Structural and thermodynamic signatures of marine microlayer surfactant films

Natural surface film experiments in inland waters and shallow offshore regions of the Baltic and Mediterranean Seas were carried out in the time period 1990–1999 under calm sea conditions using a novel device for sampling and force-area studies. The sampler-Langmuir trough-Wilhelmy filter paper plate system ‘cuts out’ an undisturbed film-covered sea area to perform π-A studies without any initial physico-chemical sample processing. The limiting specific area Alim (2.68–31.57 nm2/molecule) and mean molecular mass Mw (0.65–9.7 kDa) of microlayer surfactants were determined from the 2D virial equation of state applied to the isotherms. Enthalpy ΔH and entropy ΔSt of the 2D first-order phase transitions were evaluated using the Clausius-Clapeyron equation applied to the isotherms. Miscibility of film components and film structure evolution is expressed by the scaling exponent y adopting the 2D polymer film scaling theory. The stress-relaxation measurements revealed a two-step relaxation process at the interface with characteristic times τ1=1.1–2.8 and τ2=5.6–25.6 seconds suggesting the presence of diffusion-controlled and structural organisation relaxation phenomena. The obtained results suggest that natural films are a complex mixture of biomolecules covering a wide range of solubilities, surface activity and molecular masses with an apparent structural organisation exhibiting a spatial and temporal variability.