No abstract

A simple densimetric method for the separation of free and occluded particulate organic materials was developed and applied to five virgin soils. The free organic matter was isolated by suspending the soil in sodium polytungstate solution (d = 1.6 Mg m-3) and decanting the light material. The remaining soil was disaggregated by sonification for liberation of occluded organic materials. The free light fraction consisted of large, undecomposed or partly decomposed root and plant fragments. This fraction comprised 0.59-4.34% of soil dry weight and accounted for 6.9-31.3% and 5.9-22.1% of total soil carbon and nitrogen respectively. Identifiable components of the occluded fraction were small particles of incompletely decomposed organic residues, pollen grains, particles of plant tissue such as lignin coils and phytoliths. This fraction comprised 0.69-1.81% of soil dry weight and represented 9.2-17.5% and 6.2-14.1% of the total soil carbon and nitrogen. The proportion of soil organic carbon recovered as the occluded fraction was high in soils with high clay contents. The chemical composition of occluded and free organic materials was investigated by solid-state 13C CP/MAS NMR spectroscopy. Despite the differences in soils, environmental conditions and vegetation, the organic structure of the free light fraction was similar in four of the five soils. This fraction consisted of 55-63% O-alkyl C, 18-25% alkyl C, 14-18% aromatic C, and 5-7% carbonyl C. In the other soil, this fraction showed a higher proportion of alkyl C (31%) and lower O-alkyl C (46%). Most of the differences between soils were associated with organic materials contained in the occluded light fraction. The differences in chemical structure between the occluded light fraction and free light fractions were similar in all examined soils. The NMR data showed that the proportion of O-alkyl C was lower and alkyl C higher in the occluded light fractions than in the free light fractions. The proportion of aromatic and carbonyl carbon was higher in the occluded fractions of three soils while the percentage of these two types of carbon remained unchanged in the two other soils. It is considered that the occluded organic matter is an old pool of carbon that has been accreted within aggregates during decades of root growth and it is that pool which is lost due to cultivation.

The nature of organic carbon in the <2, 2-20, 20-53, 53-200, and 200-2000 pm fractions of four surface soils was determined using solid state 13C nuclear magnetic resonance (n.m.r.) spectroscopy with cross polarisation and magic angle spinning (CP/MAS). Analyses were repeated after high energy ultraviolet photo-oxidation was performed on the three finest fractions. All four soils studied contained appreciable amounts of physically protected carbon while three of the soils contained even higher amounts of charcoal. It was not possible to measure the charcoal content of soils directly, however, after photo-oxidation, charcoal remained and was identified by its wood-like morphology revealed by scanning electron microscopy (SEM) together with a highly aromatic chemistry determined by solid state 13C n.m.r. Charcoal appears to be the major contributor to the 130 ppm band seen in the n.m.r. spectra of many Australian soils. By using the aromatic region in the n.m.r. spectra, an approximate assessment of the charcoal distribution through the size fractions demonstrated that more than 88% of the charcoal present in two of the soils occurred in the <53 pm fractions. These soils contained up to 0.8 g C as charcoal per 100 g of soil and up to 30% of the soil carbon as charcoal. Humic acid extractions performed on soil fractions before and after photo-oxidation suggest that charcoal or charcoal-derived material may also contribute significantly to the aromatic signals found in the n.m.r. spectra of humic acids. Finely divided charcoal appears to be a major constituent of many Australian soils and probably contributes significantly to the inert or passive organic carbon pool recognised in carbon turnover models.

Samples from the surface horizons of six virgin soils were collected and separated into density fractions. Based on the spatial distribution of organic materials within the mineral matrix of soil, the soil organic matter (SOM) contained in various density fractions was classified as: (a) free particulate OM, (b) occluded particulate OM, and (c) colloidal or clay-associated OM. The compositional differences noted among these three components of SOM were used to describe the changes that OM undergoes during decomposition when it enters the soil, is enveloped in aggregates and eventually is incorporated into microbial biomass and metabolites and associated with clay minerals. The occluded organic materials, released as a result of aggregate disruption, were in various stages of decomposition and had different degrees of association with mineral particles. Changes in the degree of association of occluded organic materials and mineral particles with decomposition are discussed and form the basis of a model which illustrates the simultaneous dynamics of microaggregates and their organic cores. This model indicates a major role for carbohydrate-rich plant debris in formation and stabilization of microaggregates.

Summary. Recent developments in infrared spectroscopy and computer software, together with decreasing spectrometer costs, have resulted in an increase in the potential for soil analysis. Infrared spectroscopy in both the near and mid infrared ranges allows rapid acquisition of soil information at quantitative and qualitative, or indicator, levels for use in agriculture and environmental monitoring. In this paper, we describe how mid infrared diffuse reflectance analysis can provide results comparable in accuracy with many traditional extractive and digestion laboratory methods in soil studies, with the possibility of either replacing or enhancing them. Examples are given for estimation of lime requirement, organic carbon, exchangeable cations, air-dry moisture, clay content and biological indicators. Infrared methodology appears to have advantages in facilitating some soil analyses that are otherwise very time-consuming or expensive, or where spatially dense data is required.