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Humification is a ubiquitous natural process of biomass degradation that creates multicomponent systems of nonliving organic matter, including dissolved organic matter (DOM) and humic substances (HS) in water environments, soils, and organic rocks. Despite significant differences in molecular composition, the optical properties of DOM and HS are remarkably similar, and the reason for this remains largely unknown. Here, we employed fluorescence spectroscopy with (sub)picosecond resolution to elucidate the role of electronic interactions within DOM and HS. We revealed an ultrafast decay component with a characteristic decay lifetime of 0.5-1.5 ps and spectral diffusion originating from excitation energy transfer (EET) in the system. The rate of EET was positively correlated to the fraction of aromatic species and tightness of aromatic species packing. Diminishing the number of EET donor-acceptor pairs by reduction with NaBH4 (decrease of the acceptor number), decrease of pH (decrease of the electron-donating ability), or decrease of the average particle size by filtration (less donor-acceptor pairs within a particle) resulted in a lower impact of the ultrafast component on fluorescence decay. Our results uncover the role of electronic coupling among fluorophores in the formation of DOM and HS optical properties and provide a framework for studying photophysical processes in heterogeneous systems of natural fluorophores.

The goal of this study was to establish a relationship between the optical properties of soil dissolved organic matter (DOM) and acidic functions carried out by its individual constituents. We obtained 12 fractions of DOM samples using sequential solid phase extraction on nonionic sorbent at steadily lowered pH values: 7, 5, 3, 2, which correspond to low bounds of p

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.

The objective was to study plutonium partitioning between immobile and mobile humic materials at the water-solid interfaces. Immobilization of the humic materials on solid supports was performed in situ using self-adhesive silanized humic derivatives. The presence of the humic adlayers on solid supports was shown to significantly enhance Pu sorption and its retention under both steady state and dynamic conditions. While plutonium may exist in multiple oxidations states plus colloidal forms, the major thrust in this work was to study the behavior of most mobile--the PuO2(+) form in dilute solutions. The values of the plutonium partition coefficients (Kd) between water and humics-coated silica gels after 10 days exposure reached 1.6 × 10(4) L · kg(-1) at pH 7.5 under anaerobic conditions with a total plutonium concentration of 1.2 × 10(-8) M exceeding those for the uncoated SiO2 (6.3 × 10(2) L · kg(-1)). Column tests showed substantial sequestration of water-borne plutonium (up to 73%) on the humics-coated silica gels. Remobilization experiments conducted under batch conditions at different pH values (3.5, 4.5, 7.5) showed that no more than 3% of the sequestered Pu was remobilized from the humics-coated silica gels by treatment with dissolved humic materials at environmentally relevant pH of 7.5. Consequently, silanized humic materialas can be seen as both molecular probes and as potent candidate materials for scavenging mobile Pu from an aqueous phase.

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.

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 HAchernozemic soil HA and HFsod-podzolic soil HA approximately = peat HFsod-podzolic soil FApeat 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.

Effects of 27 different humic materials on the toxicity of polycyclic aromatic hydrocarbons (PAH) were studied for crustacean Daphnia magna. Sources included isolated humic acids, fulvic acids, and their combination from soil, peat, and freshwater. The PAH used were pyrene, fluoranthene, and anthracene. The observed reduction in toxicity of PAH in the presence of humic substances (HS) was shown to be a result of the detoxification effect caused by the chemical binding of PAH to HS and of the direct effect of HS on D. magna. An approach was developed to quantify the detoxifying impact of humic materials related to their chemical binding to PAH with a use of the "constant of detoxification" or "toxicological partition coefficient" K(oc)D. The latter was proposed to determine by fitting the experimental relationships of the detoxification effect versus concentration of HS. The obtained K(oc)D values were well tracked by the corresponding partition coefficients determined by the fluorescence quenching technique (K(oc)fq): K(oc)D=b x K(oc)fq, b (mean+/-Cl, n=26, P=95%)=2.6+/-0.3, 4.6+/-0.6, and 6.0+/-1.4 for pyrene, fluoranthene, and anthracene, respectively. The predictive relationships between the structure and detoxifying properties of humic materials in relation to PAH were developed. It was shown that the magnitude of the K(oc)D values correlated closely with the aromaticity of humic materials characterized with the 13C NMR descriptors (sigma(C)Ar, sigma(C)Ar/sigma(C)Alk) and atomic H/C ratio. The obtained relationships showed the highest detoxifying potential of the humic materials enriched with aromatics and allowed a conclusion on the chemical binding as the governing mechanism of the mitigating action of HS on the toxicity of PAH.