Computer modelling of partial specific volumes of humic substances

The determination of the structure of humic substances from peat soils and natural waters is a major problem in soil science. Humic substances are chemically heterogeneous and consist of molecules covering a wide distribution of molecular size. A quantity related to both molecular size and structure in the hydrated state is the volume of the humic molecules per unit mass or partial specific volume (<(nu)over bar>(2)). The partial specific volumes of humic substances have been estimated from atom and chemical group volume contributions for 17 proposed structures of fulvic and humic acids taken from the literature. The results show that the partial specific volume reflects the composition of humic substances, decreasing with increase in the carbon: hydrogen (C:H) molar ratio. The more oxidized the humic material the smaller is its partial specific volume. These trends agree with our experimental measurements of partial specific volumes for a range of humic materials (aquatic fulvics, aquatic and peat humics). The predicted values of partial specific volumes for the proposed structures, however, are overestimated by approximately 15% compared to the experimental values. There is little difference between values of <(nu)over bar>(2) calculated from the detailed humic structures and those calculated from their empirical formulae; calculations of partial specific volumes using a random modelling approach leads to overestimation by approximately 37%. It seems that the estimates based on additivity of atom and chemical group volumes do not take into account an overall contraction of the structures because of hydrophobic interactions. In general terms the values of the partial specific volumes of humic substances suggest they are more compact molecules than globular proteins, and intrinsic viscometry studies suggest that aqueous salt solutions approach theta-solvent conditions for humic substances.