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Humic acids (HA) are natural organic compounds that are important components of organic matter. The accumulation, distribution, and fate of tritium-labeled HA prepared from coal were analyzed using wheat (Triticum aestivum L.) seedlings. There was a period of rapid accumulation of HA followed by a slower one in the period from 1 to 24h. There was a significant decrease in HA accumulation at low temperature, indicating that the slower rate of HA accumulation represented a membrane-mediated process. HA distribution in plant tissues was analyzed using autoradiography. In all cases, HA concentration was considerably higher in the roots than in the shoots. Detailed examination of autoradiograms showed that there was preferential accumulation of HA in the apices of roots and shoots of wheat seedlings. Lipid fractions were extracted from seedlings and analyzed with thin layer chromatography and gas chromatography–mass spectrometry. These analyses revealed that labeled HA were present in the neutral lipid fraction consisting mainly of alkanes and alkenes, which are usually found in plant waxes, associated with the cuticle and suberized tissues. Based on these data, it is suggested that HA-derived hydrocarbons may be used in wax biosynthesis. This role could explain the mitigating activity of humic substances under stress conditions.

Natural organic matter as complex biogeochemical non-repetitive material was investigated with ion mobility mass spectrometry (IMS) and ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) approaches in order to unravel the existence of multiply charged state constituents. Hereby we describe and assign the potential molecular formulae of these doubly charged species, derived from FTICR-MS, and the existence of these species was confirmed via IMS. The parallel application of these powerful techniques enabled the boundaries of the understanding of natural organic matter to be pushed further.

Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na-kaolin clay. The adsorption affinity (K L ), maximum adsorption capacity (b), a coefficient of desorption hysteresis (H), and the concentration of irreversibly adsorbed HS (IHS) were derived from adsorption-desorption isotherms. These parameters were correlated with structural features of the HS. The adsorption affinity was shown to correlate directly with the aromaticity of the HS and inversely with their polarity, expressed as the O/C atomic ratio. A dependency between polarity and maximum adsorption capacity was not confirmed. The parameters b, H, Rand IHS expose close correlation with the molecular weight (MW) and the partial negative charge of HS (Z) at the operating pH value. The following quantitative relationship was obtained: b = 715 - 0.06 × MW -529 × Z (r = 0.92). It allows a selection of HS with respect to the largest content of organic matter in HS-kaolin clay complexes. Among the HS studied the high molecular weight materials enriched with C-and H-substituted aromatics, such as coal and peat humic acids (HAs), are shown to be the most preferential materials for preparing stable HS-clay complexes.

Nuclear magnetic resonance (NMR) resonance integrals obtained from one-dimensional NMR spectra provide semiquantitative contents of humic constituents with limited resolution in structural detail. When supplemented by connectivity information available from homo- and heteronuclear two-dimensional NMR spectra a more reliable assignment of humic substructures becomes available. This is demonstrated with a comparative one- and two-dimensional NMR analysis of a fulvic and a humic acid obtained from Eriophorum peat. An example of a detailed analysis of the proton chemical shift region normally attributed to carbohydrates shows substantial contributions from amino acids, amino and desoxy sugars, and highly oxidized aliphatic chains of intermediate length. The very good resolution of structural detail by a combined analysis of all NMR spectra shows that the effect of the fractionation procedure on the composition and chemical structure of humic materials is very significant. The comparison of the partial structures comprising humic acid (HA) and fulvic acid (FA) of the peat humic materials studied indicates that FA is diagenetically downstream of HA, favoring the biopolymer degradation (BD) model of humification.

By transforming the time-based x-axis of electropherograms in capillary zone electrophoresis (CZE) into the corresponding effective mobility-scale, we propose a simple and robust data representation for a better qualitative and quantitative capillary electrophoresis (CE) analysis. The time scale of the raw electrophoretic data (detection signal versus time) is transformed into an effective electrophoretic mobility scale (mu eff-scale) with account of the electroosmotic flow (EOF) peak or of an internal standard of known effective mobility. With the new scaling (detection signals versus effective mobility), the obtained electropherograms are more representative of the velocity-based electrophoretic separation and the comparison of complete electropherograms is directly possible. This is of importance when tracking peaks in real samples where alteration in EOF stability can occur or when comparing electrophoretic runs from different experimental setups (independence in column length and voltage). Beside the qualitative possibilities, a quantitative improvement is achieved in the mu eff-scale with significant better peak area reproducibility and equal to more precision in quantitative analysis than with the primary time-scale integration.

In freshwater ecosystems, dissolved humic substances (HS) can sorb hydrophobic organic chemicals and thereby reduce their bioconcentration and toxicity. The extent of the sorption depends both on the concentration and on the origin of HS. This paper summarizes work that characterized HS from different origins by various spectroscopic and chemical properties, and related these properties to (1) the sorption of polycyclic aromatic hydrocarbons (PAHs) by HS (measured by a fluorescence quenching method), (2) effects of HS on the bioconcentration of PAHs and (3) effects of HS on the toxicity of PAHs. The most powerful predictor of the association between 26 different HS and the PAHs pyrene, fluoranthene, and anthracene was the content of aromatic carbons of the HS. The influence of HS on the bioconcentration of PAHs was investigated by measuring the effect of seven different humic and fulvic acids on the uptake of pyrene and benzo[a]pyrene into the nematode Caenorhabditis elegans. Again, parameters describing aromatic properties of the HS, such as the content of aromatic carbons, or the specific absorptivity at 254 nm gave the best prediction of HS effects on bioconcentration. Studies on the effect of HS on the toxicity of PAHs (impact on grazing activity of Daphnia magna) gave similar results: The detoxifying ability (= reduction of toxicity) of HS could be correlated to the quotient between aromatic carbons and aliphatic carbons in the HS. Taking these results together, we can describe the relationship between structure and effects of HS on bioavailability and toxicity of PAHs as follows: HS associate with PAHs, making the PAHs unavailable for uptake into organisms, and consequently reducing toxic effects of the PAHs. Aromatic properties of the HS can be used to predict the effect of HS in each of these steps.