Paddy management on different soil types does not promote lignin accumulation

Paddy soil management is generally thought to promote the accumulation of soil organic matter (SOM) and specifically lignin. Lignin is considered particularly susceptible to accumulation under these circumstances because of the recalcitrance of its aromatic structure to biodegradation under anaerobic conditions (i.e ., during inundation of paddy fields). The present study investigates the effect of paddy soil management on SOM composition in comparison to nearby agricultural soils that are not used for rice production (non‐paddy soils). Soil types typically used for rice cultivation were selected, including Alisol, Andosol and Vertisol sites in Indonesia (humid tropical climate of Java) and an Alisol site in China (humid subtropical climate, Jiangxi province). These soil types represent a range of soil properties to be expected in Asian paddy fields. All upper‐most A horizons were analysed for their SOM composition by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy and for lignin‐derived phenols by the CuO oxidation method. The SOM composition was similar for all of the above named parent soil types (non‐paddy soils) and was also not affected by paddy soil management. A substantial proportion (up to 23%) of the total aryl‐carbon in some paddy and non‐paddy soils was found to originate from condensed aromatic‐carbon (e.g ., charcoal). This may be attributed to the burning of crop residues. On average, the proportion of lignin was low and made up 20% of the total SOM, and showed no differences between straw, particulate organic matter (POM), and the bulk soil material. The results from CuO oxidation are consistent with the data obtained from solid‐state ¹³C NMR spectroscopy. The extraction of lignin‐derived phenols revealed low VSC (vanillyl, syringyl, cinnamyl) values for all investigated soils in a range (4 to 12 g kg⁻¹ OC) that was typical for agricultural soils. In comparison to adjacent non‐paddy soils, the data do not provide evidence for a substantial accumulation of phenolic lignin‐derived structures in the paddy soils, even for those characterized by higher organic carbon (OC) contents (e.g ., Andosol‐ and Alisol (China)‐derived paddy soils). We conclude that the properties of the parent soil types are more important for the lignin content of the soils than the effect of paddy management itself.     

The influence of soil processes on carbon isotope distribution and turnover in the British uplands

Understanding the natural variation of carbon within the soil, and between soil types, is crucial to improve predictive models of carbon cycling in high and mid-latitude ecosystems in response to global warming. We measured the carbon isotope distributions (¹²C, ¹³C and ¹⁴C) in soil organic matter (SOM) from Podzols, Brown Podzolic soils and Stagnohumic Gleysols from the British uplands, which were then compared with the total amounts and turnover of carbon in these soils. We did so by sampling at 2-cm intervals down six profiles of each soil type. The average amount of carbon stored in the top 28 cm of the Stagnohumic Gleysols is twice that of the other two soils. The ¹³C content and ¹⁴C age show a general increase with depth in all soils, and there is also a significant correlation between isotopic variation and the main pedogenic features. The latter suggests that soil-forming processes are significant in determining the carbon isotope signatures retained in SOM. Organic matter formed since 1960 is not found below 5 cm in any of the soils. Evidently organic detritus in the surface layers (LF and Oh) is rapidly mineralized. This accords with our modelled net annual C fluxes which show that more than 80% of the CO₂ emanating from these soils is derived from the top 5 cm of each profile. Although these soils contain much carbon, they do not appear to assimilate and retain SOM rapidly. The mean residence time of most of their carbon is in the 2–50 years range, so the soils are fairly ineffective sinks for excess CO₂ in the atmosphere. Under the predicted future ‘greenhouse’ climate, likely to favour more rapid microbial decomposition of organic materials, these soils are a potential source of CO₂ and are therefore likely to accelerate global warming.     

Changes in the chemical composition of soil organic matter after application of compost

Is the composition of soil organic matter changed by adding compost? To find out we incubated biowaste composts with agricultural soils and a humus‐free mineral substrate at 5°C and 14°C for 18 months and examined the products. Organic matter composition was characterized by CuO oxidation of lignin, hydrolysis of cellulosic and non‐cellulosic polysaccharides (CPS and NCPS) and ¹³C cross‐polarization magic angle spinning nuclear magnetic resonance (CPMAS ¹³C‐NMR) spectroscopy. The lignin contents in the compost‐amended soils increased because the composts contained more lignin, which altered little even after prolonged decomposition of the composts in soil. A pronounced decrease in lignin occurred in the soils amended with mature compost only. Polysaccharide C accounted for 14–20% of the organic carbon at the beginning of the experiment for both the compost‐amended soils and the controls. During the incubation, the relative contents of total polysaccharides decreased for 9–20% (controls) and for 20–49% (compost‐amended soils). They contributed preferentially to the decomposition as compared with the bulk soil organic matter, that decreased between < 2% and 20%. In the compost‐amended agricultural soils, cellulosic polysaccharides were decomposed in preference to non‐cellulosic ones. The NMR spectra of the compost‐amended soils had more intense signals of O–alkyl and aromatic C than did those of the controls. Incubation for 18 months resulted mainly in a decline of O–alkyl C for all soils. The composition of the soil organic matter after compost amendment changed mainly by increases in the lignin and aromatic C of the composts, and compost‐derived polysaccharides were mineralized preferentially. The results suggest that decomposition of the added composts in soil is as an ongoing humification process of the composts themselves. The different soil materials affected the changes in soil organic matter composition to only a minor degree.     

APPLICATIONS OF NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY TO THE STUDY OF THE STRUCTURE OF SOIL ORGANIC MATTER

Recent developments in the application of nuclear magnetic resonance (n.m.r.) spectroscopy to soil science are reviewed. Progress in ¹H, ¹³C and CP-¹³C n.m.r. spectroscopy of humic substances is reported. Methods of determining the fraction of aromatic carbon in soil organic matter extracts are discussed, and methods by which structural group analysis can be carried out on in situ organic matter of whole soils are reviewed.     

Structure of humic acids in zonal soils from <Superscript>13</Superscript>C NMR data

The structure of humic acids (HAs) in zonal soil types—soddy-podzolic soils (two samples), gray forest soil (one sample), and chernozems (two samples)—was quantitatively studied by ¹³C NMR spectros-copy. In the series considered, the content of unsubstituted carbon in the aromatic fragments of HAs increased, and the fraction of unsubstituted aliphatic structures decreased. HAs of soddy-podzolic soils were found to be enriched with carbohydrate fragments compared to HAs of chernozems and gray forest soil. The carbon skeleton of HAs from typical rich chernozem contained significantly more aliphatic and carbohydrate fragments compared to typical chernozem, which probably reflected the lower degree of HA transformation in rich chernozem.     

美国8种土壤的活性腐植酸和难溶性钙质腐植酸盐中碳官能团的特性分析

Solid state13C nuclear magnetic resonance(NMR)spectroscopy is a common tool to study the structure of soil humic fractions;however,knowledge regarding carbon structural relationships in humic fractions is limited.In this study,mobile humic acid(MHA)and recalcitrant calcium humate(CaHA)fractions were extracted from eight soils collected from six US states and representing a variety of soils and ecoregions,characterized by this spectroscopic technique and analyzed for statistical significance at P≤0.05.We found that the abundances of COO and N–C=O functional groups in the MHA fractions were negatively correlated to soil sand content,but were positively correlated to silt,total N and soil organic carbon contents.In contrast,the abundances of the COO and N–C=O functional groups were only positively correlated to the content of clay in the CaHA fractions,indicating that the two humic fractions were associated with diferent soil components.The two13C NMR peaks representing alkyls and OCH3/NCH were negatively correlated to the peaks representing aromatics,aromatic C–O and N–C=O/COO.Comparison of the sets of data from13C NMR spectroscopy and ultrahigh resolution mass spectrometry revealed that the aromatic components identified by the two methods were highly consistent.The comparison further revealed that protein in MHA was associated with,or bound to,the nonpolar alkyl groups,but a component competitively against(or complementary to)aromatic groups in the MHA composition.These observations provided insight on the internal correlations of the functional groups of soil humic fractions.     

The carbon content of soil and its geographical distribution in Great Britain

Abstract. England and Wales have 155 314 1 × 1 km squares, of which 140049 have more than 50% soil cover. The total soil organic carbon content, based on the dominant soil series and dominant land cover type, is estimated to be 2773 × 10⁶ t C. Scotland has 84929 1 × 1 km squares, of which 82 420 have a nominated dominant soil series. The total soil organic carbon content is estimated to be 19011 × 10⁶ t C, 6.85 times the total organic carbon content of the soil of England and Wales. The total organic carbon content of the soil of Great Britain is estimated to be 21 784 × 10⁶ t C, of which 87% is in Scottish soils and 75% is in Scottish peats. A map of the mean soil organic carbon content of 10 × 10 km squares of the National Grid using classes of equal range illustrates the narrow range of organic carbon contents of the soils of England and Wales and the dominance of organic carbon in Scottish soils. A map using the same data, but with classes of unequal ranges increasing in size with increasing carbon content, is better for showing detailed differences within England and Wales.     

Cesium and soil carbon in a small agricultural watershed

Scientific, political, and social interests have developed recently in the concept of using agricultural soils to sequester carbon. Studies supporting this concept indicate that soil erosion and subsequent redeposition of eroded soils in the same field may establish an ecosystem disequilibrium that promotes the buildup of carbon on agricultural landscapes. The problem is to determine the patterns of soil erosion and redeposition on the landscape and to relate these to soil carbon patterns. Radioactive ¹³⁷cesium (¹³⁷Cs) can be used to estimate soil erosion patterns and, more importantly, redeposition patterns at the field level. The purpose of this study was to determine the relationship between ¹³⁷Cs, soil erosion, and soil carbon patterns on a small agricultural watershed. Profiles of soils from an upland area and soils in an adjacent riparian system were collected in 5 cm increments and the concentrations of ¹³⁷Cs and carbon were determined. ¹³⁷Cs and carbon were uniformly mixed in the upper 15–20 cm of upland soils. ¹³⁷Cs (Bq g⁻¹) and carbon (%) in the upland soils were significantly correlated (r²=0.66). Carbon content of the 0–20 cm layer was higher (1.4±0.3%) in areas of soil deposition than carbon content (1.1±0.3%) in areas of soil erosion as determined by the ¹³⁷Cs technique. These data suggest that measurements of ¹³⁷Cs in the soils can be useful for understanding carbon distribution patterns in surface soil. Carbon content of the upland soils ranged from 0.5 to 1.9% with an average of 1.2±0.4% in the 0–20 cm layer while carbon below this upper tilled layer (20–30 cm) ranged from 0.2 to 1.5% with an average of 0.5±0.3%. Total carbon was 2.66 and 3.20 kg m⁻² in the upper 20 cm and upper 30 cm of the upland soils, respectively. Carbon content of the 0–20 cm layer in the riparian system ranged from 1.1 to 67.0% with an average 11.7±17.1%. Carbon content below 20 cm ranged from 1.8 to 79.3% with an average of 18.3±17.5%. Soil carbon in the upper 20 cm of the riparian profile was 10.1 and 15.0 kg m⁻² in the upper 30 cm of the riparian profiles. This is an increase of organic carbon by a factor of 3.8 and 4.7 for the upper 20 cm and upper 30 cm of the riparian profiles, respectively, when compared to the upland soil profiles.     

Chemical characteristics of glomalin-related soil protein (GRSP) extracted from soils of varying organic matter content

Glomalin is described in the literature as a N-linked glycoprotein and the putative gene product of arbuscular mycorrhizal fungi (AMF). Since the link between glomalin and various protein fractions in soil is not yet clearly defined, glomalin-related soil protein (GRSP) more appropriately describes glomalin's existence in natural organic matter (NOM). The objective of this study was to examine the chemical characteristics of GRSP present in several mineral and organic soils of varying organic carbon content. GRSP was isolated using high temperature sodium citrate extraction followed by either trichloroacetic acid (TCA) or hydrochloric acid (HCl) precipitation. GRSP was characterized by quantitative solid-state ¹³C DPMAS NMR, infrared (IR) spectroscopy, elemental analysis, and the Bradford assay for protein content. GRSP accounted for 25% and 52% of total C in the mineral soils and organic soil, respectively. Molar C/N and H/C ratios reveal that GRSP has less nitrogen than bovine serum albumin (BSA), and that GRSP extracted from the Pahokee peat soil possessed a more unsaturated, and thus aromatic character relative to the mineral soil GRSP, respectively. GRSP's high aromatic (42-49%) and carboxyl (24-30%) carbon contents and low aliphatic (4-11%) and carbohydrate-type carbon contents (4-16%) suggests that GRSP does not resemble a typical glycoprotein. In fact, the NMR spectra of GRSP closely resemble that of humic acid. GRSP extracted from mineral and organic soils possessed the same NMR fingerprint regardless of the precipitation method used (i.e., either TCA or HCl). It is likely that the current GRSP extraction methods, because of their similarity to the method used to extract humic acid, are coextracting both materials.     

Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar

Purpose  

Polycyclic aromatic hydrocarbon (PAHs) are ubiquitous pollutants in agricultural soils in China. Biochar is the charred product of biomass pyrolysis, which is widely applied to soils to sequestrate atmospheric carbon dioxide and guarantees a long-term benefit for soil fertility. Knowledge about the impacts of various biochars on soil sorption affinity remains obscure. In this study, we evaluated the effects of various biochars on PAHs sorption to biochar-amended agricultural soil.     

Amount and composition of clay-associated soil organic matter in a range of kaolinitic and smectitic soils

In the global carbon cycle, soil organic matter (SOM) is a major source/sink of atmospheric carbon. Clay minerals stabilize part of the SOM through mineral–organic matter binding. Stabilization of organic matter is essential for tropical soils. Since the climatic conditions of the tropics favor decomposition of organic matter, tropical soils would be very poor in organic matter without this stabilization process. This research aims at determining the effect of clay mineralogy on the amount and composition of organic matter that is bound to the mineral surface. We focused on organic matter that is associated with kaolinite and smectite. We characterized kaolinite- and smectite-associated SOM in soils from seven countries, employing ¹³C NMR spectroscopy and Py-GC/MS. The content of carbon in the total clay-size fraction showed no significant difference between kaolinitic and smectitic soils. This suggests that the total amount of organic carbon in the clay-size fraction is independent of the clay mineralogy. We first extracted the clay fraction with NaOH and thereafter with Na₄P₂O₇. About half of the kaolinite-associated SOM was extractable by NaOH. In the smectitic soils, pyrophosphate extracted more organic carbon than did NaOH. The Py-GC/MS and NMR results indicate that kaolinite-associated SOM is enriched in polysaccharide products, while smectite-associated organic matter contains many aromatic compounds. We suggest that different clay minerals use different binding mechanisms to complex SOM. As a result, the composition of clay-associated organic matter would be influenced by the type of clay that is dominantly present in the soil.     

Particle size fractionation of soil containing coal and combusted particles

Standard procedure for dispersing natural soils for particle size fractionation can be too aggressive for soil containing coal and other organic particles from coal industries. We have investigated ultrasonic dispersion for the latter in four soils differing in pedogenesis (Phaeozem, Podzol, reclaimed mine soils), carbon content (27.5–138.6 g kg^–1), clay content (80–153 g kg^–1) and sources of particles (airborne coal dust, combustion residues, lignite particles). As we found previously for natural soils, the ultrasonic energy needed for complete dispersion varies between 450 and 500 J ml^–1, but the resulting particle size distributions differ from those obtained by standard textural analysis. This is probably related to the different properties of native soil organic matter and coal and combusted particles. Coal and soot particles may partly resist oxidation with hydrogen peroxide, depending on material and particle size. The diameter of lignite particles, remaining after oxidation, is overestimated in sedimentation analysis by a factor of 1.66. Sand-sized lignite particles can be disrupted by ultrasonication and redistributed to finer particle size fractions. The ultrasonic dispersion and particle size fractionation procedure can be applied to soils containing coal and combusted particles, but caution is needed in interpreting the results if they contain large proportions of coal particles.     

Potential for carbon sequestration after biochar-P fertilizer application: A biological and chemical assessment

Innovation is required on many fronts in agriculture, not only to improve nutrient use efficiency but also to mitigate the effects of climate change. Our previous studies presented the high agronomic efficiency of an experimental phosphate fertilizer using a biochar-matrix, called ‘BioFert’. However, the efficiency of BioFert for soil carbon sequestration goals has not yet been evaluated. We incubated BioFert and initial raw sugarcane-biochar over 56 days in two soils (i.e., Ferralsol and Alisol) and measured the total CO₂ and δ¹³C-CO₂ to quantify the contribution of native soil organic matter, sugarcane-biochar, or BioFert to carbon mineralization. There was no significant difference in cumulative CO₂ release between BioFert and the control (without carbon addition), and BioFert was less mineralized than carbon from sugarcane-biochar regardless of soil type. In addition, accelerated aging by thermal oxidation of these carbon sources revealed that more than 80% of BioFert-carbon was prevented from accelerated mineralization, while sugarcane-biochar achieved ~80% of carbon mineralization. The residual solids after oxidation were analysed by X-ray photoelectron spectroscopy and indicated aliphatic/aromatic and carboxylic chemical bonds on the BioFert surface, which might offer new cation exchange sites over time. We conclude that BioFert is not only a phosphate fertilizer with high phosphorus use efficiency but also a stable source of carbon for soil carbon sequestration purposes.     

应用~(13)C核磁共振技术研究土壤有机质化学结构进展

土壤有机质化学结构对准确评价土壤有机质的稳定性及其在土壤中的功能具有重要意义。土壤有机质化学结构的研究方法中,固态~(13)C核磁共振波谱技术(Solid-state ~(13)C-NMR spectroscopy)具有独特优势,对土壤有机质化学结构的解析更贴近真实状态,近年来已取得诸多新进展和新突破。综述了近年来应用~(13)C-NMR测定土壤全土、团聚体和密度组分、腐殖质组分的有机碳化学结构特征,分析了影响化学结构变化的因素。不同气候条件、植被类型、土地利用管理方式、土壤类型、土壤有机碳含量的全土中有机碳化学结构比较相似,均表现为烷氧碳比例最高,其次为烷基碳和芳香碳,羧基羰基碳比例最低。土壤有机碳主要来源于外源植物残体,植物残体化学结构的相似性可能是导致土壤有机碳化学结构相似的主要原因,环境条件、土壤自身属性和微生物活性的差异使土壤有机碳化学结构产生微小差异。土壤颗粒及化学组分间的有机碳分子结构差异较大,大颗粒有机碳中烷氧碳比例最高,小粒径及与矿物颗粒结合的有机碳中烷基碳和羧基羰基碳比例更高,粉黏粒和腐殖酸组分的有机碳化学结构在土壤类型间差异较大。今后的研究重点应更多地关注土壤有机质来源的定量化分析、土壤微生物对土壤有机碳组分和结构稳定性的贡献及调控机制、土壤有机碳稳定性的生物物理化学保护机制、空间大尺度环境因子/土壤生态过程与微观尺度的有机碳化学分子结构的耦合作用机制、跨学科的多种土壤有机碳化学分子结构测定辨识技术等方面的研究。     

城郊土壤不透水表面有土壤机碳转化及其相关性质的研究

Installation of impervious surface in urban area prevents the exchange of material and energy between soil and other environmental counterparts, thereby resulting in negative effects on soil function and urban environment. Soil samples were collected at 0-20 cm depth in Nanjing City, China, in which seven sites were selected for urban open soils, and fourteen sites with similar parent material were selected for the impervious-covered soils, to examine the effect of impervious surface on soil properties and microbial activities, and to determine the most important soil properties associated with soil organic carbon （SOC） transformation in the urban soils covered by impervious surfaces. Soil organic carbon and water-soluble organic carbon （WSOC） concentrations, potential carbon （C） and nitrogen （N） mineralization rates, basal respiration, and physicochemical properties with respect to C transformation were measured. Installation of impervious surface severely affected soil physicochemical properties and microbial activities, e.g., it significantly decreased total N contents, potential C mineralization and basal respiration rate （P 〈 0.01）, while increased pH, clay and Olsen-P concentrations. Soil organic carbon in the sealed soils at 0-20 cm was 2.35 kg m-2, which was significantly lower than the value of 4.52 kg m-2 in the open soils （P 〈 0.05）. Canonical correlation analysis showed WSOC played a major role in determining SOC transformation in the impervious-covered soil, and it was highly correlated with total N content and potential C mineralization rate. These findings demonstrate that installation of impervious surface in urban area, which will result in decreases of SOC and total N concentrations and soil microbial activities, has certain negative consequences for soil fertility and long-term storage of SOC.     

Carbon storage in loess derived surface soils from Central Germany: Influence of mineral phase variables

The influence of the soil mineral phase on organic matter storage was studied in loess derived surface soils of Central Germany. The seven soils were developed to different genetic stages. The carbon content of the bulk soils ranged from 8.7 to 19.7 g kg^—1. Clay mineralogy was confirmed to be constant, with illite contents > 80 %. Both, specific surface area (SSA, BET‐N₂‐method) and cation exchange capacity (CEC) of bulk soils after carbon removal were better predictors of carbon content than clay content or dithionite‐extractable iron. SSA explained 55 % and CEC 54 % of the variation in carbon content. The carbon loadings of the soils were between 0.57 and 1.06 mg C m^—2, and therefore in the ”︁monolayer equivalent” (ME) level. The increase in SSA after carbon removal (ΔSSA) was significantly and positively related to carbon content (r² = 0.77). Together with CEC of carbon‐free samples, ΔSSA explained 90 % of the variation in carbon content. Clay (< 2 μm) and fine silt fractions (2—6.3 μm) contained 68—82 % of the bulk soil organic carbon. A significantly positive relationship between carbon content in the clay fraction and in the bulk soil was observed (r² = 0.95). The carbon pools of the clay and fine silt fractions were characterized by differences in C/N ratio, δ¹³C ratio, and enrichment factors for carbon and nitrogen. Organic matter in clay fractions seems to be more altered by microbes than organic matter in fine silt fractions. The results imply that organic matter accumulates in the fractions of smallest size and highest surface area, apparently intimately associated with the mineral phase. The amount of cations adhering to the mineral surface and the size of a certain and specific part of the surface area (ΔSSA) are the mineral phase properties which affect the content of the organic carbon in loess derived arable surface soils in Central Germany most. There is no monolayer of organic matter on the soil surfaces even if carbon loadings are in the ME level.     

评估烧失量测定法测定中国西北干旱土壤有机和无机碳的研究

There is a need for determinations of soil organic carbon (SOC) and inorganic carbon (SIC) due to increasing interest in soil carbon sequestration. Two sets of soil samples were collected separately from the Yanqi Basin of northwest China to evaluate loss-on-ignition (LOI) method for estimating SOC and SIC in arid soils through determining SOC using an element analyzer, a modified Walkley-Black method and a LOI method with combustion at 375℃ for 17 h and determining SIC using a pressure calcimeter method and a LOI procedure estimated by a weight loss between 375 to 800℃. Our results indicated that the Walkley-Black method provided 99%recovery of SOC for the arid soils tested. There were strong linear relationships(r > 0.93, P < 0.001) for both SOC and SIC between the traditional method and the LOI technique. One set of soil samples was used to develop relationships between LOI and SOC(by the Walkley-Black method), and between LOI and SIC(by the pressure calcimeter method), and the other set of soil samples was used to evaluate the derived equations by comparing predicted SOC and SIC with measured values. The mean absolute errors were small for both SOC (1.7 g C kg-1) and SIC(1.22 g C kg-1), demonstrating that the LOI method was reliable and could provide accurate estimates of SOC and SIC for arid soils.     

Soil carbon stocks along an altitudinal gradient in different land-use categories in Lesser Himalayan foothills of Kashmir

The carbon sequestration potential of soils plays an important role in mitigating the effect of climate change, because soils serve as sinks for atmospheric carbon. The present study was conducted to estimate the carbon stocks and their variation with altitudinal gradient in the Lesser Himalayan foothills of Kashmir. The carbon stocks were estimated in different land use categories, namely: closed canopy forests, open forests, disturbed forests, and agricultural lands within the altitudinal range from 900 to 2500 m. The soil carbon content was determined by the Walkley–Black titration method. The average soil carbon stock was found to be 2.59 kg m^–2. The average soil carbon stocks in closed canopy forests, open forests, and disturbed forests were 3.39, 2.06, and 2.86 kg m^–2, respectively. The average soil carbon stock in the agricultural soils was 2.03 kg m^–2. The carbon stocks showed a significant decreasing trend with the altitudinal gradient with maximum values of 4.13 kg m^–2 at 900–1200 m a.s.l. and minimum value of 1.55 kg m^–2 at 2100^–2400 m a.s.l. The agricultural soil showed the least carbon content values indicating negative impacts of soil plowing, overgrazing, and soil degradation. Lower carbon values at higher altitudes attest to the immature character of forest stands, as well as to degradation due to immense fuel wood extraction, timber extraction, and harsh climatic conditions. The study indicates that immediate attention is required for the conservation of rapidly declining carbon stocks in agricultural soils, as well as in the soils of higher altitudes.     

13C NMR characterization of humic acids from soils of a development sequence

Humic acids were isolated from nine topsoils in New Zealand tussock grasslands. Cross-polarization ¹³C NMR spectra of solid samples were used to estimate fractions of carbon contained in different types of chemical functional groups. The degree of oxygen substitution of aromatic rings showed a strong negative correlation with soil development. Aromaticities greater than 0.25 were found in humic acids from only the two least-developed soils.     

Chemical composition of the organic matter in forest soils: The humus layer

Decomposition and humification were studied within three types of forest humus (mull, moder, and mor) by means of CPMAS ¹³C NMR spectroscopy combined with degradative methods. The NMR data show that O-alkyl carbon decreases in all soils, and alkyl as well as carboxyl carbon increase as depth and decomposition increase; the percentage of aromatic carbon remains constant at about 25%. With increasing depth the amount of carbon that can be identified as belonging to specific compound classes by wet chemical methods decreases from 60% to 40%. Microbial polysaccharides and the proportion of non polysaccharide O-alkyl carbon increase with depth. A selective preservation of recalcitrant, condensed lignin structural units is also observed. In order to relate the spectroscopic and chemical data from investigations of whole soils with studies of humification, samples were fractionated into fulvic acid, humic acid, and humin fractions. The fulvic acid fraction contains large concentrations of carbohydrates irrespective of the soil horizon. The humic acid fraction contains less polysaccharides, but high amounts of alkyl carbon and aromatic structures. The percentage of aromatic carbon existing in the humic acid fraction increases with depth, probably reflecting the amount and degree of oxidative decomposition of lignin. A loss of methoxyl and phenolic groups is evident in the ¹³C NMR spectra of the humic acid fraction. The humin fraction resembles relatively unchanged plant-derived materials as evident from the lignin parameters and carbohydrate contents. All the observed data seem to indicate that humic acids originate form oxidative degradation of humin or plant litter.