Molecular Features of Humic Acids and Fulvic Acids from Contrasting Environments.

Insight in the molecular structure of humic acid (HA) and fulvic acid (FA) can contribute to identify relationships between their molecular properties, and further our quantitative abilities to model important organic matter functions such as metal complexation and association with mineral surfaces. Pyrolysis gas chromatography/mass spectrometry (Py-GC-MS) is used to compare the molecular composition of HA and FA. A systematic comparison was obtained by using samples from different environmental sources, including solid and aqueous samples from both natural and waste sources. The chemical signature of the pyrolysates was highly variable and no significant difference between HA and FA was found for major chemical groups, that is, carbohydrates, phenols, benzenes, and lignin phenols, together accounting for 62-96% of all quantified pyrolysis products. However, factor analysis showed that within each sample, FAs consistently differed from corresponding HAs in a larger contribution from mono- and polyaromatic hydrocarbons and heterocyclic hydrocarbons, together accounting for 3.9-44.5% of the quantified pyrolysis products. This consistent difference between FAs and corresponding HAs, suggests that their binding properties may, in addition to the carboxyl and phenolic groups, be influenced by the molecular architecture. Py-GC-MS may thus contribute to identify relationships between HA and FA binding- and molecular-properties.

Selective sorption and desorption of DOM in Podzol horizons - DOC and aluminium contents of leachates from a column experiment.

Complexation of dissolved organic matter (DOM) with cations and minerals contributes to the stabilization of carbon in soils, and can enable the transport of metals in the environment. Hence, a proper understanding of mechanisms that control DOM binding properties in the soil is important for major environmental challenges, such as climate change and stream pollution. However, the role of DOM source in those mechanisms remains understudied. Here, we consider poorly drained tropical Podzols as a model environment to isolate effects of aluminium and DOM on sorption and desorption processes in podzolisation. We collected E- and Bh-horizons from a Brazilian coastal Podzol under tropical rainforest to conduct a column experiment, and percolated the columns with DOM collected from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To quantify sorption and desorption from the columns, leachates were analysed for DOC content, aluminium content, pH, and the amount of fulvic acid relative to humic acid. The results showed large differences in DOC retention between DOM-types, which were consistent over all columns. Retention of DOC in the column varied between 25 % and 92 % for DOM-type Stream, between 33 % and 63 % for DOM-type Peat, between 22 % and 47 % for DOM-type Litter, and between 8 % and 49 % for DOM-type Char. Similarly, desorption from columns with B-horizon material highly differed between DOM-types. Percolation with DOM-types Stream and Peat caused a release of native DOC from B columns that was higher than in those percolated with water only. On the other hand, percolation of B columns with DOM-types Litter and Char caused a net DOC retention. These differences reflect that certain DOM-types hindered desorption, while other DOM-types caused active desorption. The large differences in sorption/desorption between DOM-types implies that changes in environmental conditions may highly influence the fate of soil carbon in Podzols.

Selective sorption and desorption of DOM in podzol horizons - FTIR and Py-GC/MS of leachates from a column experiment.

The sorption of dissolved organic matter (DOM) depends on its interaction with the soil matrix. In hydromorphic podzols, DOM reacts mainly with aluminium (Al), which is responsible for the formation of the Bh-horizon in the subsoil. In this work, we investigated whether the retention of DOM in the soil during the podzolization process is selective in relation to the molecular composition of DOM. A column experiment was conducted to study the selective retention of sorption and desorption processes under controlled conditions. Materials used in the column experiment were representative for Brazilian coastal podzols under tropical rainforest. Materials were collected from this tropical coastal podzol ecosystem, and included soil from E- and Bh-horizons, and DOM from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To evaluate selective retention of DOM, both the initial DOM and its leachates were analyzed by Fourier transform infrared spectra absorption (FTIR) and pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS). The results showed preferential retention of DOM associated with biopolymers for soil columns with E-horizon material (E), E with Al nitrate (E-n), E with kaolinite (E-k) and E with gibbsite (E-h), except for Char. The composition of leachates after percolation through B horizon columns was mainly determined by desorption, and had a relatively large contribution from phenolic and carboxylic groups associated with Al and low molecular weight aromatic and N-containing pyrolysis products, while products from macromolecular materials such as cellulose were selectively retained in the columns for all DOM types. DOM from the Stream (taken during the rainy season) resembled that of desorbed OM from the B columns, reinforcing substantial desorption in the field as well. Our results suggest that sorption and desorption of OM in the hydromorphic Bh-horizon is continuous and that the selectivity of sorption is dependent on DOM source.

Reduced heterogeneity of a lignite humic acid by preparative HPSEC following interaction with an organic acid. Characterization of size-separates by Pyr-GC-MS and 1H-NMR spectroscopy.

Preparative high performance size exclusion chromatography (HPSEC) was used to size-fractionate a humic acid (HA) solution with 0.05 M ionic strength before and after having made the humic solution 0.5 x 10(-3) M in acetic acid (AcOH). Size-fractions were characterized by pyrolysis-gas-chromatography/mass spectrometry (Pyr-GC-MS) and 1H NMR spectroscopy. Pyr-GC-MS showed that the AcOH treatment altered the distribution of humic molecular components in the size-fractions. The unsaturated alkyl chains were moved from size-fractions of larger molecular-size into those of lower molecular-sizes. Most of the aromatic moieties, which were found in larger molecular-size fractions for the untreated HA, were spread into fractions of lower molecular size after AcOH addition to HA. Carbohydrates, which were undetectable in anyfraction of the untreated HA, appeared instead in the pyrogram of the lowest molecular-size and most hydrophilic fraction after treatment with AcOH. Our results suggested that AcOH disrupted the weakly bound association of humic supramolecularstructures and HPSEC elution separated size-fractions of different composition without losing humic matter by adsorption on the HPSEC column. The fractions with the largest apparent molecular size were the richest in alkyl chains, thereby suggesting that humic molecules were stabilized into supramolecular associations by multiple weak interactions among apolar groups such as alkyl chains and aromatic moieties. 1H NMR spectra of size-fractions were greatly simplified and more resolved after AcOH treatment. This was attributed to a less complex molecular association in the size separates which provided a larger solubility in the NMR solvent and more favorable relaxation times. Combination of the procedure used here for size-fractionation with NMR and Pyr-GC-MS methods appears to be promising to advance knowledge on the molecular composition of humic substances.