Organic phosphorus in soil water under a European beech (Fagus sylvatica L.) stand in northeastern Bavaria, Germany: seasonal variability and changes with soil depth

Organically bound phosphorus (P) is a mobile form of phosphorus in many soils and thus its dynamics relevant for the leaching and cycling of this element. Despite its importance, little is known about the chemical composition of dissolved organic P. We studied the concentrations, fluxes, and chemical composition of organic P in forest floor leachates and soil solutions in a Rendzic Leptosol under a 90-year-old European beech (Fagus sylvatica L.) forest over a 27-month period (1997–1999). The chemical composition of organic P was analysed using XAD-8 fractionation and ³¹P-nuclear magnetic resonance (NMR) spectroscopy. Organic P was the dominant P form in forest floor leachates as well as in porewaters of the mineral soil. The largest concentrations of organic P were observed during summer and peaked (330–400 g dissolved organic P l^–1) after rain storms following short dry periods, concurrently with the concentrations of organic carbon (OC). Because of high rainfall, fluxes of organic P (and C) were greatest in autumn although concentrations of organic C and P were lower than in summer. In forest floor leachates, the hydrophilic fraction of dissolved organic matter contained 83 ± 13% of the bulk organic P. In soil solutions from 90 cm depth, organic P was almost exclusively in the hydrophilic fraction. Because of the low retention of the hydrophilic fraction of dissolved organic matter in the mineral soils, concentrations of organic P in soil water remained almost constant with depth. Consequently, organic P contributed > 95% of the total P leached into deeper subsoils. The overall retention of organic P in the weakly developed mineral soils was little and so the average annual fluxes of organic P in subsoils at 90 cm depth (38 mg m^–2) comprised 67% of those from the forest floors (57 mg m^–2) during the study period. Hence, organic P proved to be mobile in the studied soil. ³¹P-NMR spectroscopy confirmed the dominance of organic P species in soil water. Signals due to inorganic P occurred only in spectra of samples collected in winter and spring months. Spectra of samples from summer and autumn revealed traces of condensed phosphates. Due to low P contents, identification of organic P species in samples from winter and spring was not always possible. In summer and autumn, monoester and diester phosphates were the dominant organic species and varied little in their relative distributions. The distribution of organic species changed little from forest floor leachates to the subsoil solutions indicating that the composition of P-containing compounds was not influenced by sorptive interactions or biological transformation.     

Soil organic carbon dynamics: variability with depth in forested and deforested soils under pasture in Costa Rica

Dynamics of soil organic carbon (SOC) inchronosequences of soils below forests that had beenreplaced by grazed pastures 3–25 years ago, wereinvestigated for two contrasting soil types (AndicHumitropept and Eutric Hapludand) in the Atlantic Zoneof Costa Rica. By forest clearing and subsequentestablishment of pastures, photosynthesis changes froma C-3 to a C-4 pathway. The accompanying changes inC-input and its ¹³C and ¹⁴Csignals, were used to quantify SOC dynamics. C-input from rootturnover at a pasture site was measured by sequentialharvesting and ¹⁴C-pulse labelling. With aspatial resolution of 5 cm, data on total SOC,¹³C and ¹⁴C of soil profileswere interpreted with a model that distinguishes threepools of SOC: active C, slow C and passive C,each with a 1^-st order decomposition rate(k_a, k_s and k_p). The modelincludes carbon isotope fractionation and depth-dependentdecomposition rates. Transport of C between soillayers was described as a diffusion process, whichaccounts for physical and biotic mixing processes.Calibrated diffusion coefficients were 0.42 cm²yr-¹ for the Humitropept and 3.97 cm²yr-¹ for the Hapludand chronosequence.Diffusional transport alone was insufficient foroptimal simulation; it had to be augmented bydepth-dependent decomposition rates to explain thedynamics of SOC, ¹³C and¹⁴C. Decomposition rates decreasedstrongly with depth. Upon increased diffusion,differences between calibrated decomposition rates ofSOC fractions between surface soils and subsoilsdiminished, but the concept of depth-dependentdecomposition had to be retained, to obtain smallresiduals between observed and simulated data. At areference depth of 15–20 cm k_s was 90 yr-¹in the Humitropept and 146 yr-¹ in the Hapludand.Slow C contributed most to total organic C in surfacesoils, whereas passive C contributed most below 40 cmdepth. After 18–25 years of pasture, net loss of C was2180 g C m-² for the Hapludand and 150 g m-²for the Humitropept soil.     

Export of DOC from forested catchments on the Precambrian Shield of Central Ontario: Clues from 13C and 14C

Export of dissolved organic carbon (DOC) from forested catchmentsis governed by competing processes of production, decomposition, sorptionand flushing. To examine the sources of DOC, carbon isotopes (¹⁴Cand ¹³C) were analyzed in DOC from surface waters, groundwatersand soils in a small forested catchment on the Canadian Shield in centralOntario. A significant fraction (greater than 50%) of DOCin major inflows to the lake is composed of carbon incorporated into organicmatter, solubilized and flushed into the stream within the last 40 years. Incontrast, ¹⁴C in groundwater DOC was old indicating extensiverecycling of forest floor derived organic carbon in the soil column beforeelution to groundwater in the lower B and C soil horizons. A small uplandbasin had a wide range in ¹⁴C from old groundwater values atbaseflow under dry basin conditions to relatively modern values during highflow or wetter antecedent conditions. Wetlands export mainly recently fixedcarbon with little seasonal range. DOC in streams entering the small lakemay be composed of two pools; an older recalcitrant pool delivered bygroundwater and a young labile pool derived from recent organic matter.The relative proportion of these two pools changes seasonally due thechanges in the water flowpaths and organic carbon dynamics. Althoughchanges in local climate (temperature and/or precipitation) may alterthe relative proportions of the old and young pools, the older pool islikely to be more refractory to sedimentation and decomposition in thelake setting. Delivery of older pool DOC from the catchment andsusceptibility of this older pool to photochemical decomposition mayconsequently be important in governing the minimum DOC concentrationlimit in lakes.     

Dissolved organic sulphur in soil water under <Emphasis Type="Italic">Pinus sylvestris</Emphasis> L. and <Emphasis Type="Italic">Fagus sylvatica</Emphasis> L. stands in northeastern Bavaria,Germany variations with seasons and soil depth

Organically bound species have been identified as prominent and mobile forms of nitrogen and phosphorus in soils. Since a large portion of sulphur (S) in soil is bonded to carbon (C) also dissolved organic S likely is a significant constituent in soil water. To investigate the role of dissolved organic forms in leaching and cycling of S in forest soils, we examined concentrations, fluxes, and chemical composition of organic S in forest floor leachates and in soil solutions of Rendzic Leptosols under 90-year-old European beech (Fagus sylvatica L.) and Haplic Arenosols under 160-year-old Scots pine (Pinus sylvestris L.) for 27 months. These soils are low in adsorbed SO₄^2- and receive little atmospheric S depositions at present. The chemical composition of organic S was estimated by fractionation with XAD-8 and wet-chemical characterisation (HI reduction) of binding forms. Although not as prominent as the organic forms of other nutrient elements, organic S proved to be an important contributor to S dissolved in forest floor leachates and in mineral soil solutions. Dissolved organic matter contained on average 29% of total S in forest floor leachates at the pine site and 34% at the beech site. The largest portion of organic S occurred in the subsoil solutions under beech in summer and autumn (up to 53%). Mean concentrations of organic S peaked (up to 1.1 mg l^-1) in summer after rainstorms that followed dry periods. Fluxes with forest floor leachates and at 90 cm soil depth were largest in autumn because of huge amounts of rainfall. Organic S contributed significantly to the fluxes of S in the subsoils under beech comprising on average 39% of total dissolved S at 90 cm depth. Organic S produced in the forest floor layers was mainly in the hydrophilic fraction of dissolved organic matter (62 ± 6% at the pine site, 85 ± 4% at the beech site). The major binding form of organic S in the hydrophobic fraction was C-bonded S while in the hydrophilic fraction ester sulphate S, possibly associated with carbohydrates, was more prominent. Since the hydrophobic fraction increased in summer and autumn, C-bonded S was of greater importance during that time of the year than in winter and spring. With depth, concentrations and composition of organic S (and also of C) hardly changed at the pine site because of little retention of dissolved organic matter, presumably because of the small sorption capability of that soil. At the beech where organic C showed a marked decrease with depth, only a slight decrease in organic S, exclusively from the hydrophobic fraction, was found indicating that organic S was mobile compared with organic C. This was probably due to the concentration of S in the hydrophilic fraction of dissolved organic matter. Because of being concentrated in the mobile hydrophilic fraction, ester sulphate S was more mobile in the soil under beech than C-bonded S.     

Seasonal variations in the chemical composition of dissolved organic matter in organic forest floor layer leachates of old-growth Scots pine (Pinus sylvestris L.) and European beech (Fagus sylvatica L.) stands in northeastern Bavaria, Germany

Organic matter dissolved in thepercolation water of forest soils contributeslargely to element cycling and transport ofnatural and anthropogenic compounds. The wayand extent to which these processes areaffected depends on the amount and the chemicalcomposition of soluble organic matter. Becausethe amount of soluble organic matter variesseasonally with changes in the microbialactivity in soil, it seems reasonable to assumethat there may be also seasonal changes in thechemical composition of dissolved organicmatter. We examined dissolved organic matter inthe seepage waters of organic forest floorlayers over a 27-month period (1997–1999) intwo forest ecosystems, a 160-year-old Scotspine (Pinus sylvestris L.) stand and a90-year-old European beech (Fagussylvatica L.) forest. The forest floorleachates were analysed for bulk dissolvedorganic C, C in hydrophilic and hydrophobicdissolved organic matter fractions,lignin-derived phenols (CuO oxidation),hydrolysable neutral carbohydrates and uronicacids, hydrolysable amino sugars, and stablecarbon isotope composition. In addition, westudied the samples by use of liquid-state¹³C-nuclear magnetic resonance (NMR)spectroscopy.For both investigated forest sites we foundthat the dissolved organic carbonconcentrations in forest floor leachates werelargest during summer. They peaked after rainstorms following short dry periods (106–145 mgdissolved organic C l^–1). The proportionsof C in the hydrophilic fractions were largestin winter and spring whereas in summer andautumn more C was found in the hydrophobicfraction. According to liquid-state ¹³C-NMR spectroscopy, summer and autumn samples hadlarger abundances of aromatic and aliphaticstructures as well as larger proportions ofcarboxyl groups whereas the winter and springsamples were dominated by resonances indicatingcarbohydrates. Wet-chemical analyses confirmedthese results. Winter and spring samples wererich in neutral carbohydrates and amino sugars.The summer and autumn samples contained morelignin-derived phenols which were also strongeroxidised than those in the winter and springsamples. Seasonal changes of ¹³C valueswere found to reflect the changes in thechemical composition of dissolved organicmatter. Most negative values occurred whenisotopically light lignin-derived compoundswere abundant and less negative values whencarbohydrates predominated.The different vegetation, age of thestands, and underlying mineral soils resultedin different concentrations of dissolvedorganic carbon and in differences in thedistribution between hydrophobic andhydrophilic organic carbon. Despite of this,the results suggest that the trends in temporalvariations in the composition of dissolvedorganic matter in forest floor seepage waterwere remarkably similar for both sites.Dissolved organic matter in winter and springseems to be mainly controlled by leaching offresh disrupted biomass debris with a largecontribution of bacterial and fungal-derivedcarbohydrates and amino sugars. Dissolvedorganic matter leached from the forest floor insummer and autumn is controlled by thedecomposition processes in the forest floorresulting in the production of stronglyoxidised, water-soluble aromatic and aliphaticcompounds. The chemical composition ofdissolved organic matter in forest floorseepage water in winter and spring indicateslarger mobility, larger biodegradability, andless interaction with metals and organicpollutants than that released during summer andautumn. Thus, the impact of dissolved organicmatter on transport processes may varythroughout the year due to changes in itscomposition.     

Studies on litter characterization using 13C NMR and assessment of microbial activity in natural forest and plantation crops’ (teak and rubber) soil ecosystems of Kerala, India

The leaf litter is the major source of soil organic matter in natural and many plantation crop ecosystems. Quantity and quality of organic matter in a soil ecosystem is of utmost importance in regulating the soil health. Hence assessment of quality of organic matter input, viz., litter is important and is attempted in this study. The leaf litter of rubber (Hevea brasiliensis), pueraria (Pueraria phaseoloides), mucuna (Mucuna bracteata), teak (Tectona grandis) and forest (mixed species) were analyzed using solid state ¹³C nuclear magnetic resonance (NMR) to study the relative abundance of different carbon compounds present. The spectra revealed that litter of all species studied contain relatively larger amounts of polysaccharides compared to other C containing compounds. Also it could be observed that the alkyl-C to O-alkyl-C ratio of rubber litter was much higher compared to that of others. Aromatics and carbonyl compounds were also present in all litter species. The resource quality based on alkyl-C to O-alkyl-C ratio of the litter samples studied can be arranged in the order pueraria > teak > mucuna > forest > rubber. The respiration rate, substrate induced respiration rate and biomass-C (Cmic) of the litter samples were estimated. It could be observed that litter associated microbial activity decreased as alkyl-C to O-alkyl-C ratio increased. Resource quality derived from the NMR spectra and the litter biological properties were complementary. Soil samples (0–15 cm) from the five soil ecosystems (rubber, pueraria, mucuna, teak and forest) were analyzed for respiration rate, substrate induced respiration rate, Cmic, total-C and total-N. The forest soil had higher respiration rate, total-C and total-N compared to cultivated soil systems. Pueraria, mucuna and teak soils were comparable for their biological properties while rubber soil recorded comparatively lower microbial activity.     

可溶性有机质输入对杉木人工林表层土壤有机碳矿化的激发效应

可溶性有机质(dissolved organic matter,DOM)是生态系统主要的可移动碳库及重要的养分库,它对森林土壤碳吸存的影响已引起高度关注,但DOM对森林土壤有机碳矿化的影响及机制仍不清楚。通过室内为期36 h的短期培养实验,利用~(13)C稳定同位素示踪技术,探究杉木(Cunninghamia lanceolata)凋落叶DOM、米槠(Castanopsis carlesii)凋落叶DOM、杉木死根DOM、米槠死根DOM输入对11年生杉木人工林表层(0—10 cm)土壤有机碳矿化的激发效应,以期揭示DOM在森林碳循环中的作用,对于完善森林碳循环模型有重要意义。研究结果表明:通过~(13)C标记区分不同来源CO_2后发现添加米槠凋落叶DOM和杉木凋落叶DOM处理中来自DOM的CO_2排放速率前期迅速升高,至12 h达到最大值,分别为第2小时的8.0和3.4倍,之后下降,第12小时分别为第36小时的4.6和7.0倍;来自土壤有机碳的CO_2排放速率同样在第12小时达到最大值,分别为同时间点对照的10.1倍和6.3倍。对不同来源CO_2累积排放量进行区分发现,土壤添加凋落叶DOM后来自DOM的CO_2累积排放量显著大于添加死根DOM的(P0.01),其中来自米槠凋落叶DOM的CO_2累积排放量显著大于来自杉木凋落叶DOM的(P0.05),这与添加不同来源DOM中DOC含量呈显著正相关(P0.001)。不同DOM添加对土壤有机碳矿化的激发效应强度不同,培养36h期间添加凋落叶DOM后土壤有机碳激发效应强度始终高于添加死根DOM的。添加米槠凋落叶DOM、杉木凋落叶DOM、米槠死根DOM、杉木死根DOM所引起的激发效应都在第5小时达到峰值,第36小时时添加杉木死根DOM出现负激发效应。可见,添加不同来源DOM对土壤原有有机碳矿化产生了不同的激发效应,这除了与不同来源DOM性质有关外,还可能与DOM添加后土壤微生物群落组成变化有关。有关DOM添加对土壤有机碳矿化影响的微生物学机制有待进一步研究。     

Determination of low molecular weight dicarboxylic acids and organic functional groups in rhizosphere and bulk soils of Tsuga and Yushania in a temperate rain forest

Low molecular weight organic acids (LMWOAs) derived from root exudates, decomposing organic matter, and other sources are important ligands. The species of these LMWOAs in the Tsuga rhizosphere soil (TRS), and Yushania rhizosphere soil (YRS), and bulk soil (BS) from an alpine forest region were identified. LMWOA and organic functional groups were used to those fresh twigs and leaves, litters, and roots as comparison. The objectives of this study were to (i) develop a method that could be used to determine LMWOAs in soil solution by gas chromatography (GC), (ii) assess methods for processing LMWOAs in soil samples, and (iii) determine the relative proportions of organic carbon functional groups in the TRS, YRS and BS, and fresh plant materials with¹³C nuclear magnetic resonance (¹³C NMR) analysis. The proportion of organic acid contents followed the order of YRS > TRS > BS, and also showed significant differences (P < 0.05) from GC analysis. The amounts of malonic, fumaric and succinic acids in the YRS samples were greater than in the TRS and BS. Samples analyzed after 1 month of deep freeze storage (–24°C) showed no signs of decomposition. The proportion of organic functional groups in the rhizosphere and bulk soils quantified by ¹³C NMR analyses followed the general order: alkyl-C > O-alkyl-C > N-alkyl-C > acetal-C > aromatic-C > carboxylic-C > phenolic-C.     

Chemical and seasonal controls on the dynamics of dissolved organic matter in a coniferous old-growth stand in the Pacific Northwest,USA

Soil organic matter (SOM) is the largest terrestrial C pool, and retention and release of dissolved organic matter (DOM) cause formation and loss of SOM. However, we lack information on how different sources of DOM affect its chemical composition, and how DOM chemical composition affects retention. We studied seasonal controls on DOM production and chemical controls on retention in soils of a temperate coniferous forest. The O horizon was not usually the dominant source for dissolved organic C (DOC) or N (DON) as has been reported for other sites. Rather, net production of both DOC and DON was often greater in the shallow mineral soil (0–10 cm) than in the O horizon. DOM production in the shallow mineral soil may be from root exudation as well as turnover of fine roots and microflora in the rhizosphere. In the field, the two acid fractions (hydrophobic and hydrophilic acids) dominated the soil solution at all depths. A major portion of net production and removal of total DOC within the soil column was explained by increases and decreases in these fractions, although a shift in chemical composition of DOM between the O and mineral soil horizons suggested different origins of DOM in these layers. A larger loss of the free amino fraction to deep soil water at this study site than at other sites suggested lower retention of labile DON. Field DOM removal measurements suggest that field-measured parameters may provide a good estimate for total DOM retained in mineral soil.     

1H, 13C and 15N random coil NMR chemical shifts of the common amino acids. I. Investigations of nearest-neighbor effects

Summary In this study we report on the ¹H, ¹³C and ¹⁵N NMR chemical shifts for the random coil state and nearest-neighbor sequence effects measured from the protected linear hexapeptide Gly-Gly-X-Y-Gly-Gly (where X and Y are any of the 20 common amino acids). We present data for a set of 40 peptides (of the possible 400) including Gly-Gly-X-Ala-Gly-Gly and Gly-Gly-X-Pro-Gly-Gly, measured under identical aqueous conditions. Because all spectra were collected under identical experimental conditions, the data from the Gly-Gly-X-Ala-Gly-Gly series provide a complete and internally consistent set of ¹H, ¹³C and ¹⁵N random coil chemical shifts for all 20 common amino acids. In addition, studies were also conducted into nearest-neighbor effects on the random coil shift arising from a variety of X and Y positional substitutions. Comparisons between the chemical shift measurements obtained from Gly-Gly-X-Ala-Gly-Gly and Gly-Gly-X-Pro-Gly-Gly reveal significant systematic shift differences arising from the presence of proline in the peptide sequence. Similarly, measurements of the chemical shift changes occurring for both alanine and proline (i.e., the residues in the Y position) are found to depend strougly on the type of amino acid substituted into the X position. These data lend support to the hypothesis that sequence effects play a significant role in determining peptide and protein chemical shifts.     

Synthesis and solid state 13C and 1H NMR analysis of new oxamide derivatives of methyl 2-amino-2-deoxy-alpha-D-glucopyranoside and ester of amino acids or dipeptides

The syntheses of new oxamide derivatives of methyl 2-amino-2-deoxy-alpha-D-glucopyranoside and amino acid or peptide esters are presented. The reaction of methyl 3,4,6-tri-O-acetyl-2-acetamido-2-deoxy-alpha-D-glucopyranoside and oxalyl chloride gave N-(methyl 3,4,6-tri-O-acetyl-2-deoxy-alpha-D-glucopyranosid-2-yl) oxamic acid chloride which on reaction with the ester of Gly, L-Ala, L-Phe, GlyGly, Gly-L-Phe and Gly-L-Ala afforded N-(methyl 3,4,6-tri-O-acetyl-2-deoxy-alpha-D-glucopyranosid-2-yl), N'-oxalyl-amino acid or dipeptide esters. The structure of the oxamides was studied using 1H, 13C NMR in solution and solid state.     

The dynamics of neutral sugars in the rhizosphere of wheat. An approach by13C pulse-labelling and GC/C/IRMS

Rhizodeposition, i.e. the release of carbon into the soil by growing roots, is an important part of the terrestrial carbon cycle. However thein situ nature and dynamics of root-derived carbon in the soil are still poorly understood. Here we made an investigation of the latter in laboratory experiments using¹³CO₂ pulse chase labelling of wheat (Triticum aestivum L.). We analyzed the kinetics of¹³C-labelled carbon and more specially¹³C carbohydrates in the rhizosphere. Wheat seedlings-soil mesocosms were exposed to¹³CO₂ for 5 hours in controlled chambers and sampled repeatedly during two weeks for¹³C/C analysis of organic carbon. After a two-step separation of the soil from the roots, the amount of total organic¹³C was determined by isotope ratio mass spectrometry as well as the amounts of¹³C in arabinose, fructose, fucose, glucose, galactose, mannose, rhamnose and xylose. The amount and isotopic ratio of monosaccharides were obtained by capillary gas chromatography coupled with isotope ratio mass spectrometry (GC/C/IRMS) after trimethyl-silyl derivatization. Two fractions were analyzed : total (hydrolysable) and soluble monomeric (water extractable) soil sugars. The amount of organic¹³C found in the soil, expressed as a percentage of the total photosynthetically fixed¹³C at the end of the labelling period, reached 16% in the day following labelling and stabilised at 9% after one week. We concluded that glucose under the form of polymers was the dominant moietie of rhizodeposits. Soluble glucose and fructose were also present. But after 2 days, these soluble sugars had disappeared. Forty percent of the root-derived carbon was in the form of neutral sugars, and exhibited a time-increasing signature of microbial sugars. The composition of rhizospheric sugars rapidly tended towards that of bulk soil organic matter.     

Specific 15N, NH correlations for residues in15 N, 13C and fractionally deuterated proteins that immediately follow methyl-containing amino acids

A triple-resonance pulse scheme is described which records¹⁵N, NH correlations of residues that immediately follow amethyl-containing amino acid. The experiment makes use of a¹⁵N, ¹³C and fractionally deuterated proteinsample and selects for CH₂D methyl types. The experiment isthus useful in the early stages of the sequential assignment process as wellas for the confirmation of backbone ¹⁵N, NH chemical shiftassignments at later stages of data analysis. A simple modification of thesequence also allows the measurement of methyl side-chain dynamics. This isparticularly useful for studying side-chain dynamic properties in partiallyunfolded and unfolded proteins where the resolution of aliphatic carbon andproton chemical shifts is limited compared to that of amide nitrogens.     

Effects of six years atmospheric CO2 enrichment on plant,soil, and soil microbial C of a calcareous grassland

Stimulated plant production and often even larger stimulation of photosynthesis at elevated CO₂ raise the possibility of increased C storage in plants and soils. We analysed ecosystem C partitioning and soil C fluxes in calcareous grassland exposed to elevated CO₂ for 6 years. At elevated CO₂, C pools increased in plants (+23%) and surface litter (+24%), but were not altered in microbes and soil organic matter. Soils were fractionated into particle size and density separates. The amount of low-density macroorganic C, an indicator of particulate soil C inputs from root litter, was not affected by elevated CO₂. Incorporation of C fixed during the experiment (C_new) was tracked by C isotopic analysis of soil fractions which were labelled due to ¹³C depletion of the commercial CO₂ used for atmospheric enrichment. This data constrains estimates of C sequestration (absolute upper bound) and indicates where in soils potentially sequestered C is stored. C_new entered soils at an initial rate of 210±42 g C m^–2 year^–1, but only 554±39 g C_new m^–2 were recovered after 6 years due to the low mean residence time of 1.8 years. Previous process-oriented measurements did not indicate increased plant–soil C fluxes at elevated CO₂ in the same system (¹³C kinetics in soil microbes and fine roots after pulse labelling, and minirhizotron observations). Overall experimental evidence suggests that C storage under elevated CO₂ occurred only in rapidly turned-over fractions such as plants and detritus, and that potential extra soil C inputs were rapidly re-mineralised. We argue that this inference does not conflict with the observed increases in photosynthetic fixation at elevated CO₂, because these are not good predictors of plant growth and soil C fluxes for allometric reasons. C sequestration in this natural system may also be lower than suggested by plant biomass responses to elevated CO₂ because C storage may be limited by stabilisation of C_new in slowly turned-over soil fractions (a prerequisite for long-term storage) rather than by the magnitude of C inputs per se.     

Cultivation effects on the nature of organic matter in soils and water extracts using CP/MAS 13C NMR spectroscopy

The objective of this study was to examine the chemical structure of the organic matter (SOM) of Oxisols soils in slash and burn agriculture, in relation to its biological properties and soil fertility. The CP/MAS ¹³C technique was used to identify the main structural groups in litter and fine roots as SOM precursors; to identify the changes on the nature of the SOM upon cultivation and the proportion of labile and stable components; and to identify the nature of the organics present in water extracts (DOC). Carbohydrates were the main structural components in litter whereas components such as carbonyl C, carboxyl C,O-alkyl C and alkyl C were more common in SOM. Phenolic C and the degree of aromaticity were similar in litter and SOM. Cultivation resulted in a small decrease in the relative proportion of carbohydrates in SOM, little change in the levels of O-alkyl C and carbonyl C, but an increase in carboxyl C, phenolic C and aromaticity of the SOM. The level of alkyl C in soil was higher than the level of O-alkyl C, indicating the importance of long-chain aliphatics along with lignins in the stabilization of the SOM in Oxisols. The SOM of Mollisols from the Canadian Prairies differed from the Oxisol, with a generally stronger expression of aromatic structures, particularly in a cultivated soil in relation to a native equivalent. Carbohydrate components were the predominant structures in the DOC, indicating their importance in nutrient cycling and vertical translocations in the Oxisol.     

Soil carbon stabilization in jack pine stands along the Boreal Forest Transect Case Study

Boreal forests, containing >20% of the total organic carbon (OC) present at the surface of the Earth, are expected to be highly vulnerable to global warming. The objective of this study was to compare soil OC stocks and chemistry in jack pine stands located along a latitudinal climatic transect in central Canada. Total OC stocks (0–1 m) increased with decreasing mean annual temperature (MAT). We used a combination of physical fractionation of soil OC pools, ¹³C isotopic determination and cross‐polarization, magic‐angle spinning ¹³C nuclear magnetic resonance (NMR) spectroscopy to further characterize OC composition at all sites. Soil OC was dominated by labile pools. As illustrated by the C/N ratios, δ¹³C data and results from the ¹³C NMR analysis, the light fraction showed little alteration within the soil profiles. Instead, this fraction reflected the importance of fresh litter inputs and showed an increase in root contribution with depth. As opposed to the light fraction, the clay‐ and silt‐stabilized OC exhibited an increase in δ¹³C and a decrease in C/N with depth, indicating an increase in its degree of decomposition. These changes with depth were more marked at the southern than the northern sites. Results hence suggest that if the MAT were to increase in the northern boreal forest the overall jack pine soil OC stocks would decrease but the remaining OC would become more decomposed, and likely more stabilized than what is currently present within the soils.     

Crystal structure and solid-state 13C NMR analysis of N-o-, N-m- and N-p-nitrophenyl-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosylamines, and their N-acetyl derivatives

The X-ray diffraction analysis of N-o-nitrophenyl-2,3,4,6-tetra-O-acetyl-β-d-glucopyranosylamine (1), N-m-nitrophenyl-2,3,4,6-tetra-O-acetyl-β-d-glucopyranosylamines, N-p-nitrophenyl-2,3,4,6-tetra-O-acetyl-β-d-glucopyranosylamines, and their N-acetyl derivatives was performed. The sugar moieties always adopt ⁴C₁ conformations, however, due to crystal packing forces they are always slightly distorted. It was found that except N-acetyl, N-m-nitrophenyl-2,3,4,6-tetra-O-acetyl-β-d-glucopyranosylamine (5), none of the glucopyranosylamines studied in this paper form strong hydrogen bonds in the crystal lattice. Additionally, (5) crystallizes with a molecule of water, which occupies a special crystallographic position (on the twofold axis) and links two sugar molecules by hydrogen bonds. The CP MAS NMR spectra confirmed the presence of the intermolecular hydrogen bond involving the molecule of water in (5). Moreover, it was proved that in (1) an intramolecular hydrogen bond is formed between the glycosidic linkage and the nitro group.     

Boric acid complexes with organic biomolecules: Mono-chelate complexes with salicylic and glucuronic acids

Two mono-chelate borate complexes, lithium mono-salicylatoborate and sodium mono-glucuronatoborate, are reported for the first time. The complexes were isolated from aqueous solutions and characterized by FTIR (Fourier Transform Infrared) and ¹³C MAS (Magic Angle Spinning) NMR techniques. Thermal stabilities of the complexes were examined by recording their TGA (Thermogravimetric Analysis) curves. Lithium mono-salicylatoborate, Li[B(Sal)(OH)₂], was isolated in crystal form and presented as a novel hybrid metal-organic framework possessing zeolitic structure. X-ray analysis revealed an original crystal structure constructed with solvate-free lithium ions adopting two different types of coordination polyhedra, corner-sharing LiO₄ (tetrahedral) and LiO₅ (distorted square pyramidal), in the same framework.     

Characterization of solid and dissolved carbon in a spruce-fir Spodosol

Organic substances are an integral part of the biogeochemistry of many elements in forest ecosystems. However, our understanding of the composition, chemistry, and reactions of these materials are incomplete and sometimes inconsistent. Therefore, we examined in detail dissolved organic carbon (DOC) in forest floor leachates over a two-year period (1992–1993), soil C, and DOC adsorption by a mineral soil to determine the relationship between soil solid and solution C characteristics in a spruce-fir ecosystem. The structural composition of DOC, DOC fractions (hydrophobic and hydrophilic acids, hydrophilic neutrals), and soil samples from the organic and mineral horizons were also analyzed using¹³C nuclear magnetic resonance (NMR) spectroscopy.Total DOC in forest floor leachates ranged from 7.8 to 13.8 mmol L^–1 with an average of 8.6 mmol L^–1. Concentrations were highest in September of both 1992 and 1993. Fractionation of the forest floor DOC indicated these solutions contained high organic acid contents that averaged 92% of the total DOC. Hydrophobic acids were also preferentially adsorbed by the B horizon. The¹³C NMR data suggested alkyl, carbohydrate, aromatic, and carboxylic C were the primary constituents for organic and mineral soils, DOC, and DOC fractions. Compositional changes of C were observed as aromatic and carbohydrate decreased, whereas alkyl, methoxy, and carbonyl moieties increased with depth. However, C composition changed little among the three organic layers based on the similarity of alkyl/carbohydrates ratios as determined from NMR area integration, suggesting that in this acid soil, decomposition proceeds rather slowly. Hydrophobic acids contained high contents of aromatic C, whereas hydrophilic acids were comprised primarily of carboxylic C. Hydrophilic neutrals were rich in carbohydrate C. Results indicated that these DOC fractions were unaltered during the isolation process. Carboxylic C groups appeared to dissolve easily and were probably the primary contributor to organic acidity in our organic dominate leachates. Results also suggested that DOC materials adsorbed on the B horizon underwent further biodegradation. Several seasonal patterns of C composition were observed in the forest floor leachates and DOC fractions collected between 1992 and 1993.Overall, the evidence from this study suggested that (i) DOC levels were mainly controlled by biological activity, (ii) forest floor DOC was comprised primarily of organic acids, (iii) contact of soil leachates with B horizon material affected DOC quantitatively and qualitatively, (iv) phenolic, carboxylic, and carbonyl C appeared to dissolve readily in the forest Oa horizon, (v) DOC materials adsorbed on the B horizon selectively underwent further decomposition, and (vi) C composition is a function of the extent of decomposition and DOC fractions.     

Changes of the forest-savanna boundary in Brazilian Amazonia during the Holocene revealed by stable isotope ratios of soil organic carbon

The possibility of ecosystem boundary changes in northern Brazilian Amazonia during the Holocene period was investigated using soil organic carbon isotope ratios. Determination of past and present fluctuations of the forest-savanna boundary involved the measurement of natural ¹³C isotope abundance, expressed as ¹³C, in soil organic matter (SOM). SOM ¹³C analyses and radiocarbon dating of charcoal fragments were carried out on samples derived from soil profiles taken along transects perpendicular to the ecotonal boundary. SOM ¹³C values in the upper soil horizons appeared to be in equilibrium with the overlying vegetation types and did not point to a movement of the boundary during the last decades. However, ¹³C values obtained from deeper savanna and forest soil layers indicated that the vegetation type has changed in the past. In current savanna soil profiles, we observed the presence of mid-Holocene charcoals derived from forest species: fire frequency at that time was probably greater, and more extensive savanna may have resulted. Isotope data and the presence of these charcoals thus suggest that the forest-savanna boundary has shifted significantly in the recent Holocene period, forest being more extensive during the early Holocene than today. During the middle Holocene, the forest could have strongly regressed, and fires appeared, with a maximum development of the savanna vegetation. At the beginning of the late Holocene, the forest may have invaded a part of this savanna, and fires occurred again.