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Nanoscale surface films are known to develop on surfaces exposed to natural waters and have potential impacts on many environmental processes. A new method using atomic force microscopy is presented which physically removes the developed film in a defined area and then quantifies the difference in height between the film and the area where the film has been removed. The difference gives the absolute thickness of the surface film, which has not previously been measured. Suwannee River humic acid was exposed to substrates, and the surface film thickness as a function of pH and exposure time was measured. Discrete and very small colloids in the range 1-5 nm were observed as expected, and these sat on a coherent surface film, notthe original mica substrate. Low pH values of 2 gave rise to relatively thick surface films of about3 nm, although these films were not continuous at higher pH values. At pH 4.8, the film thickness increased with exposure time up to about 5 h and did not subsequently increase. The maximum film thickness measured was about 1 nm at that pH. The method is applicable to the measurement of many environmental surfaces, although resolution will depend on the substrate and film roughness.

Measurements of the diffusion coefficients of five different humic substances (HS) have been performed in water and in agarose hydrogels at several pH values (in the range of 3-10) and gel concentrations (in the range of 0.7-3% w/w). Fluorescence correlation spectroscopy (FCS) and classical diffusion cells were used in parallel to probe diffusion over both microscopic and mesoscopic distance scales. In general, agreement between the techniques was reasonable, which indicated that local nonhomogenities in the gel did not play an important role. Diffusion coefficients (D) in the gel were generally in the range of 0.9-2.5 x 10(-10) m2 s(-1) but were generally only 10-20% lower than in solution. At low pH values, one of the studied humic substances (a peat humic acid, PPHA) formed large aggregates that could not penetrate into the gel and therefore could not be defined by a single D value. The observed decreases of D in the gel for other HS were too large to be explained by the tortuousity and obstructive effects of the gel alone. D decreased slightly with increasing gel concentration and increased slightly with pH. Because modifications of D due to pH were similar in both the gel and the free solution, it is unlikely that complexation with the gel was greatly influenced by the pH. Rather, the main effect that appeared to decrease the diffusive flux in gels was likely small increases in the hydrodynamic radii of the humic macromolecules. An anomalous diffusion model was used to describe the FCS data in the gel. The characteristic exponent determined by fitting the autocorrelation functions with this model decreased only slightly (from 0.96 to 0.90) with increasing gel concentration providing support that HS complexation with the gel fibers was not very important. The results have important implications for our understanding of the fate and behavior of the HS and their associated pollutants and for interpreting metal speciation data obtained using gel-covered analytical sensors.