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The applicability of environmental scanning electron microscopy (ESEM; imaging of hydrated samples) and conventional high vacuum scanning electron microscopy (SEM; imaging of dried samples at high vacuum) for the observation of natural aquatic colloids and particles was explored and compared. Specific attention was given to the advantages and limitations of these two techniques when used to assess the sizes and morphologies of complex and heterogeneous environmental systems. The observation of specimens using SEM involved drying and coating, whereas ESEM permitted their examination in hydrated form without prior sample preparation or conductive coating. The two techniques provided significantly different micrographs of the same sample. SEM provided sharper images, lower resolution limits (10 nm or lower), but more densely packed particles, suggesting aggregation, and different morphological features than ESEM, suggesting artefacts due to drying. ESEM produced less easily visualised materials, more complex interpretation, slightly higher resolution limits (30-50 nm), but these limitations were more than compensated for by the fact that ESEM samples retained, at least to some extent, their morphological integrity. The results in this paper show that SEM and ESEM should be regarded as complementary techniques for the study of aquatic colloids and particles and that ESEM should be more widely applied to aquatic environmental systems than hitherto. © The Royal Society of Chemistry 2005.

The binding of Eu to fulvic acid (FA) as a function of pH was determined by Schubert's method and by equilibrium dialysis. Data obtained by both methods showed a strong pH dependence, which was reproduced well by the model used to interpret the data (humic ion-binding model VI). The model was also able to account for five other data sets from the literature, and there was reasonable agreement among the values of the characteristic binding parameter for Eu–FA interactions. Data sets investigating the effects of aluminum competition were also explained well by Model VI. The model was used to calculate the speciation of Eu in natural waters as a function of the most-likely competitive solution species (protons, aluminium and calcium). The calculations indicate that under environmentally realistic concentrations both, aluminium and calcium can be significant competitors at low and high pH, respectively, although FA binding appears to dominate Eu speciation under most conditions.

Sequential extractions, according to a modified scheme proposed by Tessier et al. (Tessier A, Campbell PGC, Bisson M. Sequential extraction procedure for the speciation of trace metals. Anal Chem 1979;51:844–851), were performed on suspended particulate material (SPM) from the River Mersey, North-West England. The resulting solid-phase fractions were spiked with trace levels of Cd and Cu and their metal-binding properties were investigated as a function of pH. The results indicated that metal binding decreased as the material was successively extracted, i.e. the unextracted fraction bound the most metal, while the particles which had undergone all of the extractions bound the least metal. This effect was attributed to the loss of particle mass during the extractions and to the relative metal affinities of the newly exposed surfaces. The exposure of new potential binding sites was not an overriding influence on metal binding. The strongest binding of Cd appears to be to the nominal manganese oxyhydroxide phase, with no measurable binding of Cd by the residual mineral fraction. By contrast, the nominal iron and manganese oxyhydroxides, organic material and the residual mineral fraction all appear to affect Cu binding significantly. The effect of the extractions on the particles was also investigated by transmission electron microscopy. Micrographs indicated that the biological material in the sample had undergone significant alteration after treatment with the first and second extractants (acetate and hydroxylamine, respectively), i.e. before removal of the nominal organic fraction. These changes in biological material may affect metal binding, complicating the interpretation in terms of simple mineral and organic phases.

The binding of europium and americium by an aquatic fulvic acid was investigated using an equilibrium ion exchange technique (Schubert's method). The results for europium were consistent with literature data. Americium gave anomalous results for both the Do values (partition coefficient of the metal between the resin and solution phases in the absence of the fulvic acid) and D values (partition coefficient of the metal between the resin and solution phases in the presence of the fulvic acid). The values for americium were unexpectedly low and, in the case of D values, only slightly pH dependent. The cause of the discrepancy was found to be the partial dissolution of the resin or the loss of small colloidal material from the resin. The effects on the europium results were minimal due to the use of lower resin weights and higher metal concentrations.

Humic substances (HS) were extracted from the soil and water of an upland catchment and characterised with respect to molecular weight, C, H, O, N and S contents and ash content. Three samples were obtained: peat humic acid, aquatic humic acid and aquatic fulvic acid. The weight average molecular weights were found to increase from 2400 for aquatic fulvic acid, to 6300 for aquatic humic acid and to 16500 for peat humic acid. Acid-base titrations were performed to assess the proton binding behaviour at different ionic strengths in NaCl and in the presence of important cation competitors (calcium and magnesium). The results from the titrations were fitted to a recently developed discrete-site/electrostatic model of cation-humic binding. Model parameters showed systematic trends with molecular weight and good agreement with parameters derived from the analysis of literature data. In the order peat humic, aquatic humic and aquatic fulvic acid, the milli-equivalents of carboxylic acid groups per gram of HS (nA) increased. In the same order both the negative log10 of the mid-range intrinsic proton dissociation constant for the strong acid groups (pKA) and the empirical constant, P, which accounts for electrostatic effects, decreased.