Pinus sylvestris L. needle surface wettability parameters as indicators of atmospheric environment pollution impacts: Novel contact angle hysteresis methodology

An investigation of water contact angles (CAs), contact angle hysteresis (CAH) was carried out for 1-year to 4-year old needles (Pinus sylvestris) collected in urban (Gdansk) and rural (Karsin) locations using an original measuring technique based on the geometry of the drop on a vertical filament. Concentrations of air pollutants (SO2, NOx, C6H6, and suspended particular matter - SPM) currently considered to be most important in causing direct damage to vegetation were simultaneously monitored. A set of the surface wettability parameters: the apparent surface free energy gamma(sv), adhesive film tension H, work of adhesion W-Lambda, and spreading W-S, were determined from CAH data using the approach developed by Chibowski (2003) to quantify the surface energetics of the needle substrata affected by aging and pollution impacts. This formalism relates the total apparent surface free energy of the solid gamma(SV) with only three measurable quantities: the surface tension of the probe liquid gamma(LV) and its advancing theta(A) and receding OR contact angle hysteresis. Since CAH depends on the outermost wax layer surface roughness and spatial physicochemical heterogeneity of a solid surface, CA data were corrected using surface architecture profiles registered with confocal scanning laser microscopy. It was found that the roughness parameter r is significantly negatively correlated (R = -0.74) with the needle age (collected at Karsin). The needle surface aging process resulted in its surface hydrophilization (CA and CAH with gamma SV and W(A)t). A temporal evolution of the needles wettability was traced with the data point distribution in the 2D space of CAH plotted versus 14/s. The wettability parameters were closely correlated to pollutant concentrations as evidenced from Spearman's rank correlation procedure (R = 0.63-0.91; p < 0.05). The aim of the study was to validate the established CA methodology to create a new non-invasive, low-cost technique suitable for monitoring of structural changes at interfaces of biological systems. (C) 2013 Elsevier B.V. All rights reserved.