J. O. Skjemstad

Role of the soil matrix and minerals in protecting natural organic materials against biological attack

Natural organic materials in soils consist of a complex mixture of different biochemicals exhibiting numerous morphologies and stages of biological oxidation. A continuum of decomposability exists based on chemical structure; however, this continuum can be altered by interactions with minerals within matrices capable of stabilising potentially labile organic matter against biological oxidation. Protection is not considered to equate to a permanent and complete removal of organic C from decomposition, but rather to a reduced decomposition rate relative to similar unprotected materials. The stabilisation of organic materials in soils by the soil matrix is a function of the chemical nature of the soil mineral fraction and the presence of multivalent cations, the presence of mineral surfaces capable of adsorbing organic materials, and the architecture of the soil matrix. The degree and amount of protection offered by each mechanism depends on the chemical and physical properties of the mineral matrix and the morphology and chemical structure of the organic matter. Each mineral matrix will have a unique and finite capacity to stabilise organic matter. Quantifying the protective capacity of a soil requires a careful consideration of all mechanisms of protection and the implications of experimental procedures.

Comparison of quantification methods to measure fire‐derived (black/elemental) carbon in soils and sediments using reference materials from soil, water, sediment and the atmosphere

Black carbon (BC), the product of incomplete combustion of fossil fuels and biomass (called elemental carbon (EC) in atmospheric sciences), was quantified in 12 different materials by 17 laboratories from different disciplines, using seven different methods. The materials were divided into three classes: (1) potentially interfering materials, (2) laboratory-produced BC-rich materials, and (3) BC-containing environmental matrices (from soil, water, sediment, and atmosphere). This is the first comprehensive intercomparison of this type (multimethod, multilab, and multisample), focusing mainly on methods used for soil and sediment BC studies. Results for the potentially interfering materials (which by definition contained no fire-derived organic carbon) highlighted situations where individual methods may overestimate BC concentrations. Results for the BC-rich materials (one soot and two chars) showed that some of the methods identified most of the carbon in all three materials as BC, whereas other methods identified only soot carbon as BC. The different methods also gave widely different BC contents for the environmental matrices. However, these variations could be understood in the light of the findings for the other two groups of materials, i.e., that some methods incorrectly identify non-BC carbon as BC, and that the detection efficiency of each technique varies across the BC continuum. We found that atmospheric BC quantification methods are not ideal for soil and sediment studies as in their methodology these incorporate the definition of BC as light-absorbing material irrespective of its origin, leading to biases when applied to terrestrial and sedimentary materials. This study shows that any attempt to merge data generated via different methods must consider the different, operationally defined analytical windows of the BC continuum detected by each technique, as well as the limitations and potential biases of each technique. A major goal of this ring trial was to provide a basis on which to choose between the different BC quantification methods in soil and sediment studies. In this paper we summarize the advantages and disadvantages of each method. In future studies, we strongly recommend the evaluation of all methods analyzing for BC in soils and sediments against the set of BC reference materials analyzed here.

The chemistry and nature of protected carbon in soil

The nature of organic carbon in the < 2, 2–20, 20–53, 53–200, and 200–2000 mu m 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 µm 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.

Importance of mechanisms and processes of the stabilisation of soil organic matter for modelling carbon turnover

This paper reviews current knowledge of soil organic carbon (SOC) dynamics with respect to physical protection, soil moisture and temperature, and recalcitrant carbon fractions (such as charcoal) in predominantly agricultural soils. These factors are discussed within the framework of current soil organic matter models. The importance of soil structure in the stabilisation of organic residues through physical protection has been documented previously in various studies. In addition, changes in soil structure associated with tillage can significantly affect soil organic matter decomposition rates. The concept of physical protection has been incorporated into several soil carbon models as a function of soil texture. While soil texture can affect the soils capacity for aggregation and adsorption, factors such as soil moisture and temperature may further enhance or reduce the extent of physical protection. While adsorption and aggregation can slow decomposition processes, it is unlikely that these processes are solely responsible for the high mean residence times measured in biologically active surface soils. Accordingly, chemical recalcitrance appears to be the only mechanism by which soil organic carbon can be protected for long periods of time.

Comparative analysis of black carbon in soils

Black carbon (BC), produced by incomplete combustion of fossil fuels and vegetation, occurs ubiquitously in soils and sediments. BC exists as a continuum from partly charred material to highly graphitized soot particles, with no general agreement on clear-cut boundaries of definition or analysis. In a comparative analysis, we measured BC forms in eight soil samples by six established methods. All methods involved removal of the non-BC components from the sample by thermal or chemical means or a combination of both. The remaining carbon, operationally defined as BC, was quantified via mass balance, elemental composition or by exploiting benzenecarboxylic acids as molecular markers or applying 13C MAS NMR (magic angle spinning nuclear magnetic resonance) spectroscopy. BC concentrations measured for individual samples vary over 2 orders of magnitude (up to a factor of 571). One possible explanation for this wide range of results is that the individual BC methods rely on operational definitions with clear-cut but different boundaries and developed for specific scientific questions, whereas BC represents a continuum of materials with widely contrasting physicochemical properties. Thus the methods are inherently designed to analytically determine different parts of the continuum, and it is crucial to know how measurements made by different techniques relate to each other. It is clear from this preliminary comparative analysis that a collection of BC reference materials should be established as soon as possible 1 ) to ensure long-term intralaboratory and interlaboratory data quality and 2) to facilitate comparative analyses between different analytical techniques and scientific approaches

Calibration of the Rothamsted organic carbon turnover model (RothC ver. 26.3), using measurable soil organic carbon pools

A fractionation scheme that provided the measurement of a labile pool (particulate organic carbon), a charcoal-carbon pool, and a humic pool by difference was tested as a means of initialising the Rothamsted organic carbon turnover model version 26.3. Equating these 3 fractions with the resistant plant material, inert organic matter, and humic pools of the model, respectively, gave good agreement between measured and modelled data for 2 long-term rotation trials in Australia using a soil depth of 30 cm. At one location, Brigalow Research Station in Queensland, there were 3 distinct soil types, two clays and a duplex soil, in a semi-arid, subtropical climate. At this site, continuous wheat with some sorghum was established after clearing land under brigalow (Acacia harpophylla) and continued for 18 years. The second location was near Tarlee, South Australia, and was established on existing agricultural land. One soil type (red brown earth) with 2 rotations (continuous wheat and wheat–fallow) were available over a period of 8 years. The modelled and measured data were in good agreement for both locations but the level of agreement was substantially improved when the resistant plant material decomposition rate was reduced from 0.3 to 0.15/year. No other modifications were required and the resulting values provided excellent agreement between the modelled and measured data not only for the total soil organic carbon but also for the individual pools. Using this fractionation scheme therefore provides an excellent means of initialising and testing the Rothamsted model, not only in Australia, but also in countries with similar soil types and climate. For the first time, the work reported here demonstrates a methodology linking measured soil carbon pools with a conceptual soil carbon turnover model. This approach has the advantage of allowing the model to be initialised at any point in the landscape without the necessity for historical data or for using the model itself to generate an initial equilibrium pool structure. The correct prediction of the changing total soil organic carbon levels, as well as the pool structure over time, acts as an internal verification and gives confidence that the model is performing as intended.

Estimation of charcoal (char) in soils.

Abstract A method for the semiquantitative estimation of charcoal (char) in soils is reported. The technique, performed on the 90% of soil char in the <53 μm fraction. Because of the assumptions used, estimates of char by this approach must be considered to be semiquantitative, but are conservative and provide estimates of the minimum char content of a soil.

The prediction of soil carbon fractions using mid-infrared-partial least square analysis

This paper describes the application of mid-infrared (MIR) spectroscopy and partial least-squares (PLS) analysis to predict the concentration of organic carbon fractions present in soil. The PLS calibrations were derived from a standard set of soils that had been analysed for total organic carbon (TOC), particulate organic carbon (POC), and charcoal carbon (char-C) using physical and chemical means. PLS calibration models from this standard set of soils allowed the prediction of TOC, POC, and char-C fractions with a coefficient of determination (R2) of measured v. predicted data ranging between 0.97 and 0.73. For the POC fraction, the coefficient of determination could be improved (R2 = 0.94) through the use of local calibration sets. The capacity to estimate soil fractions such as char-C rapidly and inexpensively makes this approach highly attractive for studies where large numbers of analyses are required. Inclusion of a set of soils from Kenya demonstrated the robustness of the method for total organic carbon and charcoal carbon prediction.

The effects of cultivation on the composition of organic matter and structural stability of soils

Soil samples were obtained from the surface horizons of five untilled sites and adjacent sites under short- and long-term cultivation. The soil samples were fractionated based on density and organic materials were concentrated in various fractions which enabled comparative chemical composition of the organic materials in cultivated and uncultivated sites by solid-state C-13 CP/MAS NMR spectroscopy. Changes in the nature of organic carbon with cultivation were different in different soils and resulted from variations in the chemistry of carbon inputs to the soils and a greater extent of decomposition of organic materials in cultivated soils. Differences in the chemical composition of organic carbon between cultivated and uncultivated soils resided mostly in organic materials occluded within aggregates, whereas the chemistry of organic matter associated with clay particles showed only small changes. The results indicate a faster decomposition of O-alkyl C in the cultivated soils. Wet aggregate stability, mechanically dispersible clay and modulus of rupture tests were used to assess the effects of cultivation on structural stability of soils. In four of five soils, the virgin sites and sites which had been under long-term pasture had a greater aggregate stability than the cultivated sites. Neither total organic matter nor total O-alkyl C content was closely correlated with aggregate stability, suggesting that only a part of soil carbon or carbohydrate is involved in aggregate stability. The fractions of carbon and O-alkyl C present in the form of particulate organic matter occluded within aggregates were better correlated with aggregate stability (r = 0.86** and 0.88**, respectively). Cultivation was not the dominant factor influencing water-dispersible clay across the range of soil types used in this study. The amount of dispersible clay was a function of total clay content and the percentage of clay dispersed was controlled by factors such as clay mineralogy, CaCO3 and organic matter content of soils. The tendency of different soils for hard-setting and crusting, as a result of structural collapse, was reflected in the modulus of rupture (MOR). The cultivated sites had significantly higher MOR than their non-tilled counterparts. The soils studied had different MOR due to differences in their physical and chemical properties.

Soil structure: carbon and nitrogen metabolism

Abstract Physical factors confer biological stability on organic matter in soils through the constraints they place on the opportunities for reactions between substrate and enzyme and/or decomposer organism; and, in the context of C and nutrient turnover through decomposer biomass, on the limitations they impose on the activities of predators on prey. The concept of protection afforded to substrates because of their location in micropores of sizes which deny access to decomposer cells, or to microflora in pores which deny access to microfaunal predators, has heightened interest in soil microstructure as a determinant of the availability of organic substrates for decomposition and of the rates of survival of decomposer cells. Widely different methodologies have been used in studies which have attested to the importance of physical protection as mechanisms for stabilization of organic matter in soils. In this review we appraise some of the established methodologies and offer suggestions for extending their usefulness; and we briefly consider some new approaches where methodologies have not as yet been fully developed and whose potential for successful application to soils is unknown. Studies considered include those which seek to characterize enzymes, substrates and organic residues, and their location in situ, in soil aggregates. Characterization of enzymes in situ derives from the use of electron microscopy in conjunction with cytochemical techniques. Characterization of substrates and residues in situ derives from the application of techniques of electron microscopy (SEM, TEM), and spectroscopy (NMR, IR), to soil aggregates or to fractions thereof. The successful development of methodologies combining electron microscopy and autoradiography could demonstrate directly within soil aggregates, sites of activity of specific microorganisms or enzymes in response to selected conditions of substrate addition. Other studies seek to define more closely the relationships between decomposer activities and processes of C and N turnover and soil properties, especially those properties pertaining to soil microstructure. Water retention characteristics of a soil have been utilized to introduce substrates to different pore size locations within aggregates, in order to determine the effects of substrate location on C turnover. Physical fractionation techniques have been utilized to determine the location within aggregates of decomposer organisms, in order to assess the stability of fraction C and N in microbial biomass and organic residues resulting from the metabolism of introduced substrates.