Soil Research

Despite the recent interest in biochars as soil amendments for improving soil quality and increasing soil carbon sequestration, there is inadequate knowledge on the soil amendment properties of these materials produced from different feed stocks and under different pyrolysis conditions. This is particularly true for biochars produced from animal origins. Two biochars produced from poultry litter under different conditions were tested in a pot trial by assessing the yield of radish (Raphanus sativus var. Long Scarlet) as well as the soil quality of a hardsetting Chromosol (Alfisol). Four rates of biochar (0, 10, 25, and 50 t/ha), with and without nitrogen application (100 kg N/ha) were investigated. Both biochars, without N fertiliser, produced similar increases in dry matter yield of radish, which were detectable at the lowest application rate, 10 t/ha. The yield increase (%), compared with the unamended control rose from 42% at 10 t/ha to 96% at 50 t/ha of biochar application. The yield increases can be attributed largely to the ability of these biochars to increase N availability. Significant additional yield increases, in excess of that due to N fertiliser alone, were observed when N fertiliser was applied together with the biochars, highlighting the other beneficial effects of these biochars. In this regard, the non activated poultry litter biochar produced at lower temperature (450°C) was more effective than the activated biochar produced at higher temperature (550°C), probably due to higher available P content. Biochar addition to the hardsetting soil resulted in significant but different changes in soil chemical and physical properties, including increases in C, N, pH, and available P, but reduction in soil strength. These different effects of the 2 different biochars can be related to their different characteristics. Significantly different changes in soil biology in terms of microbial biomass and earthworm preference properties were also observed between the 2 biochars, but the underlying mechanisms require further research. Our research highlights the importance of feedstock and process conditions during pyrolysis on the properties and, hence, soil amendment values of biochars.

Interactions between biochar, soil, microbes, and plant roots may occur within a short period of time after application to the soil. The extent, rates, and implications of these interactions, however, are far from understood. This review describes the properties of biochars and suggests possible reactions that may occur after the addition of biochars to soil. These include dissolution–precipitation, adsorption–desorption, acid–base, and redox reactions. Attention is given to reactions occurring within pores, and to interactions with roots, microorganisms, and soil fauna. Examination of biochars (from chicken litter, greenwaste, and paper mill sludges) weathered for 1 and 2 years in an Australian Ferrosol provides evidence for some of the mechanisms described in this review and offers an insight to reactions at a molecular scale. These interactions are biochar- and site-specific. Therefore, suitable experimental trials—combining biochar types and different pedoclimatic conditions—are needed to determine the extent to which these reactions influence the potential of biochar as a soil amendment and tool for carbon sequestration.

Biochar properties can be significantly influenced by feedstock source and pyrolysis conditions; this warrants detailed characterisation of biochars for their application to improve soil fertility and sequester carbon. We characterised 11 biochars, made from 5 feedstocks [Eucalyptus saligna wood (at 400°C and 550°C both with and without steam activation); E. saligna leaves (at 400°C and 550°C with activation); papermill sludge (at 550°C with activation); poultry litter and cow manure (each at 400°C without activation and at 550°C with activation)] using standard or modified soil chemical procedures. Biochar pH values varied from near neutral to highly alkaline. In general, wood biochars had higher total C, lower ash content, lower total N, P, K, S, Ca, Mg, Al, Na, and Cu contents, and lower potential cation exchange capacity (CEC) and exchangeable cations than the manure-based biochars, and the leaf biochars were generally in-between. Papermill sludge biochar had the highest total and exchangeable Ca, CaCO3 equivalence, total Cu, and potential CEC, and the lowest total and exchangeable K. Water-soluble salts were higher in the manure-based biochars, followed by leaf, papermill sludge, and wood biochars. Total As, Cd, Pb, and polycyclic aromatic hydrocarbons in the biochars were either very low or below detection limits. In general, increase in pyrolysis temperature increased the ash content, pH, and surface basicity and decreased surface acidity. The activation treatment had a little effect on most of the biochar properties. X-ray diffraction analysis showed the presence of whewellite in E. saligna biochars produced at 400°C, and the whewellite was converted to calcite in biochars formed at 550°C. Papermill sludge biochar contained the largest amount of calcite. Water-soluble salts and calcite interfered with surface charge measurements and should be removed before the surface charge measurements of biochar. The biochars used in the study ranged from C-rich to nutrient-rich to lime-rich soil amendment, and these properties could be optimised through feedstock formulation and pyrolysis temperature for tailored soil application.

The sensitivity of soil organic carbon (Corg) and microbial carbon (Cmic) measurements, and the Cm~,/Co,, ratio, to reflect climatic, vegetation, cropping and management history was investigated using a range of topsoils in New Zealand. The Cmic generally comprised 1-4% of Corg, with the proportion being consistently greater under pastures, than the equivalent soil under native forest, exotic forest or arable cropping. However, absolute values differed markedly between soils and were greatly influenced by texture, mineralogy and the Corg content. The Cmic recovered more rapidly than Corg on returning to pasture following cropping. There was a generally greater Corg content in those soils from the areas with higher precipitation, but the precipitation-evaporation quotient proposed by Insam et al. (Soil Biol. Biochem. 1989, 21, 211-21) to predict the relationship between Cmic and Corg, greatly underestimated the Cmic content of New Zealand soils and there was too great a scatter in the data to derive a revised regression formula. The Cmic and the Cmic/Cor, ratio are useful measures to monitor soil organic matter and both provide a more sensitive index than COrg measured alone. However, under typical climatic and land use conditions in New Zealand, the values do not appear readily transferrable between soils. To ascertain whether a soil has achieved equilibrium in organic matter status, it will be necessary to establish reference values to which a tested soil can be compared.

Increases in the concentrations of greenhouse gases, carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), and halocarbons in the atmosphere due to human activities are associated with global climate change. The concentration of N2O has increased by 16% since 1750. Although atmospheric concentration of N2O is much smaller (314 ppb in 1998) than of CO2 (365 ppm), its global warming potential (cumulative radiative forcing) is 296 times that of the latter in a 100-year time horizon. Currently, it contributes about 6% of the overall global warming effect but its contribution from the agricultural sector is about 16%. Of that, almost 80% of N2O is emitted from Australian agricultural lands, originating from N fertilisers (32%), soil disturbance (38%), and animal waste (30%). Nitrous oxide is primarily produced in soil by the activities of microorganisms during nitrification, and denitrification processes. The ratio of N2O to N2 production depends on oxygen supply or water-filled pore space, decomposable organic carbon, N substrate supply, temperature, and pH and salinity. N2O production from soil is sporadic both in time and space, and therefore, it is a challenge to scale up the measurements of N2O emission from a given location and time to regional and national levels.Estimates of N2O emissions from various agricultural systems vary widely. For example, in flooded rice in the Riverina Plains, N2O emissions ranged from 0.02% to 1.4% of fertiliser N applied, whereas in irrigated sugarcane crops, 15.4% of fertiliser was lost over a 4-day period. Nitrous oxide emissions from fertilised dairy pasture soils in Victoria range from 6 to 11 kg N2O-N/ha, whereas in arable cereal cropping, N2O emissions range from <0.01% to 9.9% of N fertiliser applications. Nitrous oxide emissions from soil nitrite and nitrates resulting from residual fertiliser and legumes are rarely studied but probably exceed those from fertilisers, due to frequent wetting and drying cycles over a longer period and larger area. In ley cropping systems, significant N2O losses could occur, from the accumulation of mainly nitrate-N, following mineralisation of organic N from legume-based pastures. Extensive grazed pastures and rangelands contribute annually about 0.2 kg N/ha as N2O (93 kg/ha per year CO2-equivalent). Tropical savannas probably contribute an order of magnitude more, including that from frequent fires. Unfertilised forestry systems may emit less but the fertilised plantations emit more N2O than the extensive grazed pastures. However, currently there are limited data to quantify N2O losses in systems under ley cropping, tropical savannas, and forestry in Australia. Overall, there is a need to examine the emission factors used in estimating national N2O emissions; for example, 1.25% of fertiliser or animal-excreted N appearing as N2O (IPCC 1996). The primary consideration for mitigating N2O emissions from agricultural lands is to match the supply of mineral N (from fertiliser applications, legume-fixed N, organic matter, or manures) to its spatial and temporal needs by crops/pastures/trees. Thus, when appropriate, mineral N supply should be regulated through slow-release (urease and/or nitrification inhibitors, physical coatings, or high C/N ratio materials) or split fertiliser application. Also, N use could be maximised by balancing other nutrient supplies to plants. Moreover, non-legume cover crops could be used to take up residual mineral N following N-fertilised main crops or mineral N accumulated following legume leys. For manure management, the most effective practice is the early application and immediate incorporation of manure into soil to reduce direct N2O emissions as well as secondary emissions from deposition of ammonia volatilised from manure and urine.Current models such as DNDC and DAYCENT can be used to simulate N2O production from soil after parameterisation with the local data, and appropriate modification and verification against the measured N2O emissions under different management practices.In summary, improved estimates of N2O emission from agricultural lands and mitigation options can be achieved by a directed national research program that is of considerable duration, covers sampling season and climate, and combines different techniques (chamber and micrometeorological) using high precision analytical instruments and simulation modelling, under a range of strategic activities in the agriculture sector.

Solid-state 13C nuclear magnetic resonance (NMR) spectroscopy has become an important tool for examining the chemical structure of natural organic materials and the chemical changes associated with decomposition. In this paper, solid-state 13C NMR data pertaining to changes in the chemical composition of a diverse range of natural organic materials, including wood, peat, composts, forest litter layers, and organic materials in surface layers of mineral soils, were reviewed with the objective of deriving an index of the extent of decomposition of such organic materials based on changes in chemical composition. Chemical changes associated with the decomposition of wood varied considerably and were dependent on a strong interaction between the species of wood examined and the species composition of the microbial decomposer community, making the derivation of a single general index applicable to wood decomposition unlikely. For the remaining forms of natural organic residues, decomposition was almost always associated with an increased content of alkyl C and a decreased content of O-alkyl C. The concomitant increase and decrease in alkyl and O-alkyl C contents, respectively, suggested that the ratio of alkyl to O-alkyl carbon (A/O-A ratio) may provide a sensitive index of the extent of decomposition. Contrary to the traditional view that humic substances with an aromatic core accumulate as decomposition proceeds, changes in the aromatic region were variable and suggested a relationship with the activity of lignin-degrading fungi. The A/O-A ratio did appear to provide a sensitive index of extent of decomposition provided that its use was restricted to situations where the organic materials were derived from a common starting material. In addition, the potential for adsorption of highly decomposable materials on mineral soil surfaces and the impacts which such an adsorption may have on bioavailability required consideration when the A/O-A ratio was used to assess the extent of decomposition of organic materials found in mineral soils.

The incorporation of organic matter (OM) in soils that are able to rapidly sorb applied phosphorus (P) fertiliser reportedly increases P availability to plants. This effect has commonly been ascribed to competition between the decomposition products of OM and P for soil sorption sites resulting in increased soil solution P concentrations. The evidence for competitive inhibition of P sorption by dissolved organic carbon compounds, derived from the breakdown of OM, includes studies on the competition between P and (i) low molecular weight organic acids (LOAs), (ii) humic and fulvic acids, and (iii) OM leachates in soils with a high P sorption capacity. These studies, however, have often used LOAs at 1–100 mm, concentrations much higher than those in soils (generally <0.05 mm). The transience of LOAs in biologically active soils further suggests that neither their concentration nor their persistence would have a practical benefit in increasing P phytoavailability. Higher molecular weight compounds such as humic and fulvic acids also competitively inhibit P sorption; however, little consideration has been given to the potential of these compounds to increase the amount of P sorbed through metal–chelate linkages. We suggest that the magnitude of the inhibition of P sorption by the decomposition products of OM leachate is negligible at rates equivalent to those of OM applied in the field. Incubation of OM in soil has also commonly been reported as reducing P sorption in soil. However, we consider that the reported decreases in P sorption (as measured by P in the soil solution) are not related to competition from the decomposition products of OM breakdown, but are the result of P release from the OM that was not accounted for when calculating the reduction in P sorption.

The compulsive exchange method for the measurement of cation and anion exchange capacities of soil as described by Gillman and subsequently recommended by the American Society of Agronomy for acid soils has been modified to achieve greater simplicity. Though originally intended for the measurement of highly weathered soils, the method has be extended to saline and non-saline calcareous soils, and also to the measurement of the variation of exchange capacity with pH.

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 �m 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.