RESUMEN

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.

RESUMEN

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.

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RESUMEN

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.

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Replacing pastures (PA) with sugarcane (SG) has been deemed an agronomically feasible strategy for sugarcane expansion in Brazil. However, there are some uncertainties about the environmental impacts regarding this land use change (LUC), mainly related to soil organic matter (SOM), a key factor of environmental sustainability of Brazilian ethanol. LUC-related losses of SOM can overcome the C savings from biofuels. The molecular composition of SOM was evaluated to understand the C dynamics regarding LUC from PA to SG, using native vegetation (NV) as reference. Our study area was located in the south-central region of Brazil. Soil sampling was performed at three depths (0-0.1m, 0.2-0.3m and 0.9-1m) in three representative sites with known LUC history and management practice since 1970. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was chosen to study SOM chemistry. Content and isotopic composition of soil organic C and N were also determined. The LUC caused decreases on C and N contents and on δ(13)C isotopic values. Depth was the major factor that influenced SOM composition, while the influence of LUC was mainly evident in surface soils and diminished rapidly with depth. The main difference in SOM composition undergoing the conversion PA-SG was a higher contribution from compounds associated to fresh litter inputs. The high contribution from fresh litter, having a relatively low mean residence time and increasing decomposition rates, is probably a major factor that drives C losses in areas undergoing sugarcane expansion.