Klaas G.J. Nierop

Origin of aliphatic compounds in a forest soil.

Abstract The aliphatic organic matter fraction in a forest soil in the Leuvenum Forest (central Netherlands) was examined by pyrolysis–GC/MS and thermochemolysis. In addition, roots were analyzed for their aliphatic composition. Pyrolysis of soil organic matter and the roots revealed an alkene and alkane pattern, usually attributed to cutan or suberan, whereas thermochemolysis elucidated the presence of suberin. The origin of the soil organic matter could be largely ascribed to root input.

Composition of plant tissues and soil organic matter in the first stages of a vegetation succession

Differences in soil organic matter (SOM) composition in consecutive soil profiles (under algae, grass, moss, heather and pine) from a primary vegetation succession (central Netherlands) were investigated by Cross Polarization-Magic Angle Spinning (CPMAS) 13C NMR, chemical degradation (acid hydrolysis of polysaccharides) and pyrolysis-GC/MS (Py-GC/MS) in relation to the vegetation. All mineral soil horizons had lower contents of polysaccharides than the ectorganic layer and/or the fresh plant material as suggested by the diminishing O-alkyl peaks by NMR. The monosaccharide distribution pointed to an increase of microbial sugars in the soil as suggested by the raising C6/C5 ratios. Soil polysaccharides may be accompanied by a significant contribution of carbohydrates from mosses in the first stages, because the undecomposed moss tissues have high C6/C5 ratios, which falsify the usual interpretation that such high ratios may be due to microbial sugars. Fresh litter and ectorganic layers under heather and pine had similar contents of aromatics, but the contribution of lignin (guaiacols and syringols) was lower in the ectorganic horizons. The degree of oxidation, as determined by the acid/aldehyde ratio, increased with progressive humification. All Ah horizons contained less aromatics, more oxidized lignin remnants and higher amounts of aliphatic compounds than the litter. One or two macromolecules, which produced n-alkenes/n-alkanes and branched alkenes/alkanes upon pyrolysis and were derived from mosses, were mainly responsible for the accumulation of aliphatics in soil, although other aliphatic polymers, such as suberin, might also play an important role. Preservation of components from earlier vegetation might significantly influence SOM composition.

Amorphous and condensed organic matter domains: the effect of persulfate oxidation on the composition of soil/sediment organic matter

The composition of amorphous and condensed soil/sediment organic matter (SOM) domains was investigated for one soil sample and four sediment samples. These samples were oxidized with persulfate to remove amorphous SOM, before and after which the composition of SOM was studied by thermogravimetric analysis, pyrolysis-GC/MS, and cross polarization magic angle spinning 13C-NMR. Comparison of the SOM composition before and after oxidation showed that condensed SOM was more thermostable and less polar than amorphous SOM. Condensed SOM was relatively low in O-alkyl C and carboxyl C and it was likely to contain only small amounts of labile organic components (carbohydrates, peptides, fatty acids). Apart from these general characteristics, the composition of the condensed and amorphous domains appeared to be highly dependent on the origin and nature of the SOM investigated. Condensed domains in relatively undecomposed SOM were enriched in aliphatic C, whereas condensed domains in relatively weathered SOM were enriched in aromatic C. Altogether, the compositional changes upon persulfate oxidation were similar to the compositional changes upon humification, which supports the idea that weathered SOM is more condensed than the original material.

Dissolved organic matter, aluminium and iron interactions: precipitation induced by metal/carbon ratio, pH and competition

To better understand the precipitation behaviour of dissolved organic matter induced by interactions with metals, a systematic titration experiment was conducted mimicking the soil solution conditions in an acidic, sandy soil. The variables of interest included the type of metal species (Al, Fe), the redox state [Fe(II), Fe(III)], the pH (3.5, 4.0, 4.5), the metal to organic carbon (M/C) ratio and the competition between Al and Fe. Precipitation of DOM-Al appeared to be strongly correlated with M/C ratio and the pH. For Fe(II) only little precipitation occurred, while the strongest flocculation degree was found after addition of Fe(III). In contrast to Al, hardly any correlation between DOM-Fe precipitation and pH was observed. Both reduction and oxidation of Fe was found and exhibited a strong effect on the precipitated amounts of DOM and Fe. In competition, Al determined the precipitation behaviour at lower M/C ratios (<0.10), while at higher M/C ratios Fe determined the flocculation. Below a M/C ratio of 0.06 Al was the dominant metal in the precipitates, especially at lower pH levels, while the opposite trend was found at M/C ratios above 0.06. Overall, Fe(III) gave the strongest flocculation, although Al influenced the impact of Fe(III) interactions with DOM in relation to pH and M/C ratio.

Occurrence and distribution of ester-bound lipids in Dutch coastal dune soils along a pH gradient

The base-hydrolysable fraction of roots and soil organic matter (SOM) in mineral subsoils from oak forests (coastal dunes, The Netherlands) with a soil pH varying from pH (CaCl2) 6.9 to 3.5 were analysed both quantitatively and qualitatively. Comparison of thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide (TMAH) with base hydrolysis data confirmed that base hydrolysis is an efficient way of analysing ester-linked compounds in soils. The compounds released from SOM upon base hydrolysis comprised largely suberin-derived lipids, which were clearly related to the oak vegetation and, in particular, to oak roots. Compared with fresh (fine) roots, which are largely responsible for the input of SOM in the subsoils, unsaturated and epoxy compounds decreased in soil, probably due to oxidation. The amounts of the saponifiable fraction increased upon acidification, whilst hardly any changes were observed in their composition. This accumulation, without significant compositional alteration of ester-bound moieties in acidic soils, indicates that these chemically labile compounds can be preserved in soils.

Mobility of Fe(II), Fe(III) and Al in acidic forest soils mediated by dissolved organic matter: influence of solution pH and metal/organic carbon ratios

Abstract The mobility of Al and Fe in acidic sandy forest soils is greatly influenced by interactions with dissolved organic matter (DOM). We determined the distribution of Al, Fe(II) and Fe(III) over dissolved ‘free’ metal, dissolved metal–DOM complexes and metal–DOM precipitates as influenced by solution pH, redox potential and metal/organic carbon (M/C) ratios. For this, we used water extracts of the Oh horizon of a Fimic Anthrosol brought at pH=3.5, 4.0 and 4.5, and added increasing amounts of Fe(II), Fe(III) and Al. For all three metals, soluble metal–DOM complexes were dominant at low M/C ratios (

Synthesis and photopolymerization of cholesteric liquid crystalline diacrylates

Abstract The synthesis of chiral liquid crystalline diacrylates is described. By mixing one of them with non-chiral liquid crystalline diacrylates. cholesteric phases are obtained of which the wavelength of reflection can be chosen by the composition of the mixture. After isothermal photopolymerization of the mixture a crosslinked network is obtained with thermally stable properties.

Management induced organic matter differentiation in grassland and arable soil: a study using pyrolysis techniques

Abstract Differences in agricultural management and land use lead to differences in soil structure, soil organic matter (SOM) dynamics and composition. We investigated the SOM composition at three depth layers in a permanent pasture (PP), an organic arable (OA) and a conventional arable (CA) field within one soil series in marine loam deposits in The Netherlands. Both arable fields were in the grass phase of the rotation. The chemical composition of SOM was determined by a combination of conventional pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and of thermally assisted hydrolysis and methylation (THM) with tetramethylammonium hydroxide (TMAH). In PP, SOM was composed of relatively little decomposed, mainly grass-derived material comprising polysaccharides, lignin, aliphatic compounds (extractable lipids, cutin, suberin) and proteins. With depth, plant-derived constituents decreased, whereas microbial and humified material predominated. Both arable soils contained mainly strongly humified plant material and microbially altered proteineous material that showed heterocyclic N-compounds together with alkylbenzenes and phenols upon pyrolysis. With THM small traces of plant-derived alkanols and cutin/suberin were observed in the arable soils. The upper layers of OA contained little lignin, which can only be derived from the grass vegetation or manure inputs since last ploughing (2 years before) since it was not found in the whole plough layer. Overall SOM composition is therefore hardly affected by organic farming compared to conventional management. The differences in SOM content and composition between the pasture and arable fields can be ascribed to differences in input and depth distribution of fresh organic materials. But a difference in physical protection of easily mineralisable SOM between pasture and arable soils is also likely to contribute.

Organic matter formation in sandy subsurface horizons of Dutch coastal dunes in relation to soil acidification

Abstract Subsurface horizons contain considerable amounts of soil organic matter (SOM), which has generally a relatively recalcitrant nature and may be an important key in the examination of the role of soils in the sequestration of carbon. Nonetheless, this part of SOM is hardly studied. This paper focuses on the effects of soil acidification on the formation of SOM in sandy subsurface horizons under Corsican pine ( Pinus nigra var. maritime ) and common oak ( Quercus robur L.) forests in coastal dunes (The Netherlands) as characterized by pyrolysis and thermally assisted hydrolysis and methylation. In the pine forests of 50–70 y old SOM appeared to be only slightly affected by soil pH, whereas SOM from oak forests (100–200 years) showed pronounced changes upon soil acidification. With decreasing soil pH in the oak forests, lignin was more degraded (decrease in syringyl/guaiacyl ratio, reduction of the relative concentration) and the contribution of suberin-derived aliphatic moieties increased. The latter compounds may therefore play an important role in the formation of SOM in the studied subsoils.

Temporal and vertical organic matter differentiation along a vegetation succession as revealed by pyrolysis and thermally assisted hydrolysis and methylation

Abstract The origin and chemical nature of soil organic matter (SOM) in the ectorganic (L, F and H) horizons from four profiles from different stages of a primary vegetation succession on drift sand was studied to evaluate the impact of the vegetation on organic matter formation. In addition, the main sources of SOM, i.e. needles, leaves and (fine) roots of the covering species were analysed. Using conventional pyrolysis, virtually no differences were found between profiles in the same pine forest but with (chemically) different undergrowths ( Deschampsia flexuosa vs. Empetrum nigrum ) that clearly delivered leaf and root litter to SOM. Thermally assisted hydrolysis and methylation (THM) of the same samples released compounds that were not detected by conventional pyrolysis without methylation. These compounds included methyl ethers and methyl esters of ((poly)hydroxy)alkanoic acids and were identified as building blocks of cutin and suberin. Both biopolymers appeared to be better tracers of the various inputs of plant material than lignin, particularly in case of the most humified SOM. Although there was evidence of alteration of cutin and suberin compositions in the course of the succession in the beech forest, an inventory was still possible of above- and below ground litter as sources of SOM.