Paul G. Saffigna

Recent advances in the application of 13C and 15N NMR spectroscopy to soil organic matter studies.

Nuclear magnetic resonance (NMR) spectroscopy has been applied to many studies in soil science, geochemistry, and environmental science. In recent years, the study of soil organic matter (SOM) using NMR techniques has progressed rapidly. NMR spectroscopy has been used to study chemical changes of SOM during decomposition, and also of soil extract fractions such as humic acid and fulvic acid. NMR spectroscopy of soils has improved rapidly in recent years with the introduction of pre-treatment and particle-size fractionation. In addition to routine liquid- and solid-state 13C NMR applications, 15N NMR spectra of natural abundant samples have been reported, but 15N-enriched material is more convenient to use due to the low natural abundance of 15N. Some newly developed NMR techniques have also been utilised, such as 2-dimensional NMR spectroscopy and improved 1H NMR techniques. These are reviewed and commented on in this paper.

Tissue carbon sources for Pontoscolex corethrurus (Oligochaeta:Glossoscolecidae) in a sugarcane ecosystem.

Abstract The pantropical, geophagous earthworm species Pontoscolex corethrurus (Muller) is common in lowland soils supporting sugarcanc in notheastern Queensland. In comparison with situations where harvest residues are burned, its populations are substantially increased under cultural treatments in which harvest residues are retained as a surface mulch or are mechanically incorporated into the topsoil. The δ 13 C values of stem and leaf materials, soil organic matter and the earthworm whole-body tissues and casts were determined. It is unlikely that P. corethrurus assimilates much of its tissue C from the more complex fractions of soil organic matter or directly from decomposing residues, at least until a late stage of breakdown. No differences in δ5 13 C values were apparent in samples of this species from the different cultural treatments. From field observations of an intimate association between P. corethrurus and the sugarcane roots, we suggest that this species may derive much of its tissue C from rhizospherc sources.

Hydrofluoric acid pre-treatment for improving 13C CPMAS NMR spectral quality of forest soils in south-east Queensland, Australia.

Hydrofluoric acid (HF) was used to pre-treat forest soils of south-east Queensland for assessing the effectiveness of iron (Fe) removal, carbon (C) composition using C-13 cross-polarisation (CP) with magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) before and after the HF pre-treatment, and the improvement of C-13 CPMAS NMR spectra. Soil samples were collected from 4 experimental sites of different soil types, harvest residue management or prescribed burning, and tree species. More than 86% of Fe was in all soil types removed by the HF treatment. The C-13 NMR spectral quality was improved with increased resolution, especially in the alkyl C and O-alkyl C regions, and reduced NMR run-time (1-5 h per sample compared with >20 h per sample without the pre-treatment). The C composition appeared to alter slightly after the pre-treatment, but this might be largely due to improved spectrometer conditions and increased resolution leading to more accurate NMR spectral integration. Organic C recovery after HF pre-treatment varied with soil types and forest management, and soluble soil organic matter (SOM) could be lost during the pre-treatment. The Fourier Transform-Infrared (FT-IR) spectra of HF extracts indicated the preferential removal of carboxylic C groups during the pre-treatment, but this could also be due to adsorbed water on the mineral matter. The NMR spectra revealed some changes in C composition and quality due to residue management and decomposition. Overall, the HF treatment was a useful pre-treatment for obtaining semi-quantitative C-13 CPMAS NMR spectra of subtropical Australian forest soils.

Effect of fertilizer placement on nitrogen loss from sugarcane in tropical Queensland

This paper reports on the fate of nitrogen (N) in a first ratoon sugarcane (Saccharum officinarum L.) crop in the wet tropics of Queensland when urea was either surface applied or drilled into the soil 3–4 days after harvesting the plant cane. Ammonia volatilization was measured with a micrometeorological method, and fertilizer N recovery in plants and soil, to a depth of 140 cm, was determined by mass balance in macroplots with 15N labelled urea 166 and 334 days after fertilizer application. The bulk of the fertilizer and soil N uptake by the sugarcane occurred between fertilizing and the first sampling on day 166. Nitrogen use efficiency measured as the recovery of labelled N in the plant was very low. At the time of the final sampling (day 334), the efficiencies for the surface and subsurface treatments were 18.9% and 28.8%, respectively. The tops, leaves, stalks and roots in the subsurface treatment contained significantly more fertilizer N than the corresponding parts in the surface treatment. The total recoveries of fertilizer N for the plant-trash-soil system on day 334 indicate significant losses of N in both treatments (59.1% and 45.6% of the applied N in the surface and subsurface treatments, respectively). Drilling the urea into the soil instead of applying it to the trash surface reduced ammonia loss from 37.3% to 5.5% of the applied N. Subtracting the data for ammonia loss from total loss suggests that losses by leaching and denitrification combined increased from 21.8% and 40.1% of the applied N as a result of the change in method of application. While the treatment resulted in increased denitrification and/or leaching loss, total N loss was reduced from 59.1% to 45.6%, (a saving of 13.5% of the applied N), which resulted in an extra 9.9%of the applied N being assimilated by the crop.

Composition and quality of harvest residues and soil organic matter under windrow residue management in young hoop pine plantations as revealed by solid-state 13C NMR spectroscopy

Solid-state C-13 nuclear magnetic resonance (NMR) with cross-polarisation (CP) and magic-angle-spinning (MAS) was used to: (a) examine the changes in carbon (C) composition of windrowed harvest residues during the first 3 years of hoop pine plantations in subtropical Australia; (b) assess the impacts of windrowed harvest residues on soil organic matter (SOM) composition and quality in the 0-10 cm soil layer. Harvest residues were collected from 0-, 1-, 2- and 3-year-old windrows of ca. 2.5 m width (15 m apart for 0-, 1- and 2-year-old sites and 10 m apart for 3-year-old site). Soils from the 0 to 10 cm soil layer were collected from the 1-, 2- and 3-year-old sites. The 13C NMR spectra of the harvest residues indicated the presence of lignin in the hoop pine wood, foliage and newly incorporated organic matter (NIOM). Condensed tannin structures were found in the decay-resistant bark, small wood and foliage, but were absent in other residue components and SOM. The NMR spectra of small wood samples contained condensed tannin structures because the outer layer of bark was not removed. NIOM showed a shift from foliage-like structures (celluloses) to lignin-type structures, indicating an incorporation of woody residues from the decomposing harvest residues. Suberins were also present in the small wood, foliage and bark. The 13C CP NMR spectra of SOM indicated that in areas where windrows were present, SOM did not show compositional changes. However, an increase in SOM quality under the windrows in the second year after their formation as characterised by the alkyl C/O-alkyl C (A/O-A) ratio was mainly due to inputs from the decomposition of the labile, readily available components of the windrowed harvest residues

Impacts of repeated fuel reduction burning on tree growth, mortality and recruitment in mixed species eucalypt forests of southeast Queensland, Australia

Abstract The long-term effects of repeated prescribed burning on diameter growth of trees in mixed species dry and wet sclerophyll forest sites in southeast Queensland, Australia were assessed. In addition, fire effects on tree mortality and recruitment in the wet sclerophyll site were evaluated. The results show that growth responses of species to fire were variable. Nevertheless, for most species, recurrent burning had no deleterious effect on tree growth. At the dry sclerophyll site, annual burning since 1952 did not affect growth rates of Eucalyptus drepanophylla and E. acmenoides. On the other hand, E. tereticornis responded positively to annual burning. Smaller Corymbia variegata (formerly Eucalyptus maculata) trees appeared to respond positively to annual burning, while larger trees appeared to respond negatively but this response lessened over time. Periodic burning (every 2–3 years) since 1973 did not significantly affect the growth rates of any tree species. At the wet sclerophyll site, biennial burning since 1972 has enhanced the diameter growth of Lophostemon confertus but depressed that of Syncarpia glomulifera. Quadrennial burning did not affect the diameter growth of L. confertus but depressed that of S. glomulifera. The diameter growth of E. pilularis, C. intermedia, E. microcorys and E. resinifera was not affected by either burning treatment. Basal area growth of most eucalypts at this site was unaffected by burning. However, basal area growth of both S. glomulifera and L. confertus was adversely affected by burning due to tree mortality. For most species, tree mortality was both diameter-dependent and fire-related, that is, smaller trees have a lower chance of survival than larger trees and frequent burning further reduces this probability. Without fire, recruitment was dominated by S. glomulifera and to a lesser extent by L. confertus. Recruitment of these species was adversely affected by burning. This result and the greater mortality of smaller trees with frequent burning suggest that if these trends continue, future stand growth and hence productivity of these species could be jeopardized because of the reduction of the regenerative capacity of the forest. Recruitment was negligible for other tree species in this forest regardless of fire treatment.

Fate of urea nitrogen applied to a banana crop in the wet tropics of Queensland

This paper reports a study in the wet tropics of Queensland on the fate of urea applied to a dry or wet soil surface under banana plants. The transformations of urea were followed in cylindrical microplots (10.3 cm diameter × 23 cm long), a nitrogen (N) balance was conducted in macroplots (3.85 m × 2.0 m) with 15N labelled urea, and ammonia volatilization was determined with a mass balance micrometeorological method. Most of the urea was hydrolysed within 4 days irrespective of whether the urea was applied onto dry or wet soil. The nitrification rate was slow at the beginning when the soil was dry, but increased greatly after small amounts of rain; in the 9 days after rain 20% of the N applied was converted to nitrate. In the 40 days between urea application and harvesting, the macroplots the banana plants absorbed only 15% of the applied N; at harvest the largest amounts were found in the leaves (3.4%), pseudostem (3.3%) and fruit (2.8%). Only 1% of the applied N was present in the roots. Sixty percent of the applied N was recovered in the soil and 25% was lost from the plant-soil system by either ammonia volatilization, leaching or denitrification. Direct measurements of ammonia volatilization showed that when urea was applied to dry soil, and only small amounts of rain were received, little ammonia was lost (3.2% of applied N). In contrast, when urea was applied onto wet soil, urea hydrolysis occurred immediately, ammonia was volatilized on day zero, and 17.2% of the applied N was lost by the ninth day after that application. In the latter study, although rain fell every day, the extensive canopy of banana plants reduced the rainfall reaching the fertilized area under the bananas to less than half. Thus even though 90 mm of rain fell during the volatilization study, the fertilized area did not receive sufficient water to wash the urea into the soil and prevent ammonia loss. Losses by leaching and denitrification combined amounted to 5% of the applied N.

Carbon transformations during wheat straw decomposition

Abstract Following field studies of wheat straw decomposition under different management techniques, experiments were conducted under controlled temperature and moisture conditions to further study straw decomposition during the first 35 days after its addition to soil. Two methods of applying straw (incorporation, surface retention) were compared. Also decomposition was studied in the presence or absence of the water-soluble fraction of straw. The 14C-labelled and unlabelled components of evolved CO2-C, soil soluble and total C, retrieved straw and biomass C were measured for up to 35 days. Incorporating the straw hastened its decomposition only within the first 15 days, thereafter the decomposition rate was similar to that of straw retained on the soil surface. Decomposition rates generally peaked between 4 and 15 days. Applying the soluble fraction of straw to soil after its extraction from straw showed it to be an important substrate during the early stages of straw decomposition. This C source, however, is quickly exhausted. Continued straw decomposition is largely dependent on mineralization of the initially insoluble pool of straw C.

How does residue management impact soil organic matter composition and quality under Eucalyptus globulus plantations in southwestern Australia

This study investigated the influence of harvest residue management practices on soil organic matter (SOM) composition and quality from two second-rotation Eucalyptus globulus plantations in southwestern Australia, using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy with cross-polarisation and magic-angle-spinning (CPMAS). Soil samples (0–5 cm) were collected every 12 months for 5 years from two sites that had contrasting soil types and fertility. Harvest residue management treatments established at both sites were (a) no harvest residues; and (b) double harvest residues. The use of 13C CPMAS and DD NMR spectroscopy enabled the successful non-destructive detection of SOM quality changes in the two E. globulus plantations. Relative intensities of 13C CPMAS NMR spectral regions were similar at both sites, and for both harvest residue treatments, indicating that SOM composition was also similar. Dipolar dephasing (DD) NMR spectra revealed resonances in SOM assigned to lignin and tannin structures, with larger resonances in the carbonyl and alkyl C regions that were indicative of cuticular material, enabling detection of changes in SOM quality. Retention of double harvest residues on the soil surface increased the soil quality compared with removal of all harvest residues at both sites as indicated by the NMR aromaticities, but this was most noticeable at Manjimup, which had greater initial soil fertility.

Genetic variation in foliar carbon isotope composition in relation to tree growth and foliar nitrogen concentration in clones of the F1 hybrid between slash pine and Caribbean pine

The objectives of this study were: (1) to quantify the genetic variation in foliar carbon isotope composition (delta(13)C) of 122 clones of ca. 4-year-old F-1 hybrids between slash pine (Pinus elliottii Engelm var. elliottii) and Caribbean pine (Pinus caribaea var. hondurensis Barr.,et Golf.) grown at two field experimental sites with different water and nitrogen availability in southeast Queensland, Australia, in relation to tree growth and foliar nitrogen concentration (N-mass); and (2) to assess the potential of using delta(13)C measurements, in the foliage materials collected from the clone hedges at nursery and the 4-year-old tree canopies in the field, as an indirect index of tree water use efficiency for selecting elite F-1 hybrid pine clones with improved tree growth. There were significant differences in foliar delta(13)C between the nursery hedges and the 4-year-old tree canopies in the field, between the summer and winter seasons, between the two experimental sites, and between the upper outer and lower outer canopy positions sampled. This indicates that delta(13)C measurements in the foliage materials are significantly influenced by the sampling techniques and environmental conditions. Significant differences in foliar delta(13)C, at the upper outer canopy in both field experiments in summer and winter, were detected between the clones, and between the female parents of the clones. Clone means of tree height at age ca. 3 years were positively related to those of the upper outer canopy delta(13)C at both experimental sites in winter, but only for the wetter site in summer. There were positive, linear relationships between clone means of canopy delta(13)C and those of canopy N-mass, indicating that canopy photosynthetic capacity might be an important factor regulating the clonal variation in canopy delta(13)C. Significant correlations were found between clone means of canopy delta(13)C at both experimental sites in summer and winter, and between those at the upper outer and lower outer canopy positions. Mean clone delta(13)C for the nursery hedges was only positively related to mean clone stem diameter at 1.3 m height at age 3 years on the wetter site. The clone by site interaction for foliar delta(13)C at the upper outer canopy was significant only in summer. Overall, the relatively high genetic variance components for foliar delta(13)C and significant, positive correlations between clone means of foliar delta(13)C and tree growth have highlighted the potential of using foliar delta(13)C measurements for assisting in selection of the elite F-1 hybrid pine clones with improved tree growth