ALBERT

Notes: This study tested the hypothesis that, like dissolved organic nitrogen (N), dissolved organic phosphorus (P) and sulphur (S) are more mobile in soil than is organic carbon (C). To do so, I compared the sorption of organic P and S to subsoil materials with that of organic C. Soil samples were equilibrated with water-soluble organic matter from the forest floor at pH 4 and in the equilibrium solutions organic C, P, and S, and their distributions between the hydrophilic and hydrophobic fraction were determined. Sorption of C within the organic matter did not differ from that of P and S. However, the hydrophilic fraction contained the vast majority of P and S and sorbed far less than the hydrophobic fraction. So the overall retention of organic P and S was smaller than that of organic C. This result suggested that dissolved organic matter is more important in the loss of plant nutrients than in the release of C from soil.

Notes: Dissolved organic matter is important in translocation and export of nutrients from forest ecosystems. Its mobility in soil is restricted by sorption to mineral surfaces which depends on its chemical properties. Carboxyl and hydroxyl groups form strong bondings to mineral surfaces, whereas the role of N-containing functional groups in the sorption process is less well understood. We examined in laboratory experiments the binding of dissolved organic matter from the forest floor to amorphous Al(OH)3, goethite, kaolinite, and illite and to subsoils in order to compare the sorption and desorption of dissolved organic C with that of dissolved organic N. The mineral samples were equilibrated with acidic solutions of organic matter at pH 4. In the equilibrium solutions organic C and N and their contribution to two operationally defined fractions, namely the so-called hydrophilic and hydrophobic fractions, were determined. We measured neutral and acidic amino sugars to discover the nature of the binding of organic N. Within the hydrophilic and hydrophobic fractions, the sorption and desorption of organic C and N did not differ, indicating that there was no preferential binding of N-containing compounds. The hydrophilic fraction contained more N and sorbed less than the hydrophobic fraction, and so the overall retention of organic N by the mineral phases and subsoils was smaller than that of organic C. Among the amino sugar compounds, muramic acid was preferentially removed from the solution, whereas the neutral amino sugars were sorbed similar to organic C. The results suggest that the sorption of N-containing compounds is favoured by acidic groups and not by amino groups.

Notes: The organic carbon content of soil is positively related to the specific surface area (SSA), but large amounts of organic matter in soil result in reduced SSA as determined by applying the Brunauer–Emmett–Teller (BET) equation to the adsorption of N2. To elucidate some of the controlling mechanisms of this relation, we determined the SSA and the enthalpy of N2 adsorption of separates with a density 〉 1.6 g cm−3 from 196 mineral horizons of forest soils before and after removal of organic matter with NaOCl. Likewise, we investigated these characteristics before and after sorption of increasing amounts of organic matter to four mineral soil samples, oxides (amorphous Al(OH)3, gibbsite, ferrihydrite, goethite, haematite), and phyllosilicates (kaolinite, illite).Sorption of organic matter reduced the SSA, depending on the amount sorbed and the type of mineral. The reduction in SSA decreased at larger organic matter loadings. The SSA of the mineral soils was positively related to the content of Fe oxyhydroxides and negatively related to the content of organic C. The strong reduction in SSA at small loadings was due primarily to the decrease in the micropores to which N2 was accessible. This suggests preferential sorption of organic matter at reactive sites in or at the mouths of micropores during the initial sorption and attachment to less reactive sites at increasing loadings. The exponential decrease of the heat of gas adsorption with the surface loading points also to a filling or clogging of micropores at early stages of organic matter accumulation. Desorption induced a small recovery of the total SSA but not of the micropore surface area.Destruction of organic matter increased the SSA of all soil samples. The SSA of the uncovered mineral matrix related strongly to the amounts of Fe oxyhydroxides and the clay. Normalized to C removed, the increase in SSA was small in topsoils and illuvial horizons of Podzols rich in C and large for the subsoils containing little C. This suggests that micropores preferentially associate with organic matter, especially at small loadings. The coverage of the surface of the soil mineral matrix as calculated from the SSA before and after destruction of organic matter was correlated only with depth, and the relation appeared to be linear.We conclude that mineralogy is the primary control of the relation between surface area and sorption of organic matter within same soil compartments (i.e. horizons). But at the scale of complete profiles, the surface accumulation and stabilization of organic matter is additionally determined by its input.

Notes: Sorption on the mineral matrix is an important process restricting the movement of dissolved organic matter (DOM) in soils. In this study, we aimed to identify the chemical structures responsible for the retention of DOM by sorption experiments with total DOM and acidic humic substances (AHS), containing humic and fulvic acids, on soil samples and minerals (goethite, ferrihydrite, and amorphous Al(OH)3). The AHS remaining in solution after sorption were studied by 13C nuclear magnetic resonance (NMR) analysis, and total DOM and AHS for bed on the surfaces of minerals by diffuse reflectance Fourier-transform infrared (DRIFT) spectroscopy. The soil samples were taken from strongly sorbing Bw horizons of two Inceptisols rich in pedogenetic Fe (29 and 35 g kg −1) and containing little C (7 and 22 g kg−1). The 13C-NMR spectra showed that sorption causes a preferential removal of aromatic and carboxyl C from the solution, whereas alkyl-C accumulates in the solution. No change was observed for O-alkyl C. The DRIFT spectra of sorbed total DOM and AHS showed a relative increase of the band intensity of carboxyl groups compared to DOM in the initial solution, confirming the importance of those groups for the sorption to mineral surfaces. The spectra also indicated reactions of carboxyl groups with metals at the mineral surfaces. The extent to which the carboxyl groups are bound depended on the surface coverage with DOM and the type of mineral.

Notes: Isotopic fractionation of dissolved organic carbon percolating through the soil is often interpreted as due to microbial transformation. We investigated the potential effects of sorption on the δ13C of dissolved organic C in field and laboratory experiments. We sampled the organic C in soil water at two forested sites and measured sorption with intact mineral soil and individual minerals (dolomite, ferrihydrite, goethite, and quartz). The dissolved organic C was separated into hydrophilic and hydrophobic fractions using a resin approach. The δ13C values of bulk soils, alkaline-extractable organic C, and dissolved organic C and its fractions were measured. Hydrophilic and hydrophobic fractions in forest floor seepage water were characterized by 13C-NMR spectroscopy.At both sites, δ13C of dissolved organic C increased with increasing depth, suggesting that decomposition contributes to the loss of the dissolved organic C. However, there was an enrichment of hydrophilic organic C in the soil solution as the water moved down the soil. The δ13C values of hydrophilic fractions were less negative than those of hydrophobic fractions. The smaller δ13C in the hydrophobic fraction was due to the large contribution of compounds derived from lignin that are depleted in 13C. As the isotope composition of both fractions of dissolved organic C did not change throughout the profile, changes in δ13C of total organic C reflected changes in the relative proportions of its hydrophilic and hydrophobic fractions. The sorption experiments with minerals and soil cores gave similar results. When dissolved organic C came into contact with mineral material, the δ13C of that remaining in solution increased due to preferential sorption of the 13C-depleted hydrophobic fractions. Moreover, the soils released hydrophilic organic C with large δ13C values, increasing the δ13C of organic C in effluents from soil compared with that in the inflow. Thus, selective sorption of organic C fractions changes δ13C in a way that mimics metabolic transformation and decomposition.

Notes: 3 , goethite, and a subsoil low in organic C. These sorbents were equilibrated with increasing amounts of water-extractable NOM from the Oa horizon of a mor forest-floor layer and then extracted with solutions of different ionic strengths, pH, and concentrations of inorganic anions (Cl−, SO2− 4, H2PO− 4). Sorbed NOM was extracted after 24, 48, 72, and 120 h. We investigated structural and functional characteristics of the desorbed NOM by XAD-8 (macroporous resin) fractionation and by 13C-NMR spectroscopy. Desorption of NOM from minerals and soils was negligible (〈3%) under solution conditions similar to those during the sorption (hysteresis). It was not influenced by increasing concentrations of noncompeting inorganic anions such as Cl−. Increased concentrations (≤0.1 M) of competing anions like SO2− 4 or H2PO− 4 increased the NOM desorption. Though H2PO− 4 was most efficient in desorbing NOM, the extractability was only ≤60% at the highest H2PO− 4 concentration. The most significant desorption occurred when solution pH was raised. For goethite, NOM desorption reached a maximum at a pH above the point of zero charge (PZC) of the mineral. With increasing surface coverage of the sorbent by NOM, the proportion of desorbable NOM decreased for all extractants. Increased sorption hysteresis was also observed with an increasing time period between sorption and desorption. The desorption was more pronounced for NOM compounds that exhibit hydrophilic properties and have low contents of aromatic structures and carboxyl groups. The irreversible binding of NOM, especially of the lignin-derived portion, to soil minerals seems to result from its polyelectrolytic nature. This may favor the formation of multi-site coordinative bonds and effective shielding of the binding ligands by other parts of the sorbed