The dynamics of organic matter in rock fragments in soil investigated by 14C dating and measurements of 13C

Rock fragments in soil can contain significant amounts of organic carbon. We investigated the nature and dynamics of organic matter in rock fragments in the upper horizons of a forest soil derived from sandstone and compared them with the fine earth fraction (<2 mm). The organic C content and its distribution among humic, humin and non‐humic fractions, as well as the isotopic signatures (Δ¹⁴C and δ¹³C) of organic carbon and of CO₂ produced during incubation of samples, all show that altered rock fragments contain a dynamic component of the carbon cycle. Rock fragments, especially the highly altered ones, contributed 4.5% to the total organic C content in the soil. The bulk organic matter in both fine earth and highly altered rock fragments in the A1 horizon contained significant amounts of recent C (bomb ¹⁴C), indicating that most of this C is cycled quickly in both fractions. In the A horizons, the mean residence times of humic substances from highly altered rock fragments were shorter than those of the humic substances isolated in the fine earth. Values of Δ¹⁴C of the CO₂ produced during basal respiration confirmed the heterogeneity, complexity and dynamic nature of the organic matter of these rock fragments. The weak ¹⁴C signatures of humic substances from the slightly altered rock fragments confirmed the importance of weathering in establishing and improving the interactions between rock fragments and surrounding soil. The progressive enrichment in ¹³C from components with high‐¹⁴C (more recent) to low‐¹⁴C (older) indicated that biological activity occurred in both the fine and the coarse fractions. Hence the microflora utilizes energy sources contained in all the soil compartments, and rock fragments are chemically and biologically active in soil, where they form a continuum with the fine earth.     

Land-use related organic matter dynamics in North Cameroon soils assessed by 13C analysis of soil organic matter fractions

Topsoil samples from cultivated and adjacent non‐cultivated fields on three major agricultural soils in North Cameroon were fractionated into particle‐size fractions that were analysed subsequently for their C and ¹³C contents. The aim was to obtain further insight into the dynamics of soil organic matter (SOM) in relation to land use in Cameroon. Since organic carbon contents of the fractions were often very small, samples and analyses were extensively replicated to obtain robust statistical estimates of observed differences. For each soil type, differences in δ¹³C values between fields could be related to changes in the input and decomposition of organic matter arising from soil type, land management and, for example, the nature and abundance of weeds. Turnover of organic matter appeared to be fastest in the sand fraction, which is in line with results from earlier studies. In the finer fractions, clear differences in reaction to changes in input and decomposition were observed, that seem to be linked to differences in clay mineralogy. The results illustrate that SOM in the various fractions is much less stable and more strongly affected by changes in land use than might be assumed on the basis of changes in total SOM contents alone. At the same time, they demonstrate the relevance of ¹³C isotope analyses of SOM for studies on the impact of land use on these savannah soils with little SOM that are highly susceptible to degradation.     

Following the decomposition of ryegrass labelled with 13C and 15N in soil by solid-state nuclear magnetic resonance spectroscopy

Investigating the biogeochemistry of plant material decomposition in soil has been restricted by difficulties extracting and identifying organic compounds. In this study the decomposition of ¹³C- and ¹⁵N-labelled Lolium perenne leaves mixed with mineral soil has been investigated over 224 days of incubation under laboratory conditions. Decomposition was followed using short-term rates of CO₂ evolution, the amounts of ¹³C and ¹⁵N remaining were determined by mass spectrometry, and ¹³C and ¹⁵N solid-state nuclear magnetic resonance (NMR) spectroscopy was used to characterize chemically the plant material as it decomposed. After 224 days 48% of the added ¹³C had been lost with a rapid period of C0₂ evolution over the first 56 days. The fraction of cross-polarization magic angle spinning (CP MAS) ¹³C NMR spectra represented by O-alkyl-C signal probably in carbohydrates (chemical shift, 60–90 p.p.m.) declined from 60 to 20% of the spectrum (chemical shift, 0–200 p.p.m.) over 224 days. The rate of decline of the total ¹³C exceeded that of the 60–90 p.p.m. signal during the first 56 days and was similar thereafter. The fraction of the CP MAS ¹³C NMR spectra represented by the alkyl- and methyl-C (chemical shift, 10–45 p.p.m.) signal increased from 5 to 14% over the first 14 days and was 19% after 224 days. CP MAS ¹³C NMR of ¹³C- and ¹⁵N-L. perenne contained in 100-μm aperture mesh bags incubated in the soil for 56 days indicated that the remaining material was mainly carbohydrate but there was an increase in the alkyl- and methyl-C associated with the bag's contents. After 224 days incubation of the labelled ¹³C- and ¹⁵N-L. perenne mixed with the soil, 40% of the added N had been lost. Throughout the incubation there was only one signal centred around 100 p.p.m. detectable in the CP MAS ¹⁵N NMR spectra. This signal corresponded to amide ¹⁵N in peptides and may have been of plant or microbial origin or both. Although there had been substantial interaction between the added ¹⁵N and the soil microorganisms, the associated redistribution of ¹⁵N from plant to microbial tissues occurred within the amide region. The feasibility of following some of the component processes of plant material decomposition in soil using NMR has been demonstrated in this study and evidence that microbial synthesis contributes to the increase in alkyl- and methyl-C content of soil during decomposition has been represented.     

The turnover of carbohydrate carbon in a cultivated soil estimated by 13C natural abundances

Understanding the chemical composition of soil organic matter (SOM) requires the determination of the dynamics of each class of compounds. We measured the dynamics of carbon in neutral carbohydrates by use of natural ¹³C labelling in an experimental wheat and maize sequence extending over 23 years. The isotopic composition of individual neutral monosaccharides was determined in hydrolysed particle‐size fractions by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) of trimethylsilyl (TMS) derivatives. The sensitivity in terms of ¹³C/¹²C ratios ranged between 1 and 2‰ depending on the monosaccharide. The age distribution of neutral sugar carbon was very similar to that of total soil carbon. Particulate organic matter (POM) was characterized by the predominance of glucose and xylose of vegetal origin. In POM > 200 µm, the mean age of sugar‐C (5 years) was slightly less than that of total carbon (7 years). Xylose was younger than glucose. The fine fraction 0–50 µm contained mainly glucose, arabinose, galactose, xylose, fucose and mannose, which had predominantly microbial origins. The mean age of carbohydrate carbon in the fraction 0–50 µm was between 60 and 100 years and was similar to that of total organic carbon (OC). No difference in the age of carbon between the individual monosaccharides was found. The POM fraction 50–200 µm had an intermediate signature and turnover. Considering the typical lability of carbohydrates, the relatively great age of carbohydrate carbon may be explained by physical or chemical protection from degradation, as well as by recycling of soil organic matter carbon by soil microbes.     

Sludge-derived organic carbon in an agricultural soil estimated by 13C abundance measurements

The objective of this study is to develop a method to follow the dynamics of sludge‐derived organic carbon, which will allow us to understand the behaviour of trace metals in the sludge‐treated soils. We studied, in a sandy agricultural soil of southwest France, cultivated with maize and amended with sewage‐sludge over 20 years, the dynamics of different sources of organic matter and compared this with a control, which had never received any treatment. For the first time, a method is proposed that will distinguish and quantify sludge‐derived organic carbon, maize‐derived organic carbon, and native organic carbon. This method is based on the mean differences in δ¹³C abundances between native (−26.5‰), maize (−12.5‰) and sludge (−25.4‰) organic carbon. Three hypotheses on the dynamics of soil organic matter sources are proposed: (i) isotopic differences observed between control and sludge‐treated soils are due only to the incorporation of sludge C, whereas in the others, the control was used to model the incorporation of (ii) maize C or (iii) native C in the sludge‐treated soils. The comparison of the stocks of each source (native C, maize C and sludge C) found in the bulk soil with the sum of corresponding stocks found in particle‐size fractions allowed us to reject the two first hypotheses and to validate the last one. Repeated applications of sewage‐sludge induced accumulation of sludge‐derived organic carbon in the topsoil, and simultaneously contributed to the preservation of maize‐derived organic carbon. When sludge applications ceased, the rapid decrease in soil organic matter stocks was mostly caused by the degradation of the sludge‐derived organic carbon sources. At the same time, the maize‐derived organic carbon shifted from the coarsest fraction (200–2000 μm) to the finest fraction (0–50 μm). Therefore, this study has shown that repeated applications of sewage‐sludge induced changes in soil organic matter dynamics over time.     

Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

Spin counting on solid‐state ¹³C cross‐polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32–81% of potential ¹³C NMR signal was detected. The observability of ¹³C NMR signal (C_obs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol‐ and methoxyl‐rich samples having the higher values of C_obs. The Bloch decay (BD) technique provided more quantitatively reliable ¹³C NMR spectra, as evidenced by values of C_obs in the range 91–100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O–alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low C_obs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( RE storation of S pectra via T _CH and T O ne R ho (T_1ρH) E diting). Rapid T_1ρH relaxation was found to be primarily responsible for the under‐representation of carbonyl carbon, whereas inefficient cross‐polarization was primarily responsible for the under‐representation of aryl carbon in CP spectra. Proton NMR relaxation rates T_1H and T_1ρH were found to correlate with other NMR properties and also with cropping management. Non‐uniform rates of T_1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.     

The effect of water content on solid-state 13C NMR quantitation and relaxation rates of soil organic matter

Two hydrofluoric acid‐treated soils were prepared with water contents ranging up to 22% by exposing them to a range of atmospheric humidities. There was no effect of water content on the chemical shift distribution of nuclear magnetic resonance (NMR) signal in ¹³C cross‐polarization (CP) NMR spectra. The sensitivity of the ¹³C CP NMR spectra decreased slightly with increasing water content. Much of this decrease could be attributed to decreases in T_1ρH relaxation rates, caused by enhanced molecular mobility of the organic matter in the presence of absorbed water. Rates of T_1H relaxation were very sensitive to water content, and average T_1H relaxation rates decreased four‐ to five‐fold from the smallest to the largest water content. Rates of T_1H relaxation were non‐uniform, and were better modelled by two‐T_1H component fits than one‐T_1H component fits. The ratio of rapidly to slowly relaxing components increased with increasing water content. Proton spin relaxation editing (PSRE) subspectra revealed substantial changes in the nature of these two components with increasing water content. These results indicate the presence of an organic matter component that is very sensitive to water content, transforming from slowly relaxing at a small water content to rapidly relaxing at a greater water content. This component was shown to be rich in O–alkyl and carbonyl C, and may be hemicellulosic root exudates and microbial mucilages. The slowly relaxing PSRE component was a mixture of ligno‐cellulose and alkyl biopolymers, whereas the rapidly relaxing component was primarily charcoal for one of the soils, and was reminiscent of dissolved organic carbon for the other soil. These findings show that care must be taken in controlling water contents when using PSRE to study organic matter.     

13C NMR studies of organic matter in whole soils: I. Quantitation possibilities

A detailed discussion of the quantitative nature of ¹³C CPMAS NMR spectra as applied to solid samples, such as soil, is given. In particular, the influence of the cross-polarization (CP) time constant (T_CH), the relaxation time constant of protons in the rotating frame (T_1pH) and the contact time (t_c) in the CPMAS experiment are considered. Three distinct quantitation regimes are numerically identified according to sample parameters t_CH and T_1PH > and the experimental choice of t_c: (i) quantitation obtainable from a single CPMAS spectrum; (ii) quantitation obtainable from a series of CPMAS spectra; and (iii) quantitation not possible using CPMAS. Strategies for the measurement of sample parameters T_CH and Ti_pH are reviewed. When quantitation is not possible using CPMAS it is necessary to regress to the direct polarization (DP) of ¹³C nuclei. The sensitivity problems of DPMAS are discussed, as too are general factors that affect the quantitation of ¹³C data such as spinning sidebands. More specifically in relation to soil samples, the effects on quantitation arising from the presence of paramagnetics and the actual methods for the measurement of signal intensities are covered.     

The influence of humus fractionation on the chemical composition of soil organic matter studied by solid-state 13C NMR

Four samples of soil organic matter and their humic acids, fulvic acids and humin were studied with solid-state ¹³CP MAS NMR. The whole soil samples were fractionated using NaOH and HCl in order to extract humic acids, fulvic acids and humin. This investigation indicates that conventional humus fractionation does not significantly change the content of different functional groups in soil.     

Characterization of recently 14C pulse-labelled carbon from roots by fractionation of soil organic matter

The inability of physical and chemical techniques to separate soil organic matter into fractions that have distinct turnover rates has hampered our understanding of carbon (C) and nutrient dynamics in soil. A series of soil organic matter fractionation techniques (chemical and physical) were evaluated for their ability to distinguish a potentially labile C pool, that is ‘recent’ root and root‐derived soil C. ‘Recent’ root and root‐derived C was operationally defined as root and soil C labelled by ¹⁴CO₂ pulse labelling of rye grass–clover pasture growing on undisturbed cores of soil. Most (50–94%) of total soil + root ¹⁴C activity was recovered in roots. Sequential extraction of the soil + roots with resin, 0.1 m NaOH and 1 m NaOH allocated ‘recent’ soil + root ¹⁴C to all fractions including the alkali‐insoluble residual fraction. Approximately 50% was measured in the alkali‐insoluble residue but specific activity was greater in the resin and 1 m NaOH fractions. Hot 0.5 m H₂SO₄ hydrolysed 80% of the ¹⁴C in the alkali‐insoluble residue of soil + roots but this diminished specific activity by recovering much non‐¹⁴C organic matter. Pre‐alkali extraction treatment with 30% H₂O₂ and post‐alkali treatment extractions with hot 1 m HNO₃ removed organic matter with a large ¹⁴C specific activity from the alkali‐insoluble residue. Density separation failed to isolate a significant pool of ‘recent’ root‐derived ¹⁴C. The density separation of ¹⁴C‐labelled roots, and roots remixed with non‐radioactive soil, showed that the adhesion of soil particles to young ¹⁴C‐labelled roots was the likely cause of the greater proportion of ¹⁴C in the heavy fraction. Simple chemical or density fractionations of C appear unsuitable for characterizing ‘recent’ root‐derived C into fractions that can be designated labile C (short turnover time).     

Determination of the fate of 13C labelled maize and wheat exudates in an agricultural soil during a short-term incubation

A broader knowledge of the contribution of carbon (C) released by plant roots (exudates) to soil is a prerequisite for optimizing the management of organic matter in arable soils. This is the first study to show the contribution of constantly applied ¹³C‐labelled maize and wheat exudates to water extractable organic carbon (WEOC), microbial biomass‐C (MB‐C), and CO₂‐C evolution during a 25‐day incubation of agricultural soil material. The CO₂‐C evolution and respective δ¹³C values were measured daily. The WEOC and MB‐C contents were determined weekly and a newly developed method for determining δ¹³C values in soil extracts was applied. Around 36% of exudate‐C of both plants was recovered after the incubation, in the order WEOC < MB‐C < CO₂‐C for maize and MB‐C < WEOC < CO₂‐C for wheat. Around 64% of added exudate‐C was not retrieved with the methods used here. Our results suggest that great amounts of exudates became stabilized in non‐water extractable organic fractions. The amounts of MB‐C stayed relatively constant over time despite a continuous exudate‐C supply, which is the prerequisite for a growing microbial population. A lack of mineral nutrients might have limited microbial growth. The CO₂‐C mineralization rate declined during the incubation and this was probably caused by a shift in the microbial community structure. Consequently, incoming WEOC was left in the soil solution leading to rising WEOC amounts over time. In the exudate‐treated soil additional amounts of soil‐derived WEOC (up to 110 μg g⁻¹) and MB‐C (up to 60 μg g⁻¹) relative to the control were determined. We suggest therefore that positive priming effects (i.e. accelerated turnover of soil organic matter due to the addition of organic substrates) can be explained by exchange processes between charged, soluble C‐components and the soil matrix. As a result of this exchange, soil‐derived WEOC becomes available for mineralization.     

Transformation and binding of 13C and 14C-labelled atrazine in relation to straw decomposition in soil

As a source of organic matter, crop residues affect the behaviour of pesticides in agricultural soils. The fate of [U‐ring‐¹³C] and [U‐ring‐¹⁴C] atrazine (6‐chloro‐N‐ethyl‐N‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) was investigated during laboratory incubation under controlled conditions in a loamy soil amended with wheat straw at two different states of decomposition: no preliminary decomposition or 6 months’ preliminary decomposition. After 3 months, non‐extractable, so‐called ‘bound’, ¹³C‐atrazine residues were recovered in three particle‐size fractions (> 200, 50–200 and < 50 μm), and investigated with solid‐state ¹³C‐NMR spectroscopy. Parallel incubations with [U‐ring‐¹⁴C] atrazine were carried out to quantify the bound residues as well as the extractable and mineralized fractions. The effect of straw residues on atrazine behaviour depended on whether they had been previously decomposed or not. When straw was decomposed for 6 months prior to incubation, atrazine mineralization was enhanced to 50% of the initial ¹⁴C in contrast to 15% of the initial ¹⁴C in soil alone and soil amended with fresh straw. In parallel, atrazine bound residues were formed in greater amount representing up to 20% of the initial ¹⁴C. CP/MAS ¹³C‐NMR on soil size fractions of soil–straw mixtures after incubation with ¹³C‐atrazine showed that bound residues contained mostly triazinic C, corresponding to atrazine or primary metabolites. Non‐humified organic materials recovered in size fractions > 200 and 50–200 μm contained significant amounts of bound residues, especially when straw was added to the soil. CP/MAS ¹³C‐NMR analysis of humic acids obtained from < 50‐μm fractions was difficult due to overlapping of the native carboxyl ¹³C signal with the ¹³C‐atrazine signal.     

The 14C age and residence time of organic matter and its lipid constituents in a stagnohumic gley soil

A combination of radiocarbon (¹⁴C) dating and biomarker analyses of the aliphatic hydrocarbons in soil lipids is proposed as a novel and improved method for studying the environmental history of peaty soils. The radiocarbon concentration of unfractionated bulk organic matter, hydrolysed soil residues and two lipid fractions (the aliphatic hydrocarbons and carboxylic acids) recovered from a stagnohumic gley soil, were compared using AMS (accelerator mass spectrometry) and radiometric ¹⁴C dating techniques. The radiocarbon ages recorded by the aliphatic hydrocarbon fractions were consistently older than those measured from the unfractionated soil, and were in most cases older than the residues remaining after acid hydrolysis. This pattern was observed at three different depths in the soil profile. The apparent age difference between the hydrocarbon fraction and its unfractionated substrate increased with depth. An abundance of long–chain n–alkanes, similar to those found in higher plant waxes, characterized the aliphatic hydrocarbon fraction from the deepest soil (at 21.5–24.5–cm depth). The radiocarbon age of this basal organic component (13470± 170 years bp ) indicated that it derived from the initial re–establishment of vegetation on the local deglaciated landscape with the onset of the Windermere Interstadial (c. 14000–13000 ¹⁴C years bp ). Bulk organic detritus within the basal horizon dated at some 3000 years younger, and presumably as a result of the downward penetration and retention of some mobile organic residues produced later in the development of the soil profile. The survival and apparent stratigraphical stability of these recoverable aliphatic hydrocarbons provides the opportunity, via the development of AMS dating, to measure an unambiguous radiocarbon age for the origin of organic residues retained in soils and sediments.     

Effect of tillage on soil organic carbon mineralization estimated from 13C abundance in maize fields

Three methods of cultivation, conventional tillage (CT), superficial tillage (ST) and no-tillage (NT), were applied for 17 years to continuous maize. Their effect on soil organic carbon content was investigated through measurements of carbon and ¹³C/¹²C ratios, using the natural difference in ¹³C content between C₃ plants and maize, which is a C₄ plant. Because the soil had carried C₃ plants before the experiment started, the organic carbon remaining from that time (C₃,-carbon), was distinguished from the carbon derived from maize. Comparison between continuous wheat and maize plots showed that organic matter from both maize and wheat decomposed without significant ¹³C enrichment, whereas older C₃-carbon was enriched by 1.5% compared to that of fresh wheat material. From the initial 3.6 kg C m^?2 in the topsoil (0–30 cm), 0.95 were mineralized in the CT treatment, but only 0.45 in NT. The mineralization was the same in the tilled layer of ST as in CT. The CT treatment accumulated 1.1 kg C m^?2 of maize-derived carbon and the NT treatment 0.8. The mineralization of initial C₃-carbon was the same at all depths between 0 and 30 cm in the NT treatment; 75% of the carbon derived from maize was found in the 0–5 cm layer.     

Isotopic analysis of respired CO2 during decomposition of separated soil organic matter pools

A detailed understanding of the processes that contribute to the δ¹³C value of respired CO₂ is necessary to make links between the isotopic signature of CO₂ efflux from the soil surface and various sources within the soil profile. We used density fractionation to divide soils from two forested sites that are a part of an ongoing detrital manipulation experiment (the Detrital Input and Removal Treatments, or DIRT project) into two soil organic matter pools, each of which contributes differently to total soil CO₂ efflux. In both sites, distinct biological pools resulted from density fractionation; however, our results do not always support the concept that the light fraction is readily decomposable whereas the heavy fraction is recalcitrant. In a laboratory incubation following density fractionation we found that cumulative respiration over the course of the incubation period was greater from the light fraction than from the heavy fraction for the deciduous site, while the opposite was true for the coniferous site.Use of stable isotopes yielded insight as to the nature of the density fractions, with the heavy fraction solids from both forests isotopically enriched relative to those of the light fraction. The isotopic signature of respired CO₂, however, was more complicated. During incubation of the fractions there was an initial isotopic depletion of the respired CO₂ compared to the substrate for both soil fractions from both forests. Over time for both fractions of both soils the respired δ¹³C reflected more closely the initial substrate value; however, the transition from depleted to enriched respiration relative to substrate occurs at a different stage of decomposition depending on site and substrate recalcitrance. We found a relationship between cumulative respiration during the incubation period and the duration of the transition from isotopically depleted to enriched respiration in the coniferous site but not the deciduous site. Our results suggest that a shift in microbial community or to dead microbial biomass as a substrate could be responsible for the transition in the isotopic signature of respired CO₂ during decomposition. It is likely that a combination of organic matter quality and isotopic discrimination by microbes, in addition to differences in microbial community composition, contribute to the isotopic signature of different organic matter fractions. It is apparent that respired δ¹³CO₂ cannot be assumed to be a direct representation of the substrate δ¹³C. Detailed knowledge of the soil characteristics at a particular site is necessary to interpret relationships between the isotopic values of a substrate and respired CO₂.     

Spin accounting and RESTORE – two new methods to improve quantitation in solid-state 13C NMR analysis of soil organic matter

Rapid T_1ρH relaxation and inefficient cross‐polarization have long been known to affect quantitation in solid‐state ¹³C cross‐polarization (CP) NMR spectra of soil organic matter. We have developed two new techniques to overcome these problems. The first, spin accounting, enables accurate gauging of how quantitative a spectrum is likely to be. The result is expressed as the percentage of potential NMR signal that can be accounted for (C_obs). Spin accounting improves on the established spin counting technique by correcting for rapid T_1ρH relaxation and inefficient cross‐polarization. Spin accounting identifies three components: one that is well represented in CP spectra, one that is under‐represented in CP spectra due to rapid T_1ρH relaxation, and one that is under‐represented in CP spectra due to inefficient cross‐polarization. For a range of eight de‐ashed soils, C_obs was in the range 83–106%, indicating that virtually all potential signal could be accounted for after correcting for rapid T_1ρH relaxation and inefficient cross‐polarization. The second new technique, RESTORE (RE storation of S pectra via T _CH and T O ne R ho (T_1ρH) E diting), generates subspectra for the three components identified in spin accounting. The sum of the three RESTORE subspectra is essentially a corrected CP spectrum. The RESTORE spectra of all eight soils more closely resembled the corresponding, and presumably quantitative, Bloch decay spectra than did the CP spectra. RESTORE identifies the types of structures underestimated by CP, and the cause of their underestimation. Rapid T_1ρH relaxation most affected carbonyl and carbohydrate carbons, whereas inefficient cross‐polarization most affected aromatic carbons.     

Translocation of soils to stimulate climate change: CO2 emissions and modifications to soil organic matter

The effect of climate change on CO₂ emissions was studied on undisturbed soil monoliths (40‐cm diameter, 25‐cm high), which were translocated to warmer zones than their place of origin. Thirty‐two months after the translocation, a climatic factor deduced from the moisture content of the soil and from the effective mean temperature (temperatures in excess of 5°C) revealed that translocation increased the potential of the climate to enhance the biological processes by between 73% and 26% compared with what the soil would support in its place of origin. At the end of the study, the transported soils had lost a large proportion of both total carbon and nitrogen (between 20 and 45%). During the experiment, the CO₂ emissions from the soils, measured under field conditions, were quite variable, but were usually greater than from soils in situ. The variation in labile C in the soil throughout the experiment was calculated from a first‐order kinetic equation for organic matter decay. The relative CO₂ emissions, expressed in terms of the labile carbon fraction in the soils, were clearly greater in those translocated soils that underwent the most intensive climate change, which indicates that the variations in emissions over time are basically a function of the size of the labile organic matter pool.     

A 13C-NMR study of the interactions of soil organic matter with aluminium and allophane in podzols

The stabilization of organic matter in soil by interaction with aluminium (Al) or allophane is important in maintaining soil quality, and in retarding the decomposition of soil organic matter. Complexation of Al by soil organic matter may also ameliorate Al toxicity. Here we use ¹³C-NMR spectroscopy to assess the interaction of soil organic matter with both Al and allophane in two poorly drained podzols containing only trace amounts of iron. The ¹³C-NMR spectrum of the subsoil of the allophane-rich One Tree Point podzol shows an intense peak at 179 p.p.m., assigned to carbon in carboxylic acids. This peak shifts to 177 p.p.m. after removal of allophane (11% of the soil mass) by treatment with HF. We infer that the carboxyl groups in the organic matter are bonded to structural Al on the surface of allophane spherules. In the non-allophanic Te Kopuru podzol, on the other hand, the organic matter apparently interacts with Al ions in the soil solution. This soil also has more aromatic carbon and fewer carbons in carboxyl and carbohydrate structures than the allophanic sample. There is an indication that allophane stabilizes carbohydrate groups as well as carboxyl groups.