Partition coefficients for the binding affinities of pyrene, fluoranthene, and anthracene to 26 different humic materials were determined by fluorescence quenching. Sources included isolated humic acids, fulvic acids, and combined humic and fulvic fractions from soil, peat, and freshwater as well as Aldrich humic acid. Each of the humic materials was characterized by elemental composition, ultraviolet absorbance at 280 nm, molecular weight, and for 19 samples, composition of main structural fragments determined by 13C solution-state NMR. The magnitude of the K oc values correlated strongly with the independent descriptors of aromaticity of humic materials, including atomic H/C ratio, absorptivity at 280 nm, and three interdependent 13C NMR descriptors (CAr - H,R, ΣCAr, ΣCAr/ΣCAlk). Statistical comparison of humic sources grouped by the origin revealed that binding affinities were best predicted by the 13C NMR descriptors, with a slight prevalence of ΣCAr/ΣCAlk ratio, while molecular weight was the poorest predictor. The latter produced either direct or inverse significant correlation with the K oc values depending upon the origin and/or fractional composition of the grouped humic materials.

Recorded molecular weights (MWs) for humic substances (HS) range from a few hundred to millions of daltons. For purposes of defining HS as a specific class of chemical compounds, it is of particular importance to ascertain if this broad range of MWs can be attributed to actual variability in molecular properties or is simply an artifact of the analytical techniques used to characterize HS. The main objectives of this study were (1)to establish if a preferential range of MWs exists for HS and (2) to determine any consistent MW properties of HS. To reach the goal, we have undertaken an approach to measure under standardized conditions the MW characteristics of a large set of HS from different natural environments. Seventy-seven humic materials were isolated from freshwater, soil, peat, and coal, such that each possessed a different fractional composition: humic acid (HA), fulvic acid (FA), and a nonfractionated mixture of HA and FA (HF). Size exclusion chromatography (SEC) was used as the analytical technique to determine molecular weight characteristics. The MW distributions were characterized by number (Mn) and weight (Mw) average MW, and by polydispersity. The complete range of Mw values varied within 4.7-30.4 kDa. The maximum Mw values were observed for peat HF and soil HA, whereas the smallest weights were measured for river water HF. Maximum values of polydispersity (3.5-4.4) were seen for peat HF and soil HA, while much lower values (1.6-3.1) were found for all preparations isolated with XAD-resins. Statistical evaluation showed consistent Mw and Mn variations with the HS source, while polydispersity was mostly a function of the isolation procedure used. A conclusion was made that HS have a preferential range of MW values that could characterize them as a specific class of chemical compounds.

The objectives of this study were to identify molecular features characteristic to arctic DOM from the Kolyma River basin and to elucidate structural imprints induced by a choice of the sorption technique. To achieve this goal, DOM was isolated from the Kolyma River basin with a use of three nonionic sorbents: Amberlite XAD-8 resin, PPL- and C18 - SPE cartridges, and one anion exchanging resin-diethylaminoethyl (DEAE) -cellulose. The structural studies were conducted with a use of electrospray ionization Fourier Transform Ion Cyclotron Resonance (ESI FT-ICR) mass spectrometry and liquid state (1)H NMR spectroscopy. The DOM isolates obtained with a use of PPL and C18 cartridges were characterized with higher content of aliphatic compounds as compared to XAD-8 and DEAE-isolates. In total, for all arctic DOM isolates we observed predominance of hydrogen saturated compounds with high H/C values of identified formulas from FT-ICR MS data. (1)H NMR spectroscopy studies have confirmed this trend and revealed high contribution of alkyl-chain protons into the spectral density of the arctic DOM reaching 43% for PPL isolates.

Partition coefficients for the binding affinities of atrazine to 16 different humic materials were determined by the ultrafiltration HPLC technique. Sources included humic acids (HA), fulvic acids (FA), and combined humic and fulvic fractions (HF) from soil, peat, and coal humic acid. Each of the humic materials was characterized by elemental composition, molecular weight, and composition of main structural fragments determined by 13C solution-state NMR. The magnitude of K(OC) values varied from 87 to 575 L/kg of C, demonstrating relatively low binding affinity of humic substances (HS) for atrazine. On the basis of the measured K(OC) values, the humic materials can be arranged in the following order: coal HA approximately = gray wooded soil HA > chernozemic soil HA and HF > sod-podzolic soil HA approximately = peat HF > sod-podzolic soil FA >> peat dissolved organic matter. The magnitude of the K(OC) values correlated strongly with the percentage of aromatic carbon in HS samples (r = 0.91). The hydrophobic binding was hypothesized as the key interaction underlying the binding of atrazine to HS.

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