 212Bi/212Pb ratios were consistently less than 1. The relative uncertainties, σr, of the 212Pb and 212Bi activity concentrations, and 212Bi/212Pb activity ratio are generally less than 10%. Moreover, 214Pb/222Rn ratios were about 0.7, agreeing well with previous works. The σr for 214Pb, 214Bi and 214Bi/214Pb were generally less than 6%. This methodology was applied to estimate aerosol residence times using the 214Pb/222Rn and 212Bi/212Pb activity ratios, and to obtain equilibrium factors, achieving consistent results. Furthermore, the methodology consistency and validity range were studied with time elapsed between sampling end and counting start, and the sampling durations, finding the optimum times to precisely determine 212Pb, 212Bi, 214Pb and 214Bi.

Surface ozone trends at El Arenosillo observatory from a new perspective.

Surface ozone trends observed at El Arenosillo observatory for the last 22 years (2000-2021) were investigated. The trends for daily averages and daily 5th and 95th percentiles were 1.2 ± 0.3 ppb decade-1, 2.2 ± 0.3 ppb decade-1 and -0.03 ± 0.43 ppb decade-1, respectively, thus showing a significant increase of background ozone. The surface temperature trends were also explored, obtaining trends of 0.5 ± 0.2 °C decade-1, 1.1 ± 0.2 °C decade-1 and -0.3 ± 0.2 °C decade-1 for daily averages, 5th and 95th percentiles, respectively. To identify potential changes in the ozone drivers, the weather pattern shifts were analyzed through the horizontal distribution trends of temperature at 2 m and geopotential height at 850 hPa. A strengthening of the Azores anticyclone and a regional warming were detected, which could contribute to the ozone trends obtained. The surface ozone trend in every month was explored, identifying a monthly pattern, with remarkable opposite trends in December-January (2.4 ± 0.9 ppb decade-1) vs July-August (-0.5 ± 1.1 ppb decade-1). The surface ozone trends for every hour of the day were also explored, identifying two clear patterns. The first pattern occurred from spring to autumn and was characterized by a behavior opposite to the typical daily ozone cycle. The second pattern was observed in winter, and it shows two relative peaks in the ozone trends (around 13:00 and 19:00 UTC). In a context of ozone precursor's depletion, changes in the weather conditions and warmer climate, to improve our knowledge of the ozone trends, we suggest exploring them based on daily and hourly averages.

Radon transport events associated with the impact of a NORM repository in the SW of Europe.

Two radon measurement stations located to the north and south of a NORM (Naturally Occurring Radioactive Materials) repository of phosphogypsum (southwest of Europe) were used to monitor radon behavior during 2018. The stations are located at opposing sides of the repository, one in Huelva City to the north and other one in a rural area to the south. This setup aimed to identify the influence of the NORM repository on each station and use radon levels as a marker of atmospheric transport in the local area. To achieve this, a comparison was carried out with other coastal stations in the south of Spain, finding higher average concentrations in Huelva City, ~3.3 Bq m-3. Hierarchical clustering was applied to identify days with different radon patterns at each Huelva station, detecting possible local radon transport events from the repository. Three events were investigated with WRF (Weather Research and Forecasting) and FLEXPART-WRF (FLEXible PARTicle dispersion model). It was found that both sampling sites required atmospheric stagnant conditions to reach high radon concentration. However, under these conditions the urban station showed high radon regardless of wind direction while the rural station also required radon transport from the repository, either directly or indirectly.

Behaviour of heavy metals and natural radionuclides in the mixing of phosphogypsum leachates with seawater.

Phosphogypsum (PG) is disposed worldwide in large stacks usually placed in coastal zones, as in the case of Huelva (SW of Spain), where around 100 Mt of PG are stored on the salt marshes of the Tinto River estuary covering a surface of about 1000 ha. This management generates the weathering of PG, and due to its high acidity (pH ≈ 2) and pollutant load can provoke significant emissions into their surroundings. In this work were evaluated by laboratory experiments the effects of pH increase in the behaviour of heavy metals and natural radionuclides during the mixing of phosphogypsum leachates with seawater. The acidic phosphogypsum leachates showed concentrations of heavy metals from two to three orders of magnitude higher than natural continental waters, and natural radionuclides (U-isotopes and 210Po) from four to five orders of magnitude higher than unperturbed aquatic systems. Major elements and some heavy metals as Mn, Ni, Cd, As, Sb and Co showed a conservative behaviour during the neutralisation of the leachates with seawater, remaining in the liquid phase, while other ones as Al, Fe, Cr, Zn, Cu, Pb precipitated and/or were adsorbed onto the solid phase. The U-isotopes and 210Po showed a clear non-conservative behaviour probably due to coprecipitation/adsorption processes onto the formed precipitates, but while 210Po reached a total removal at pH ≈ 7, U- isotopes after a total removal at pH ≈ 5 returned into the liquid phase due to redissolution/desorption processes at near neutral pH. The formed precipitates, mainly composed by iron phosphates particles, showed heavy metal and natural radionuclide concentrations from one to three orders of magnitude higher than unperturbed soils. All these facts demonstrate the serious environmental impact produced by the PG stacks into their surroundings and the urgency of effective restoration measures.

Ground-based and OMI-TROPOMI NO2 measurements at El Arenosillo observatory: Unexpected upward trends.

Eleven years, January 2008 to June 2019, of hourly nitrogen dioxide (NO2) levels recorded at El Arenosillo observatory (Southwestern Europe) were analyzed. Annual averages ranged between 4 µg m-3 and 6 µg m-3 with peaks exceeding 40 µg m-3. A slight monthly variation was observed with maximum and minimum values in the cold (∼6 µg m-3) and warm (∼4 µg m-3) seasons respectively. A diurnal pattern was found with a weak amplitude (∼3 µg m-3). The monthly trends were investigated using surface observations and OMI (Ozone Monitoring instrument) satellite measurements. An unexpected upward trend was obtained in the last five years. The periods with elevated NO2 concentrations in the last years were analyzed, showing an increase in its frequency and concentrations, linked with the upward trend observed. The weather conditions in these NO2 peaks were studied using local surface meteorology, mean sea level pressure and wind fields from the data reanalysis of ERA5. The transport of NO2 was explored using TROPOMI (Tropospheric Monitoring Instrument) measurements. The events occurred under conditions governed by high-pressure systems, which induced weak synoptic airflows or the development of mesoscale processes. Four scenarios of NO2 transport were identified, associated with weak synoptic flows from inland or Southern Portugal and with mesoscale processes. The gulf of Cadiz plays an important role as a reservoir where the NO2 coming from the south of Portugal, the Western Mediterranean Basin and urban-industrial areas can be accumulated and later transported inland. A strong correlation was found between the increase of NO2 observed in the last years and positive anomalies of the temperature and geopotential height at 850 and 500 hPa levels. These findings could indicate that the causes of the changes in the NO2 would be attributed to alterations in the weather patterns associated with a warmer climate.

Influence of the accumulation chamber insertion depth to measure surface radon exhalation rates.

A common method to measure radon exhalation rates relies on the accumulation chamber technique. Usually, this approach only considers one-dimensional gas transport within the soil that neglects lateral diffusion. However, this lateral transport could reduce the reliability of the method. In this work, several cylindrical-shaped accumulation chambers were built with different heights to test if the insertion depth of the chamber into the soil improves the reliability of the method and, in that case, if it could limit the radon lateral diffusion effects. To check this hypothesis in laboratory, two reference exhalation boxes were manufactured using phosphogypsum from a repository located nearby the city of Huelva, in the southwest of Spain. Laboratory experiments showed that insertion depth had a deep impact in reducing the effective decay constant of the system, extending the interval where the linear fitting can be applied, and consistently obtaining reliable exhalation measurements once a minimum insertion depth is employed. Field experiments carried out in the phosphogypsum repository showed that increasing the insertion depth could reduce the influence of external effects, increasing the repeatability of the method. These experiments provided a method to obtain consistent radon exhalation measurements over the phosphogypsum repository.

Study of the exceptional meteorological conditions, trace gases and particulate matter measured during the 2017 forest fire in Doñana Natural Park, Spain.

In late June 2017, a forest fire occurred in Doñana Natural Park, which is located in southwestern Europe. Many animal and plant species, some of which are threatened, suffered from the impact of this fire, and important ecosystems in the European Union were seriously affected. This forest fire occurred under exceptional weather conditions. The meteorological situation was studied at both the synoptic scale and the local scale using meteorological fields in the ERA-Interim global model from ECMWF (European Centre for Medium Range Weather Forecasts), the WRF (Weather Research and Forecasting) mesoscale model and ground observations collected at El Arenosillo observatory. Anomalies were obtained using records (observations and simulations) over the last two decades (1996-2016). An anticyclonic system dominated the synoptic meteorological conditions, but a strong pressure gradient was present; positive high pressure anomalies and negative low pressure anomalies resulted in intense NW flows. At the surface, wind gusts of 80 km h-1, temperatures up to 35 °C and relative humidity values <20% were observed. In terms of anomalies, these observations corresponded to positive temperature anomalies (differences of 12 °C), positive wind speed anomalies (>29 km h-1) and negative relative humidity anomalies (differences of 40%). The forest fire reached El Arenosillo observatory approximately 8 h after it began. When the fire started, record-setting maximum values were measured for all gases monitored at this site (specifically, peaks of 99,995 µg m-3 for CO, 951 µg m-3 for O3, 478 µg m-3 for NO2, 116 µg m-3 for SO2 and 1000 µg m-3 for PM10). According to the temporal evolution patterns of these species, the atmosphere over a burnt area can recover to initial atmospheric levels between 48 and 96 h after an event. The impact of the Doñana plume was studied using hourly forward trajectories computed with the HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory) model to analyse the emission source for the burnt area. The Doñana fire plume affected large metropolitan areas near the Mediterranean coast. Air quality stations located in the cities of Seville and Cadiz registered the arrival of the plume based on increases in CO and PM10. Using CO as a tracer, measurements from the AIRS and MOPITT instruments allowed us to observe the transport of the Doñana plume from the Strait of Gibraltar to the Mediterranean. Finally, after two days, the Doñana forest fire plume reached the western Mediterranean basin.