Abstract. Trace metals in ambient particulate matter and cloud are considered key elements of atmospheric processes as they affect air quality, environmental ecosystems, and cloud formation. However, they are often available at trace concentrations in these media such that their analysis requires high-precision and sensitive techniques. In this study, different analytical methods were applied to quantify trace metals in particulate matter (PM) samples collected on quartz and polycarbonate filters as well as cloud water, using the Total reflection X-Ray Fluorescence (TXRF) technique. These methods considered the measurement of filter samples directly without and with chemical pretreatment. Direct measurements involved the analysis of PM samples collected on polycarbonate filters and cloud water samples after they are brought onto TXRF carrier substrates. The chemical treatment method involved the assessment of different acid digestion procedures on PM sampled on quartz filters. The solutions applied were reverse aqua regia, nitric acid, and a combination of nitric acid and hydrogen peroxide. The effect of cold-plasma treatment of samples on polycarbonate filters before TXRF measurements was also investigated. Digestion with the reverse aqua regia solution provided lower blanks and higher recovery in comparison to other tested procedures. The detection limits of the elements ranged from 0.3 to 44 ng cm−2. Ca, K, Zn, and Fe showed the highest detection limits of 44, 35, 6, and 1 ng cm−2, while As and Se had the lowest of 0.3 and 0.8 ng cm−2, respectively. The method showed higher recovery for most trace metals when applied to commercially available reference materials and field samples. TXRF measurements showed good agreement with results obtained from ion chromatography measurements for elements such as Ca and K. Cold-plasma treatment did not significantly lead to an increase in the detected concentration, and the results were element specific. Baking of the quartz filters prior to sampling showed a reduction of more than 20 % of the filter blanks for elements such as V, Sr, Mn, Zn, and Sb. The methods were applied successfully on ambient particulate matter and cloud water samples collected from the Atlas Mohammed V station in Morocco and the Cape Verde Atmospheric Observatory. The obtained concentrations were within the range reported using different techniques from similar remote and background regions elsewhere, especially for elements of anthropogenic origins such as V, Pb, and Zn with concentrations of up to 10, 19, and 28 ng m−3, respectively. Enrichment factor analysis indicated that crustal matter dominated the abundance of most of the elements, while anthropogenic activities also contributed to the abundance of elements such as Sb, Se, and Pb. The results confirm that TXRF is a useful complementary sensitive technique for trace metal analysis of particulate matter in the microgram range as well as in cloud water droplets.
Abstract. Field measurements were conducted to determine aerosol chemical composition at a newly established remote high-altitude site in North Africa at the Atlas Mohammed V (AMV) atmospheric observatory located in the Middle Atlas Mountains. The main objectives of the present work are to investigate the variations in the aerosol composition and better assess global and regional changes in atmospheric composition in North Africa. A total of 200 particulate matter (PM10) filter samples were collected at the site using a high-volume (HV) collector in a 12 h sampling interval from August to December 2017. The chemical composition of the samples was analyzed for trace metals, water-soluble ions, organic carbon (OC/EC), aliphatic hydrocarbons, and polycyclic aromatic hydrocarbon (PAH) contents. The results indicate that high-altitude aerosol composition is influenced by both regional and transregional transport of emissions. However, local sources play an important role, especially during low wind speed periods, as observed for November and December. During background conditions characterized by low wind speeds (avg. 3 m s-1) and mass concentrations in the range from 9.8 to 12 μg m-3, the chemical composition is found to be dominated by inorganic elements, mainly suspended dust (61 %) and ionic species (7 %), followed by organic matter (7 %), water content (12 %), and unidentified mass (11 %). Despite the proximity of the site to the Sahara, its influence on the atmospheric composition at this high-altitude site was mainly seasonal and accounted for only 22 % of the sampling duration. Biogenic organics contributed up to 7 % of the organic matter with high contributions from compounds such as heneicosane, hentriacontane, and nonacosane. The AMV site is dominated by four main air mass inflows, which often leads to different aerosol chemical compositions. Mineral dust influence was seasonal and ranged between 21 % and 74 % of the PM mass, with peaks observed during the summer, and was accompanied by high concentrations of SO42- of up to 3.0 μg m-3. During winter, PM10 concentrations are low (<30 μg m-3), the influence of the desert is weaker, and the marine air masses (64 %) are more dominant with a mixture of sea salt and polluted aerosol from the coastal regions (Rabat and Casablanca). During the daytime, mineral dust contribution to PM increased by about 42 % because of road dust resuspension. In contrast, during nighttime, an increase in the concentrations of alkanes, PAHs, alkane-2-ones, and anthropogenic metals such as Pb, Ni, and Cu was found due to variations in the boundary layer height. The results provide the first detailed seasonal and diurnal variation of the aerosol chemical composition, which is valuable for long-term assessment of climate and regional influence of air pollution in North Africa.
<p>Mountain and high-altitude sites provide representative data for the lower free troposphere and various pathways for aerosol interactions, changing boundary layer heights useful in understanding atmospheric composition. However, few studies exist in African regions despite its diversity in both natural and anthropogenic emissions. For this reason, the ATLAS Mohamed V (AM5) observatory in the Middle Atlas region was established to provide the necessary infrastructure for detailed atmospheric studies in the North African high-altitude region. Here, results of a field study conducted to determine the aerosol chemical composition in this region, understand its variations, and importance in assessing global and regional changes in the atmospheric composition is reported. Particulate matter (PM<sub>10</sub>) filter samples (200) were collected using a high-volume (500l/min) collector in a 12h sampling interval from August to December 2017. The chemical composition of the samples was analyzed for trace metals, ions, elemental carbon, organic carbon, aliphatic hydrocarbons, and polycyclic aromatic hydrocarbon (PAHs) content. The results show that the high-altitude aerosol composition is influenced by regional and transregional transport of different pollutants. Local sources play an important role during periods when the wind speed is low, especially during autumn. Despite the proximity of the site to the Saharan Desert, its influence on the atmospheric composition was mainly seasonal and accounted for only 14% of the sampling duration. The chemical composition was dominated by inorganic elements, mainly suspended dust (47%) and ionic species (16%), and followed by organic matter (15%), water content (12%), and indeterminate mass (9%). Biogenic organics contributed up to 7% of the organic matter with high contributions from compounds such as Nonacosane, Heptacosane, and 2-Pentadecanone. Four main air masses characterized the inflow to the site, which often leads to different aerosol chemical compositions. Mineral dust influenced was seasonal and ranged between 20 and 70% of the PM mass with peaks observed during the summer and was accompanied by high concentrations of SO<sub>4</sub><sup>2-</sup> of up to 1.3 &#181;g/m&#179;. PM<sub>10</sub> concentrations during winter were low (< 30 &#181;g/m&#179;), with a dominance of marine air masses (53%) carrying aerosols rich in sea salt and polluted anthropogenic aerosols from the coastal regions (Rabat and Casablanca). During the day-time, mineral dust contribution to PM increased by about 42% due to road dust resuspension. In contrast, during night-time, an increase in the concentrations of PAHs, ketones, and anthropogenic metals such as Pb, Ni, and Cu was found due to variations in the boundary layer height. The results provide first insights into typical North African high-altitude background aerosol chemical composition useful for long-term assessment of climate and regional influence of air pollution in North Africa.</p><p>&#160;</p>
Abstract. Field measurements were conducted to determine aerosol chemical composition in a newly established remote high-altitude site in North Africa to investigate the variations in aerosol composition useful in assessing global and regional changes in atmospheric composition. Particulate matter (PM10) filter samples (200) were collected at the Atlas Mohammed V atmospheric observatory (AM5) located in the Middle-Atlas Mountains in Morocco using a high-volume (HV) collector in a 12 h sampling interval from August to December 2017. The chemical composition of the samples was analyzed for trace metals, ions, elemental carbon, organic carbon, aliphatic hydrocarbons, and polycyclic aromatic hydrocarbon (PAHs) content. The results indicate that high-altitudes aerosol composition is influenced by both regional as well as trans-regional transport of emissions. However, local sources play an important role, especially during low wind speed periods, as observed for November and December. Despite the proximity of the site to the Sahara Desert, its influence on the atmospheric composition at this high-altitude site was mainly seasonal and accounted for only 14 % of the sampling duration. Background conditions at this remote site are characterized by low wind speeds (Av. 2.5 m/s) and mass concentrations in the range of 9.8 and 20 µg/m3. The chemical composition is found to be dominated by inorganic elements, mainly suspended dust (47 %) and ionic species (16 %), followed by organic matter (15 %), water content (12 %), and indeterminate mass (9 %). Biogenic organics contributed up to 7 % of the organic matter with high contributions from compounds such as Nonacosane, Heptacosane, and 2-Pentadecanone. The AM5 site is dominated by four main air mass inflow, which often leads to different aerosol chemical compositions. Mineral dust influenced was seasonal and ranged between 20 and 70 % of the PM mass with peaks observed during the summer and was accompanied by high concentrations of SO42− of up to 1.3 µg/m3. During winter, PM10 concentrations are low (
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