Water-soluble main ions in precipitation over the southeastern Adriatic region: chemical composition and long-range transport

Background, aim and scope Precipitation samples collected from 1995 to 2000 at meteorological station in the eastern outskirts of Herceg Novi (Montenegro) were analysed on Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, NO₃ ⁻ and NH₄ ⁺. Four-day backward trajectory simulations were conducted during the precipitation period to investigate the regional transport of main ions and their deposition in the region of the southeastern Adriatic Sea. The air mass trajectories were classified into six trajectory categories by the origin and direction of their approach to Herceg Novi. Materials and methods A bottle and funnel with a small net between them was used for sampling at a height of 1.5 m above the ground. The concentrations of Cl⁻, NO₃ ⁻, NH₄ ⁺ and SO₄ ²⁻ were determined spectrophotometrically, the concentrations of Na⁺ and K⁺ were determined by the FAES method and the concentrations of Mg²⁺ and Ca²⁺ by the FAAS method. The factor analysis technique (PCA analysis) based on the calculation of the factors was employed to differentiate the contribution of emission sources to the content of the main ions in the precipitation. The obtained data sets were processed using the SPSS 11.5 statistical program. The Hybrid Single-Particle Lagrangian Integrated Trajectory model was used to study the air origin for the city of Herceg Novi (42°27′N, 18°33′E), Montenegro. Discussion The following origins of the air masses were considered: northern Europe (NE), eastern Europe-northeastern Europe (EE-NE); eastern Mediterranean-southeastern Europe (EM-SE); Africa-Central Mediterranean (A-CM); western Mediterranean (WM); western Europe-Central Europe (WE-CE) and undefined. The heights and frequencies of precipitation coming by air masses from northern Europe and eastern-northeastern Europe are the lowest. On the contrary, the heights and frequencies of precipitation coming by air masses from the western Mediterranean (36.6%) and Africa and the Central Mediterranean (30.6%) are the highest. The sea salt components (Na⁺, Cl⁻, Mg²⁺) are significantly correlated, except for air masses originating from the northern and eastern European regions. Significant correlations between SO₄ ²⁻ and NO₃ ⁻ are found in air masses coming from the western Europe and North Africa, over the Mediterranean. Conclusions The highest volume-weighted mean (VWM) of: SO₄ ²⁻ , NH₄ ⁺ and Mg²⁺ are for precipitation from EE-NE while the highest values of VWM of Cl ⁻ are from WM and of K⁺ are from WE-CE. Long-range transport of Sahara dust is confirmed. Recommendations and perspectives For better estimation of origins of water-soluble ions in precipitation expanding list of analysis on anions of organic acids, such as HCOO⁻, CH₃COO⁻, and C₂H₂COO⁻, could be indicative of volatile organic compounds emitted by vegetation but also traffic. The chemical composition of precipitation together with a study of air backward trajectories is the proper tool for tracking the long-range transport of water-soluble ions and estimating transboundary pollution.