C and N NMR spectroscopy as a tool in soil organic matter studies

Nuclear magnetic resonance (NMR) is a valuable tool for the characterization of soil organic matter and humification processes in soils. This review highlights soil organic matter studies based mainly on solid-state ¹³C and ¹⁵N NMR spectroscopy and some emerging applications, that may provide significant progress in our knowledge on soil organic matter. A major advantage of Nmr spectroscopy is that it can be used as a non-invasive method for solid soil samples or soil fractions. Although resolution is limited, one can obtain an overview on the organic matter structures present in the soil sample. Application of ¹³C and ¹⁵N NMR to soils has, for a long time, been confined to the study of bulk soils or humic extracts for structural characterization. The transformations of soil organic C and N are now being investigated after addition of ¹³C- and ¹⁵N-labelled parent materials to the soil and following their evolution in different C and N pools. With labelling techniques it is also possible to study the interaction of organic pollutants with soil organic matter. Contamination of a soil with man-made additives, such as soot or brown coal dust, can also be detected in soils or individual soil fractions.     

应用15N核磁共振技术对苯聚合物结合蛋白中氮形态的研究

Phenolic polymers synthesized by reactions by reactions of p-benzoquinone with 15N-labelled protein or (15NH4)2SO4 were studied by using 15N CP-MAS NMR technique in combination with chemical approaches.Results showed that more than 80% of nitrogen in quinone-protein polymers was in the form of amide with some present as aromatic and /or aliphatic amine and less than 10% of nitrogen occurred as heterocyclic N.The nitrogen distribution in the non-hydrolyzable residue of the quinone-protein polymers was basically similar to that of soil humic acid reported in literature with the exception that a higher proportion of N as heterocyclic N and aromatic amine and a lower proportion of N as amide and aliphatic amine were found in the former than in the latter,More than 70% of total nitrogen in quinone-(NH4)2OS4 polymer was acid resistant ,of which about 53% occurred as pyrrole,nitrile and imion type N.The possible roles of the reactions of phenols or quinones with proteins in the formation of humic acid.especially the non-hydrolyzable nitrogen in humicacid,are discussed.     

固态13C和15N核磁共振法研究15N标记土壤的腐殖质组分

Five humic fractions were obtained from a uniformly ^15N-labelled soil by extraction with 0.1 mol L^-1 Na4P2O7,0.1mol L^-1 NaOH ,and HF/HCl-0.1 mol L^-1 NaOH,consecutively,and analyzed by ^13C and ^15N CPMAS NMR (cross polarization and magic angle spinning nuclear magnetic resonace).Compared with those of native soils humic fractions studied as a whole contained more alkyls ,methoxyls and O-alkyls,being 27%-36%,17%-21%and 36%-40%,respectively,but fewer aromatics and carboxyls(bein 14%-20% and 13%-90%,respectively),Among those humic fractions ,the humic acid(HA)and fulvic acid(FA) extracted by 0.1 mol L^-1 Na4P2O7 contained slightly more carboxyls than corresponding humic fractions extracted by 0.1 mol L^-1 NaOH ,and the HA extacted by 0.1 mol L^-1 NaOH after treatment with HF/HCl contained the least aromatics and carboxyls.The distribution of nitrogen functional groups of soil humic fractions studied was quite similar to each other and also quite similar to that of humic fraction from native soils.More than 75% of total N in each fraction was in amide from,with 9%-13% present as aromatic and /or aliphatic amines and the remainder as heerocyclic N.     

Assessing the organic phosphorus status of an Oxisol under tropical pastures following native savanna using 31P NMR spectroscopy

³¹P nuclear magnetic resonance (NMR) spectroscopy, P fractionation, and a P sorption experiment were used to follow the changes in P in the A horizons (0–10 cm) of acid savanna soils, Colombia, after little P fertilization and 15 years' continuous growth of a grass (Brachiaria decumbens) and a grass/legume (B. decumbens+Pueraria phaseoloides) pasture. Ready P supply as analyzed by Bray P was low under native savanna (1.3 mg kg^-1 soil) and responded moderately on pasture establishment. Concurrently, the affinity of the soil for inorganic P declined slightly after pasture establishment. ³¹P NMR spectroscopy revealed that P associated with humic acids was dominated by monoester P followed by diester P. Smaller proportions were observed for phosphonates, teichoic acid P, orthophosphate, and pyrophosphate. P associated with fulvic acids had lower proportions of diester P and higher contents of orthophosphate. Under native savanna the reserves of labile organic P species (phosphonates and diester P including teichoic acid P) associated with humic and fulvic acids were 12.4 and 1.1 kg ha^-1, respectively, and increased to 18.1 and 1.8 kg ha^-1 under grass pasture, and to 19.5 and 2.3 kg ha^-1 under grass/legume pasture. These data emphasize the importance of labile organic P species in the P supply for plants in improved tropical pastures, and further indicate that humic acid P in particular responds to land-use changes within a relatively short time-scale. Earthworm casts were highly abundant in the B. decumbens+P. phaseoloides plot and were enriched in labile organic P species. We conclude that earthworm activity improves the P supply in soil under tropical pastures by creating an easily available organic P pool.Dedicated to Professor J.C.G. Ottow on the occasion of his 60th birthday     

Impact of top-pruning time on the fertilizer N use efficiency of flue-cured tobacco as assessed by 15N tracing technique

To evaluate the impact of top-pruning time on fertilizer N use efficiency (NUE) of flue-cured tobacco, we adopted ¹⁵N tracing technique and conducted a 2-year experiment from 2014 to 2015 in eastern China. The experiment included three top-pruning points of time: 5th, 25th and 45th day after flowering (DAF), abbreviated, respectively, as TP5, TP25 and TP45. The amounts of plant N derived from fertilizer (Ndff) and soil (Ndfs) were observed during 0–55th DAF. Results showed that top-pruning slowed down the increase of Ndff in tobacco organs, particularly in the leaf, but accelerated the increase of Ndfs dramatically. The proportion of Ndff (%) accounted for the total N reduced dramatically after top-pruning. This reduction might attribute to the selectivity of plant to different N sources as influenced by top-pruning while had little relationship with soil N supply, according to the analysis on the soil total mineral N and mineral ¹⁵N. The average NUE for the 2 years was 32%, 41% and 47%, respectively, for TP5, TP25 and TP45, showing significant (p < 0.05) differences. We concluded that the tobacco preferred to uptake soil N rather than fertilizer N after top-pruning; thus, optimizing the top-pruning time might be one of the approaches to improve the in-season NUE of flue-cured tobacco.     

Composition of organic matter in a subtropical Acrisol as influenced by land use, cropping and N fertilization, assessed by CPMAS 13C NMR spectroscopy

We know much about the influence of management on stocks of organic matter in subtropical soils, yet little about the influence on the chemical composition. We therefore studied by CPMAS ¹³C NMR spectroscopy the composition of the above-ground plant tissue, of the organic matter of the whole soil and of silt- and clay-size fractions of the topsoil and subsoil of a subtropical Acrisol under grass and arable crops. Soil samples were collected from three no-till cropping systems (bare soil; oats−maize; pigeon pea + maize), each receiving 0 and 180 kg N ha⁻¹ year⁻¹, in a long-term field experiment. Soil under the original native grass was also sampled. The kind of arable crops and grass affected the composition of the particulate organic matter. There were no differences in the composition of the organic matter in silt- and clay-size fractions, or of the whole soil, among the arable systems. Changes were observed between land use: the soil of the grassland had larger alkyl and smaller aromatic C contents than did the arable soil. The small size fractions contain microbial products, and we think that the compositional difference in silt- and clay-size fractions between grassland and the arable land was induced by changes in the soil's microbial community and therefore in the quality of its biochemical products. The application of N did not affect the composition of the above-ground plant tissue nor of the particulate organic matter and silt-size fractions, but it did increase the alkyl C content in the clay-size fraction. In the subsoil, the silt-size fraction of all treatments contained large contents of aromatic C. Microscopic investigation confirmed that this derived from particles of charred material. The composition of organic matter in this soil is affected by land use, but not by variations in the arable crops grown.     

Temporal changes in distribution and composition of N from labeled fertilizer in soil organic matter fractions

Variations in the amount and composition of immobilized nitrogen (N) in major soil organic matter fractions were investigated in a 730-day soil incubation experiment using ¹⁵N-labeled urea and ¹⁵N nuclear magnetic resonance spectroscopy with the cross polarization/magic angle spinning (¹⁵N CPMAS NMR) method. After 730 days, 24.7% of the applied N was recovered from the soil as organic N. The urea-derived N recovered from humic acids and humin decreased from 11.2 and 33.8% of the applied amount after 14 days to 1.6 and 20.4% after 730 days, respectively. When these values were corrected for the microbial biomass (MB) N, they ranged from 9.0 to 1.2% and 28 to 18%, respectively. The proportion of urea-derived N recovered from fulvic acids was low, ranging between 0.4 and 5.8% (with MB N) or 5.6% (without MB N) of the applied amount, whereas that from water-soluble nonhumic substances (WS-NHS; NHS in the fulvic acid fraction) remained high, 28–33% of the applied amount after correction for the contribution of MB N up to day 365, and decreased to 0.9% thereafter. The ¹⁵N CPMAS NMR spectra of humic acids, fulvic acids, and humin showed the largest signal at −254 to −264 ppm, corresponding to peptide/amide N. The proportions of heterocyclic, peptide/amide, guanidine/aniline, and free amino N in the urea-derived humic acid N were 3–7, 83–90, 5–7, and 2–4%, respectively. More than 80% loss of the urea-derived humic acid N did not markedly alter their composition. No time-dependent variations were also observed for the proportions of respective N functional groups in humin N, which were 3–5, 71–78, 12–17, and 6–10% in the same order as above. These results suggest the greater importance of physical stability than structural variation for the initial accumulation of organic N in soil.     

Plant uptake of dual-labeled organic N biased by inorganic C uptake: Results of a triple labeling study

Direct plant uptake of organic nitrogen (N) is often studied using the dual-labeling approach (¹⁵N + ¹³C or ¹⁵N + ¹⁴C). However, the method might be hampered by uptake of labeled inorganic carbon (C) produced by mineralization of labeled organic compounds. Here we report the results from a triple labeling experiment (¹⁵N + ¹³C + ¹⁴C) investigating whether root uptake of labeled inorganic C can bias the results obtained in studies of organic N uptake using dual-labeled amino acids (¹⁵N, ¹³C). In a rhizosphere tube experiment we investigated ¹³C and ¹⁴C uptake by maize either supplied with labeled glycine or , but found no differences in uptake rates between these C-sources. The uptake of inorganic C to the shoot tissue was higher for maize grown in full light compared to shading, which indicates a passive uptake of inorganic C with water. We conclude that uptake of inorganic C produced by mineralization of amino acids can significantly bias the interpretations of organic N uptake studies using dual-labeling.     

Assessing management impacts on soil organic matter quality in subtropical Australian forests using physical and chemical fractionation as well as C NMR spectroscopy

Successful soil organic matter (SOM) quality assessment is needed to improve our ability to manage forest soils sustainably. Our objective was to use a multivariate data set to determine whether the land use conversion from native forest (NF) to hoop pine plantation and the following rotation and site preparation practices had altered SOM quality at three adjacent sites of NF, first (1R) and second rotation (2R, including tree planting row (2R-T) and windrow of harvest residues (2R-W)) of hoop pine plantations in southeast Queensland, Australia. Cross-polarization magic angle spinning ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy and sequential hot water and acid hydrolysis were conducted on SOM fractions separated by wet-sieving and density fractionation procedures to characterize SOM quantitative and qualitative relevant parameters, including carbon (C) functional groups, C and nitrogen (N) contents, C/N ratios, and C and N recalcitrant indices. Analysis of variance (ANOVA) and principal component analysis (PCA) of these multivariate parameters together indicated a complicated interaction between physical protection and biochemical recalcitrance, making the land use and management induced changes of SOM quality more complex. Knowledge of PCA based on the refined set of 41 SOM quantitative and qualitative parameters identified that principal component 1 (PC1), which explained 55.7% of the total variance, was most responsible for the management induced changes in soil processes. This was reflected by the dynamics of SOM regarding the aspects of total stock, soil basal and substrate induced respirations, gross and net N mineralization and nitrification, and microbial biomass, microbial diversity of C utilization patterns. Further, the macroaggregates (F_{250-2000 μm}) and the C/N ratio of acid extracts of SOM physical fractions, which represented the most informative and unique variables loading on PC1, might be the most promising physical and chemical measures for SOM quality assessment of land use and management impacts in subtropical Australian forests.     

Organic C and N stabilization in a forest soil: Evidence from sequential density fractionation

In mineral soil, organic matter (OM) accumulates mainly on and around surfaces of silt- and clay-size particles. When fractionated according to particle density, C and N concentration (per g fraction) and C/N of these soil organo-mineral particles decrease with increasing particle density across soils of widely divergent texture, mineralogy, location, and management. The variation in particle density is explained potentially by two factors: (1) a decrease in the mass ratio of organic to mineral phase of these particles, and (2) variations in density of the mineral phase. The first explanation implies that the thickness of the organic accumulations decreases with increasing particle density. The decrease in C/N can be explained at least partially by especially stable sorption of nitrogenous N-containing compounds (amine, amide, and pyrrole) directly to mineral surfaces, a phenomenon well documented both empirically and theoretically. These peptidic compounds, along with ligand-exchanged carboxylic compounds, could then form a stable inner organic layer onto which other organics could sorb more readily than onto the unconditioned mineral surfaces (“onion” layering model).To explore mechanisms underlying this trend in C concentration and C/N with particle density, we sequentially density fractionated an Oregon andic soil at 1.65, 1.85, 2.00, 2.28, and 2.55 g cm⁻³ and analyzed the six fractions for measures of organic matter and mineral phase properties.All measures of OM composition showed either: (1) a monotonic change with density, or (2) a monotonic change across the lightest fractions, then little change over the heaviest fractions. Total C, N, and lignin phenol concentration all decreased monotonically with increasing density, and ¹⁴C mean residence time (MRT) increased with particle density from ca. 150 years to >980 years in the four organo-mineral fractions. In contrast, C/N, ¹³C and ¹⁵N concentration all showed the second pattern. All these data are consistent with a general pattern of an increase in extent of microbial processing with increasing organo-mineral particle density, and also with an “onion” layering model.X-ray diffraction before and after separation of magnetic materials showed that the sequential density fractionation (SDF) isolated pools of differing mineralogy, with layer-silicate clays dominating in two of the intermediate fractions and primary minerals in the heaviest two fractions. There was no indication that these differences in mineralogy controlled the differences in density of the organo-mineral particles in this soil. Thus, our data are consistent with the hypothesis that variation in particle density reflects variation in thickness of the organic accumulations and with an “onion” layering model for organic matter accumulation on mineral surfaces. However, the mineralogy differences among fractions made it difficult to test either the layer-thickness or “onion” layering models with this soil. Although SDF isolated pools of distinct mineralogy and organic-matter composition, more work will be needed to understand mechanisms relating the two factors.     

Manipulating the N release from N labelled celery residues by using straw and vinasses

The aim of this laboratory study was to investigate the effect of straw and vinasses on the nitrogen (N) mineralization-immobilization turnover of celery residues during two periods (each simulating a time period from autumn till spring) under laboratory conditions. During the first period (1-198 d), ¹⁵N-labelled celery residues (1.1 g dry matter (DM) kg⁻¹ soil) were incubated together with straw (8.1 g DM kg⁻¹ soil), aiming to immobilize the N released from celery residues, followed by an incorporation of vinasses (1.9 g DM kg⁻¹ soil) after 84 d, with a view to remineralizing the immobilized celery-N. During the second period (198-380 d), the experimental set-up was repeated, except that non-labelled celery residues were used. Total N, mineral N and their ¹⁵N enrichments as well as microbial biomass N were determined at regular time intervals. During both periods, mixing celery residues with straw significantly increased microbial biomass N (90.5 and 40.5 mg N kg⁻¹ extra compared to celery only treatment) and decreased the amount of mineral N (reduction of 56.1 and 45.9 mg N kg⁻¹ soil compared to celery only treatment) and the celery-derived mineral ¹⁵N (0% of mineral celery-derived ¹⁵N in straw treatment compared to 35% of mineral celery-derived ¹⁵N in celery only treatment). After maximum immobilization, a natural remineralization (without addition of vinasses) of 32.2 (at day 198) and 11.1 mg N kg⁻¹ soil (at day 380) occurred in the straw treatment, but the mineral N content remained significantly lower than in the celery only treatment during the complete experiment, and the amount of remineralized celery-¹⁵N was very low (5.4% of celery-derived ¹⁵N after 380 d). Vinasses caused no real priming effect, although it did slightly increase the amount of remineralized celery-¹⁵N (+6.4% of celery-derived ¹⁵N at day 380 compared to the straw treatment), probably due an apparent added N interaction caused by displacement reactions with the soil microbial biomass.     

Interference by amino acids during the determination of N ammonium in soil

In the study of terrestrial N cycling, NH₄⁺ concentration and ¹⁵N enrichment are routinely determined by colorimetric continuous flow analysis and microdiffusion methods. Amino acids can interfere in these determinations; consequently the aim of the present study was to evaluate the significance of the interference. Glycine and glutamine are key amino acids in soil and were therefore used as ‘models’. Both glycine and glutamine interfered during continuous flow analysis, whereas interference during microdiffusion was of little importance. The effects of interference can be significant, e.g. estimates of gross mineralisation rate were reduced up to 33%, where we allowed for amino acid interference during determination of NH₄⁺ concentration. The potential influence of amino acid interference emphasises that development of continuous flow analysis to increase NH₄⁺ specificity is needed.     

Decomposition of plant tissue submerged in an extremely acidic mining lake sediment: phenolic CuO-oxidation products and solid-state C NMR spectroscopy

In extremely acidic mining sediments of the Lusatian mining district, the alkalinisation process relies on organic C, which can serve as electron donor for microbially induced sulfate reduction. Plant material of the pioneer plant Juncus bulbosus is an important organic matter source in lake sediments. Therefore, decomposition of the plant tissue was assessed during the exposure of litterbags for 30 months in the 0-5 cm layer of waterlogged mining sediments, which have a pH between 2.5 and 3. The ash free dry weight (AFDW) and elemental content of the plant tissue were recorded several times during the exposure. Changes in chemical structure were analyzed by solid-state ¹³C cross polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy and the lignin component characterized by wet-chemical CuO oxidation. The AFDW accounted for about 34% of initial biomass after field exposure for 30 months. Mass loss of biomass occurred in two phases with decomposition rates varying between 30 and 430 mg AFDW d⁻¹. The mass loss increased considerably after 5-7 months when litterbags were invaded by fresh J. bulbosus plants. With respect to higher mass loss, ¹³C CPMAS NMR spectroscopy, showed slight changes of the bulk chemical composition after 11 months, indicating that microorganisms present in the sediments or in the rhizosphere degrade plant material as a whole, rather than selectively. During the second phase from about 11 months until the end of the exposure period, contribution of O-alkyl C most probably assignable to easily degradable polysaccharides decreased. In contrast, the contribution of alkyl, aromatic and carboxyl C increased. CuO oxidation showed that the lignin component of J. bulbosus is degraded oxidatively during field exposure. Our results indicate that the exposed plant material is decomposed in the sediment due to changes in sediment conditions that followed plant invasion of the litterbags. It is suggested that the rhizosphere of J. bulbosus by its influence on the redox potential, pH and the microbial component plays a crucial role in organic matter degradation in acidic mining sediments.     

Microbial immobilization of ammonium and nitrate in relation to ammonification and nitrification rates in organic and conventional cropping systems

Agricultural systems that receive high or low organic matter (OM) inputs would be expected to differ in soil nitrogen (N) transformation rates and fates of ammonium (NH₄⁺) and nitrate (NO₃⁻). To compare NH₄⁺ availability, competition between nitrifiers and heterotrophic microorganisms for NH₄⁺, and microbial NO₃⁻ assimilation in an organic vs. a conventional irrigated cropping system in the California Central Valley, chemical and biological soil assays, ¹⁵N isotope pool dilution and ¹⁵N tracer techniques were used. Potentially mineralizable N (PMN) and hot minus cold KCl-extracted NH₄⁺ as indicators of soil N supplying capacity were measured five times during the tomato growing season. At mid-season, rates of gross ammonification and gross nitrification after rewetting dry soil were measured in microcosms. Microbial immobilization of NO₃⁻ and NH₄⁺ was estimated based on the uptake of ¹⁵N and gross consumption rates. Gross ammonification, PMN, and hot minus cold KCl-extracted NH₄⁺ were approximately twice as high in the organically than the conventionally managed soil. Net estimated microbial NO₃⁻ assimilation rates were between 32 and 35% of gross nitrification rates in the conventional and between 37 and 46% in the organic system. In both soils, microbes assimilated more NO₃⁻ than NH₄⁺. Heterotrophic microbes assimilated less NH₄⁺ than NO₃⁻ probably because NH₄⁺ concentrations were low and competition by nitrifiers was apparently strong. The high OM input organic system released NH₄⁺ in a gradual manner and, compared to the low OM input conventional system, supported a more active microbial biomass with greater N demand that was met mainly by NO₃⁻ immobilization.     

Isotope 15N enrichment of soil-ammonium N as a reference to estimate N2 fixation by stem and root-inoculated S. rostrata

Summary A pot experiment in the greenhouse was conducted to compare the contribution of N derived from the atmosphere or from biological N₂ fixation by Sesbania rostrata inoculated with Azorhizobium caulinodans, applied either to roots or to roots and stems (single or multiple stem inoculation). Two subsequent crops were grown for 50 days under flooded conditions. N derived from air was estimated by ¹⁵N dilution using ¹⁵N enrichment of soil NH _inf4 ^sup+ -N and of Echinochloa crusgalli as the non-N₂-fixing reference datum and compared with estimates obtained by the N-difference method. The first crop was grown to stabilize the ¹⁵N into the soil organic N fraction. The ¹⁵N enrichment of soil NH _inf4 ^sup+ -N in the second crop declined slowly. The extractability ratio (¹⁵N enrichment of extractable soil N to ¹⁵N enrichment of total soil N) decreased from 4.8 to 4.1 50 days after planting. The enrichment of soil NH _inf4 ^sup+ -N was comparable to that of E. crus-galli, resulting in similar estimates of N derived from air when either soil NH _inf4 ^sup+ -N or enrichment of E. crus-galli was used as a non-fixing reference. The N-difference method did not always provide reliable estimates of N derived from air; percentages ranged from 75 to more than 80 by 50 days after planting in both crops and did not differ among treatments. The study demonstrates the potential of using ¹⁵N enrichment of soil NH _inf4 ^sup+ -N as a non-N₂-fixing reference for reliable BNF estimates of crops in lowland puddled soil.     

Cotton growth and the fate of N fertilizer as affected by saline water irrigation and N fertigation in a drip-irrigated field

The objective of this two-year field experiment was to study the effects of irrigation amount, N rate, and irrigation water salinity on cotton growth and the fate of N fertilizer. The movement of N through the plant-soil system was traced using ¹⁵N-labeled urea. The study consisted of twelve treatments, including two irrigation amounts (405 and 540?mm, I405 and I540, respectively); two N application rates (240 and 360?kg?N/ha, N240 and N360, respectively); and three irrigation water salinity levels [0.35, 4.61 and 8.04?dS/m, representing fresh water (FW), brackish water (BW), and saline water (SW), respectively]. A randomized complete block design was used with three replications. The results showed that cotton biomass, N uptake, and yield increased as irrigation amount and N amount increased; however, all three variables were significantly less in SW than in FW and BW. Plant ¹⁵N recovery rates were greater (i) in the I540 treatments than in the I405 treatments and (ii) in the N360 treatments than in the N240 treatments. Plant ¹⁵N recovery rates in BW were 7.98% and 30.01% greater than those in FW and SW, respectively. Residual soil ¹⁵N increased as N fertilizer amount increased but declined as irrigation amount increased. Residual soil ¹⁵N in BW and SW was 6.02% and 21.44% greater, respectively, than in FW. Total ¹⁵N recovery was significant greater in BW than in FW and SW. The ¹⁵N leaching losses increased significantly with increases in irrigation amount, irrigation water salinity, and N rate. Our study suggests that if appropriate amounts of irrigation water and N fertilizer are used, then brackish irrigation water (4.61?dS/m) will not affect cotton growth, yield and N recovery. In contrast, saline irrigation water (EC?>?8?dS/m) reduces cotton growth, yield, and N use efficiency.     

Soil organic matter in urban soils: Estimation of elemental carbon by thermal oxidation and characterization of organic matter by solid-state C nuclear magnetic resonance (NMR) spectroscopy

To reduce soil destruction by urban sprawl, land use planning has to promote the use of soils within cities. As soil functions are now protected by law in Germany, urban soil quality has to be evaluated before soil management. We studied contributions from elemental carbon (EC) and soil organic matter (SOM) quality in topsoil horizons at seven sites in Stuttgart, Germany, differing in impurities by technogenic substrates. The most disturbed site was found at a disused railway area while high-density areas, public parks and garden areas showed varying degrees of disturbance by anthropogenic activities. For most soils, compounds derived from plant litter dominated organic matter (OM) quality characterized by nuclear magnetic resonance (NMR) spectroscopy. Although high contents of EC (up to 70% of soil organic carbon) were indicated by thermal oxidation, this was not confirmed by aromatic C intensities in NMR spectra. Only for the highly aromatic railway soil were results for elemental carbon by thermal oxidation and NMR similar. As other technogenic substrates beside EC like plastics may also contribute in the long-term to OM in urban soils, new analytical techniques are therefore required. This knowledge will promote the evaluation of urban soil properties and their sustainable use.     

Natural N abundance of plants and soils under different management practices in a montane grassland

The natural ¹⁵N abundance (δ¹⁵N) of different ecosystem compartments is considered to be an integrator of nitrogen (N) cycle processes. Here we investigate the extent to which patterns of δ¹⁵N in grassland plants and soils reflect the effect of different management practices on N cycling processes and N balance. Investigations were conducted in long-term experimental plots of permanent montane meadows with treatments differing in the amount and type of applied fertilizer (0-200 kg N ha⁻¹ yr⁻¹; mineral fertilizer, cattle slurry, stable manure) and/or the cutting frequency (1-6 cuts per season). The higher δ¹⁵N values of organic fertilizers compared to mineral fertilizer were reflected by higher δ¹⁵N values in soils and harvested plant material. Furthermore, δ¹⁵N of top soils and plant material increased with the amount of applied fertilizer N. N balances were calculated from N input (fertilization, atmospheric N deposition and symbiotic N₂ fixation) and N output in harvest. ‘Excess N’—the fraction of N input not harvested—was assumed to be lost to the environment or accumulated in soil. Taking fertilizer type into account, strong positive correlations between δ¹⁵N of top soils and the N input-output balance were found. In plots receiving mineral N fertilizer this indicates that soil processes which discriminate against ¹⁵N (e.g. nitrification, denitrification, ammonia volatilization) were stimulated by the increased supply of readily available N, leading to loss of the ¹⁵N depleted compounds and subsequent ¹⁵N enrichment of the soils. By contrast, in plots with organic fertilization this correlation was partly due to accumulation of ¹⁵N-enriched fertilizer N in top soils and partly due to the occurrence of significant N losses. Cutting frequency appeared to have no direct effect on δ¹⁵N patterns. This study for the first time shows that the natural abundance of ¹⁵N of agricultural systems does not only reflect the type (organic or mineral fertilizer) or amount of annual fertilizer amendment (0-200 kg ha⁻¹ yr⁻¹) but that plant and soil δ¹⁵N is better described by N input-output balances.     

Transfer of N fixed by a legume tree to the associated grass in a tropical silvopastoral system

Below-ground transfer of nitrogen (N) fixed by legume trees to associated non-N₂-fixing crops has received little attention in agroforestry, although the importance of below-ground interactions is shown in other ecosystems. We used ¹⁵N natural abundance to estimate N transfer from the legume tree Gliricidia sepium (Jacq.) Kunth ex Walp. to C₄ grass Dichanthium aristatum (Poir.) C.E. Hubb. in a silvopastoral system, where N was recycled exclusively by below-ground processes and N₂ fixation by G. sepium was the sole N input to the system. Finding a suitable reference plant, a grass without contact with tree roots or litter, was problematic because tree roots invaded adjacent grass monocrop plots and soil isotopic signature in soil below distant grass monocrops differed significantly from the agroforestry plots. Thus, we used grass cultivated under greenhouse conditions in pots filled with agroforestry soil as the reference. A model of soil ¹⁵N fractionation during N mineralization was developed for testing the reliability of that estimate. Experimental and theoretical results indicated that 9 months after greenhouse transplanting, the percentage of fixed N in the grass decreased from 35% to <1%, due to N export in cut grass and dilution of fixed N with N taken up from the soil. The effect of soil ¹⁵N fractionation on the estimate of the reference value was negligible. This indicates that potted grass is a suitable reference N transfer studies using ¹⁵N natural abundance. About one third of N in field-grown grass was of atmospheric origin in agroforestry plots and in adjacent D. aristatum grassland invaded by G. sepium roots. The concentration of fixed N was correlated with fine root density of G. sepium but not with soil isotopic signature. This suggests a direct N transfer from trees to grass, e.g. via root exudates or common mycorrhizal networks.