Particle water and pH in the eastern Mediterranean: source variability and implications for nutrient availability

Abstract. Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (W_inorg) and organic (W_org) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope  =  0.92, R²  =  0.8, n  =  5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for W_org with morning and afternoon average mass concentrations being 10–15 times lower than nighttime concentrations, thus rendering W_inorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m⁻³, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, W_org, was equal to 0.56 ± 0.37 µg m⁻³; thus, organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening, and nighttime hours.

The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air mass origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.