Water Soluble Organic Nitrogen in atmospheric aerosol samples from urban, sub-urban and pristine areas of Venezuela

Concentrations of water soluble organic nitrogen (WSON) were determined in atmospheric total suspended particles (TSP) collected between September of 2005 and May of 2006, in an urban continental (Caracas, 10° 29' 09'' N, 66° 53' 48'' W), an urban coastal (Catia la mar, 10° 35' 47'' N, 67° 01' 45'' W), a sub-urban coastal (Osma, 10° 32' N, 67° 28' W), a suburban continental (Altos de Pipe, 10° 23' 41'' N, 63° 59' 10'' W), a pristine coastal (Isla de Aves, 15° 40' N, 63° 36' W) and a pristine continental (La Gran Sabana National Park, 5° 41' 30'' N, 61° 34' 20'' W) areas of Venezuela. TSP samples were collected using a Hi-Vol airborne particle sampler. TSP were impacted on a fiberglass filter pretreated under 400° C for 4 hours to minimize organic nitrogen contamination. Ultra sound water extractions of the sample filters were performed and their NH4+, NO2- and NO3- concentrations were determined by ion exchange liquid chromatography. The water extracts were UV digested and the nitrogen inorganic ions were analyzed after the UV exposure. WSON concentrations were calculated by the difference between the inorganic nitrogen concentrations before and after UV digestion. Ninety five percent of the aerosol samples collected in the suburban and pristine areas showed a WSON concentration range from 0.03 to 0.6 μg/m3 whereas in urban areas the range was 0.21 to 1.09 μg/m3. These concentration values are on the same order of magnitude than the previously found in other tropical and subtropical areas. The contribution of aerosol WSON to the total soluble nitrogen in the coastal urban, sub-urban and pristine areas ranged from 23 to 67%, while in Caracas was smaller (38±8%, n=5). Therefore, aerosol WSON provides an important source of nitrogen to these pristine and suburban ecosystems, which could potentially have implications on the nutrient cycling. There was a statistically significant linear correlation between the aerosol WSON and the water soluble inorganic nitrogen (WSIN) for the urban coastal, sub-urban and pristine zones (R2= 0.81, n=22). This correlation could be explained by a possible source of secondary water soluble organic aerosols derived by the reaction between biogenic volatile organic compounds (VOCs), such as isoprene, and nitrogen oxides (NOx) present in the atmosphere of these regions. Such correlation was not found in Caracas, possibly due to the fact that in this city the major source of VOCs is fossil fuel combustion which produces mostly non soluble aliphatic VOCs. These compounds could most likely produce low water soluble secondary organic nitrogen aerosols.