Arbuscular mycorrhizal fungi contribute to C and N enrichment of soil organic matter in forest soils

Increasing evidence suggests that accretion of microbial turnover products is an important driver for isotopic carbon (C) and nitrogen (N) enrichment of soil organic matter (SOM). However, the exact contribution of arbuscular mycorrhizal fungi (AMF) to soil isotopic patterns remains unknown. In this study, we compared ¹³C and ¹⁵N patterns of glomalin-related soil protein (GRSP), which includes a main fraction derived from AMF, litter, and bulk soil in four temperate rainforests. GRSP was an abundant C and N pool in these forest soils, showing significant ¹³C and ¹⁵N enrichment relative to litter and bulk soil. Hence, cumulative accumulation of recalcitrant AMF turnover products in the soil profile likely contributes to ¹³C and ¹⁵N enrichment in forest soils. Further research on the relationship between GRSP and AMF should clarify the exact extent of this process.     

Decomposition and the contribution of glomalin-related soil protein (GRSP) in heavy metal sequestration: Field experiment

Glomalin is a metal-sorbing glycoprotein excreted by arbuscular mycorrhizal fungi (AMF). One method of estimating glomalin in soils is as glomalin-related soil protein (GRSP). In this study the role of GRSP in sequestering Pb and Cd was investigated in an in situ field experiment. The effect of metal sequestration on the subsequent decomposition of GRSP was also investigated. GRSP was determined using the Bradford method as total glomalin-related soil protein (T-GRSP) and as easily extractable glomalin-related soil protein (EE-GRSP). After 140 days, GRSP bound Pb accounted for 0.21–1.78% of the total Pb, and GRSP bound Cd accounted for 0.38–0.98% of the total Cd content in the soil. However when compared on a soil organic matter (SOM) basis, only 4% of the Pb or Cd was bound to the GRSP fraction of the SOM compared with 40–54% of the Pb or Cd bound to the humin and fulvic acids in the SOM fraction. In soils contaminated with the highest levels of Pb and Cd, the T-GRSP (EE-GRSP) decomposition after 140 days was reduced by 8.0 (6.6)% and 7.0 (7.5)%, respectively, when compared with the controls. In the high Pb or Cd treatment groups we found that the fraction of metal bound to GRSP increased even though the total GRSP content declined over time. The mass ratio between Pb and GRSP-carbon changed from 2.3 to 271.4 mg (100 g)⁻¹ in all Pb levels soil, while with the high-Cd treatment group the mass ratio between Cd and GRSP-carbon (0.36 mg (100 g)⁻¹) was higher than the mass ratio seen with Cd-bound humic acid fractions. Our in situ field study shows that while GRSP does bind Pb and Cd, in the soils we investigated, the levels are insignificant compared to soil organic matter such as humic and fulvic acids.     

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。     

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.     

Cultivation-Induced Effects on the Organic Matter in Degraded Southern African Soils

We studied quantitative and qualitative changes in soil organic matter (SOM) due to different land uses (reference woodland versus cultivated) on six soils from Tanzania (Mkindo and Mafiga), Zimbabwe (Domboshawa and Chickwaka), and South Africa (Hertzog and Guquka). Structural characteristics of the humic acids (HAs) were measured by Curie-point pyrolysis–gas chromatography/mass spectrometry (P_y–GC/MS) and solid-state ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy. Significant changes in concentration and composition of SOM were observed between land uses. Losses of organic carbon after cultivation ranged from 35% to 50%. Virgin soils showed large proportions of colloidal humus fractions: humic acids (HAs) and fulvic acids (FAs) but negligible amounts of not-yet decomposed organic residues. The change in land use produced a contrasting effect on the composition of the HAs: a noteworthy “alkyl enhancement” in Mkindo soil and “alkyl depletion” in Chikwaka and to a lesser extent in Domwoshawa. The remaining soils displayed only minor alterations.     

Characterization of hydrophobic acid fractions in water-soluble organic matter in Dystric Cambisol and in a stream in a small forested watershed: Seasonal and vertical variations in chemical properties

Abstract

Chemical properties of hydrophobic acid (HoA) fractions in water-soluble organic matter in soil and water are concerned with its interactions with mineral soil surfaces and organic pollutants. In 2004 we examined the seasonal and vertical changes in chemical properties of the HoA fraction in a Cambisol profile and compared these properties with those in the HoA fraction of an adjacent stream (aquatic humic substances) in a temperate forested watershed using high performance size exclusion chromatography (HPSEC) and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The HoA fractions from Oi, Oe/Oa, A and B horizon soils in summer had lower O-alkyl C proportions than those recorded in samples in other seasons. The proportions of aromatic C in HoA fractions from A and B horizons were highest in summer. These seasonal variations were less significant than variations with soil depth. O-alkyl C proportions in HoA fractions decreased with increasing soil depth from the Oi to the A horizon. The HoA fractions from the B horizon showed a higher alkyl C proportion than samples from other horizons in winter and spring. These changes with soil depth from the Oi to A horizons might result from selective utilization of carbohydrate carbon by microorganisms, whereas those in the B horizon may result from sorption to mineral surfaces. The HoA fractions in the stream were similar in relative molecular weight, distribution of each type of proton and carbon species in HoA fractions from the B horizon, whereas stream HoA fractions collected in summer would be derived from organic horizons. This indicated that vertical changes in the chemical properties of HoA fractions in soil and pathways of water to the stream would largely affect the chemical properties of HoA fractions in the stream.     

Land use effects on carbon quality and soil biological properties in Eutric Cambisol

Abstract

The choice of prospective type of farming requires knowledge about the specific relationships that exist between farm management practices and base environmental conditions. Nowadays the protection of soil organic carbon is one of the main tasks, because organic carbon in addition to soil fertility can act in elimination of soil contamination and carbon sequestration. Field experiments were focused on the effect of intensive farming without organic inputs versus grassland on organic carbon content. Organic carbon content (C_ox) and humic substance fractions (C-humic acids and fulvic acid fractions), hot water extractable carbon and selected microbial characteristics in Eutric Cambisol were monitored during the period 1999–2010. A priming effect of soil cultivation was detected immediately after tillage. Arable soil with ‘intensive’ crop sequences (exclusively cash crops, cereals, oil plants) and with an optimal level of chemical inputs (mineral fertilizers, pesticides), but without organic farmyard manure had lower content of all carbon forms compared with grassland. ¹³C NMR spectroscopy and thermal analysis (TGA) were applied to characterize humic acid (HA) structure and stability. More carbon, less oxygen and more aromatic compounds were detected in grassland HA. Slight differences were found in HA thermo-oxidative stability and degradability, which was probably caused by changes in elemental composition and structure. Even the land use had no significant effect on basic microbiological characteristics (basal respiration, microbial biomass and qCO₂); the physiology of the microbial community of grassland was altered by a higher ability to utilize L- and D-glutamic acid. The L/D ratio of glutamic acid mineralization indicated no occurrence of stress in soil for both types of farming. It has been demonstrated that although losses of carbon as a result of land-use conversions are generally more rapid, gains of carbon in grassland followed by changes in management practices can also occur.     

Role of allophanes in the accumulation of glomalin‐related soil protein in tropical soils (Martinique,French West Indies)

Thermo‐stable, operationally defined soil protein, known as glomalin, may make an important contribution to carbon storage in soils. The term glomalin is used because this putative protein, or group of proteins, was originally thought to be produced only by Glomus fungi. There is currently little information on the glomalin‐related soil protein (GRSP) content of tropical soils, particularly allophanic soils that are known to have different carbon dynamics to temperate climate soils. We have measured the Bradford‐reactive GRSP content of soils sampled from forests and grasslands on the tropical island of Martinique and compared the observations with soil composition. Two operationally defined fractions of GRSP were measured, namely easily‐extractable and total GRSP. The contents of GRSP in moist soils were in the range of 2–36 g kg^?1, accounting for about 8% of soil organic carbon, and were greater in topsoils than in corresponding subsoils. Both the GRSP contents and the fraction of soil organic carbon attributed to GRSP were greater than those reported for temperate climate soils. Both total and easily extractable GRSP contents were positively correlated to soil organic carbon content. The fraction of soil organic carbon that could be attributed to soil protein decreased with increasing allophane content for allophanic soils. No other trends of GRSP content with soil properties or land use were found. GRSP extraction was decreased about seven‐fold by air‐drying of soils, confirming the irreversible change in the soil microstructure of allophanic soils. Total and easily extractable GRSP were correlated and we conclude that both are good probes of thermo‐stable soil protein content for these soils. No attempt was made to verify the fungal origin of the protein detected.     

Glomalin amount and compositional variation,and their associations with soil properties in farmland,northeastern China

Glomalin‐related soil protein (GRSP) is well‐known for its soil conditioning functions, but compositional traits are rarely considered. Farmland in northeastern China is the most important commercial grain basis, and soil degradation becomes the bottleneck for keeping crop productivity. The objective of this study was to uncover the possible associations between GRSP (amount and composition) and soil properties, and make suggestions for soil improvement from soil glomalin rehabilitation in northeastern China. Here, spatial variation in GRSP amount (Easily‐extractable‐GRSP, EE‐GRSP; Total‐GRSP, T‐GRSP) and its compositional traits from infrared spectroscopy, UV‐absorbance, X‐ray diffraction (XRD) and 3‐D fluorescence spectroscopy were surveyed in 360 soil samples across northeastern China, and their association with 11 soil properties were also analyzed for finding the possible influence of soil properties on GRSP composition in farmland. There about 3‐fold spatial variation in GRSP amount was observed, while functional group variations were ranged from 1.2‐fold (O–H & N–H stretching) to 2.4‐fold (C–O stretching & O–H bending of –COOH) in different locations. The XRD showed that grain size was 113–180Å and crystallinity was 0.71–1.42%, and GRSP contained seven fluorescent compounds of tyrosine‐like, tryptophan‐like, fulvic acid‐like, soluble microbial byproduct, humic acid‐like, nitrobenzoxadidole‐like, and calcofluor white‐like. Both, EE‐GRSP and T‐GRSP positively associated with soil organic carbon (SOC), soil N (SON), soil P (SOP), alkali‐hydrolyzed N (AN), available P (AP), available K (AK), and soil water, while negatively associated with soil pH and soil bulk density. Structural equation model (SEM) analysis indicates that direct effects on GRSP amounts were mainly from soil bulk density (coefficient: –0.27), soil pH (coefficients: –0.51 to –0.57), SOC (coefficients: 0.51 to 0.69) and AP (coefficients: 0.18 to 0.26), while all other soil properties had indirect effects on GRSP amounts via their close associations with these four parameters. Compared with the GRSP amounts, soil properties laid fewer effects on GRSP compositional traits. Of 16 compositional traits, five of them showed possible regulations from soil properties, which were three infrared functional groups (IR‐II: aliphatic C–H stretching; IR‐V: C–O stretching & O–H bending of –COOH; IR‐VII: O–H binding) and two fluorescent compounds (tyrosine‐like and humic acid‐like). SEM analysis indicates that soil water, pH and EC could directly affect IR‐II, IRV, tyrosine‐like and humic acid‐like, while available nutrients showed more evident influences on infra‐red functional groups than total amounts of N, P and K. Moreover, SOC, as a media of various soil nutrients, gave the strongest influence on GRSP compositional traits. As a supplement to previous studies, we found that GRSP is a mixture of different fluorescent compounds with different functional groups. Our findings highlight that soil properties could strongly change both GRSP accumulation in soil and their compositional traits, and the definition of the most probable soil properties in regulating glomalin amount and composition in this paper could favor good soil management in farmland at northeastern China.     

Location and chemical composition of stabilized organic carbon in topsoil and subsoil horizons of two acid forest soils

The ¹⁴C age of soil organic matter is known to increase with soil depth. Therefore, the aim of this study was to examine the stabilization of carbon compounds in the entire soil profile using particle size fractionation to distinguish SOM pools with different turnover rates. Samples were taken from a Dystric Cambisol and a Haplic Podzol under forest, which are representative soil types under humid climate conditions. The conceptual approach included the analyses of particle size fractions of all mineral soil horizons for elemental composition and chemical structure of the organic matter by ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. The contribution of phenols and hydroxyalkanoic acids, which represent recalcitrant plant litter compounds, was analyzed after CuO oxidation.In the Dystric Cambisol, the highest carbon concentration as well as the highest percentage of total organic carbon are found in the <6.3 μm fractions of the B and C horizons. In the Haplic Podzol, carbon distribution among the particle size fractions of the Bh and Bvs horizons is influenced by the adsorption of dissolved organic matter. A relationship between the carbon enrichment in fractions <6.3 μm and the ¹⁴C activity of the bulk soil indicates that stabilization of SOM occurs in fine particle size fractions of both soils. ¹³C CPMAS NMR spectroscopy shows that a high concentration of alkyl carbon is present in the fine particle size fractions of the B horizons of the Dystric Cambisol. Decreasing contribution of O-alkyl and aromatic carbon with particle size as well as soil depth indicates that these compounds are not stabilized in the Dystric Cambisol. These results are in accordance with data obtained by wet chemical analyses showing that cutin/suberin-derived hydroxyalkanoic acids are preserved in the fine particle size fractions of the B horizons. The organic matter composition in particle size fractions of the top- and subsoil horizons of the Haplic Podzol shows that this soil is acting like a chromatographic system preserving insoluble alkyl carbon in the fine particle size fractions of the A horizon. Small molecules, most probably organic acids, dominate in the fine particle size fractions of the C horizons, where they are stabilized in clay-sized fractions most likely due to the interaction with the mineral phase. The characterization of lignin-derived phenols indicated, in accordance with the NMR measurements, that these compounds are not stabilized in the mineral soil horizons.     

Minimal direct contribution of arbuscular mycorrhizal fungi to DOC leaching in grassland through losses of glomalin-related soil protein

Arbuscular mycorrhizal fungi (AMF) have multiple influences on ecosystem C cycling, but most research has focused on ecosystem C gains. We explore here the possibility of direct contributions of AMF to ecosystem C losses, namely via leaching of glomalin-related soil protein (GRSP). We tested the hypothesis that GRSP, an operationally defined SOM pool to which AMF contribute (especially as evidenced with monoclonal antibody MAb32B11-based detection), is mobile in soils and can be lost in leachate. For two New Zealand soils, we showed that only insignificant amounts of GRSP were lost: a maximum of 0.03% of MAb32B11-immunoreactive GRSP present in soils was lost during the week-long experiment, representing a minute fraction of total leachate dissolved organic carbon (0.06%). Our data showed that this pathway of C loss may be relatively unimportant in many soils. However, other indirect contributions of AMF to soil C losses remain yet to be explored.     

Incorporation of nitrogen from urea fertilizer into soil organic matter in rice paddy and cassava upland fields in Indonesia

Incorporation of newly-immobilized N into major soil organic matter fractions during a cropping period under paddy and upland cropping systems in the tropics was investigated in Jawa paddy fields with and without fish cultivation and a Sumatra cassava field in Indonesia. ¹⁵N-labelled urea (¹⁵N urea) was applied as basal fertilizer, and the soil samples were collected after harvest. The percentage of distribution of the residual N in soil from ¹⁵N urea into the humic acids, fulvic acid fraction, and humin were 13.1–13.9, 19.0–20.5, and 53.4–54.3%, respectively, for the Jawa paddy soils, and 14.9, 27.4, and 52.4%, respectively, for the Sumatra cassava soil. These values were comparable to the reported ones for other climatic zones. The percentage of distribution of ¹⁵N urea-derived N into humic acids was larger than that of total N into the same fraction in all the soils. The distribution into the fulvic acid fraction was also larger for ¹⁵N urea-derived N than for total N in the Jawa soils. Humic and non-humic substances in the fulvic acid fraction were separated using insoluble polyvinylpyrrolidone (PVP) into the adsorbed and non-adsorbed fractions, respectively. Less than 5% of the ¹⁵N urea-derived N in fulvic acid fraction was detected in the PVP-adsorbed fraction (generic fulvic acids). The proportion of non-hydrolyzable N remained after boiling with 6 M HCl in the ¹⁵N urea-derived N was 9.4–13.5%, 17.3–26.7%, and 8.4–16.6% for the humic acids, generic fulvic acids, and humin, respectively. The significantly low resistance to acid hydrolysis suggested that the ¹⁵N urea-derived N was less stable than the total N in soil regardless of the fractions of humus.     

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     

化肥配施不同剂量有机肥对黑土团聚体中有机碳与腐殖酸分布的影响

【目的】 团聚体的形成为土壤有机碳的稳定提供了重要的物理保护,施用有机肥影响着土壤团聚体的形成,量化有机肥施用剂量与团聚体有机碳稳定性之间的关系对于阐明农田土壤有机碳的固碳机制具有重要意义。 【方法】 以黑龙江省海伦市国家野外科学观测研究站为平台,选择连续10年进行化肥配施不同剂量有机肥处理[0、7.5、15、22.5 t/(hm2·a)]的黑土为研究对象,将团聚体分组与腐殖酸提取相结合,分析了不同粒径团聚体中有机碳和腐殖酸的含量与光学特性。 【结果】 1)与单施化肥相比,化肥配施有机肥增加了大团聚体( > 0.25 mm)的分配比例与团聚体的平均重量直径,二者均随着有机肥剂量的增加而逐渐升高,回归拟合分析表明,团聚体的平均重量直径与有机肥剂量之间呈现显著的正相关关系(P=0.03)。2) 2~0.25 mm团聚体是黑土有机碳的主要贮存场所,约占有机碳总量的64.8%~68.8%,大团聚体中有机碳的含量与储量均随着有机肥剂量的增加而逐渐升高, < 0.053 mm团聚体中有机碳含量与储量则维持在较稳定的水平。3)各粒级团聚体中腐殖酸碳含量以0.25~0.053 mm团聚体最高,各粒级团聚体中腐殖酸碳占有机碳百分比之间的差异不显著。化肥配施有机肥提高了各粒级团聚体中腐殖酸碳的含量,使团聚体对有机碳的固持能力增加,且各粒级团聚体中腐殖酸碳的含量随着有机肥剂量的增加逐渐升高。4)化肥配施有机肥增加了各粒级团聚体中腐殖酸的E4/E6比值,表明其分子结构简单化,且以 > 2 mm和0.25~0.053 mm团聚体中腐殖酸E4/E6比值的增加最显著。 【结论】 在黑土中,长期连续进行化肥配施有机肥,促进了团聚体的形成,改善了耕层土壤结构,增加了团聚体中有机碳的积累与固持能力,并使各粒级团聚体中腐殖酸的结构“年轻化”,这种促进作用在高剂量有机肥施用下更为显著。实际生产中,在短期内可通过适当提高有机肥的施用量以提高黑土肥力及其固碳能力。     

土壤腐殖质氮结构的X-光电能谱研究

X－ray photoelectron spectroscopy(XPS) was applied to examine the N structures of soil humic substances and some of their analogues.It was found that for soil humic substances XPS method gave similar results as those obtained by ^15N CPMAS NMR (cross-polarization magic-angle spinning nuclear magnetic resonance) method.70%-86% of total N in soil humic substances was in the form of amide,and 6%-13% was presented as ammes,with the remaining part as heterocyclic N.There was no difference in the distribution of the forms of N between the humic substances from soils formed over hundreds or thousands of years and the newly formed ones.For fulvic acid from weathered coal and benzoquinone-(NH4)2SO4 polymer the XPS results deviated significantly from the ^15N CPMAS NMR data.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.     

Retention of added copper by two soils as affected by organic matter,CaCO3, and exchangeable ions

The effects of addition and removal of organic matter and CaCO₃ and of saturating a loam and a loamy sand soil with hydrogen (HCl treated), with calcium and with sodium on the retention of added copper were studied. Removal of organic matter reduced the copper-retaining capacity in soils, while addition of 1 to 4% humic acid to H₂O₂-treated soils increased the retention. Soil organic matter had higher specific copper retaining as well as fixing capacity than the added humic acid. Humic acid fixed about 62 and 49% of the copper it retained, while soil organic matter fixed about 65 and 61% in the loam and loamy sand respectively, which could not be extracted with 0.1 N HCl. About 30% extra copper retained by the added humic acid was exchangeable. Saturating the soils with hydrogen (HCl treatment) decreased the retention of added copper considerably but addition of CaCO₃ up to 8% increased the retention by increasing the pH of the soil system. The CaCO₃ induced retention was lower than caused by humic acid additions. The specific copper retention by native CaCO₃ was slightly higher than that of added CaCO₃. However, other changes associated with the pre-treatment of the soil may have caused those differences in specif is copper retention. Although CaCO₃ had as high a copper fixing capacity as organic matter its contribution towards exchangeable copper was negligible.     

Effects of mineral surface iron on the CPMAS 13C-NMR spectroscopic detection of organic matter from soil fractions in an agricultural topsoil with different amendments

The decrease of NMR visibility of the C signal in soil samples due to the association between organic carbon (OC) and the topsoil mineral surface was investigated. CPMAS ¹³C‐NMR spectra were obtained for soil particle‐size fractions (< 2 μm, 2–20 μm, > 20 μm) and bulk soils from an agricultural topsoil (Chernozem) that had received three different amendments (no fertilization, mineral fertilization (NPK), mineral (NPK) and organic (cattle manure) fertilizations) at Bad Lauchstädt, Germany. The soil organic carbon content of the three soils depended on the degree of soil fertilization. There was no constant relationship between the total NMR signal intensity and the total amount of organic carbon (TOC) for all size fractions. Indeed, a key role played in the C signal intensity by the paramagnetic ferric ion from the clay content in soil fractions and bulk soils was confirmed. Thus, we describe the variations of C signal intensity by taking into account the distribution of clay‐associated OC and non‐associated OC pools. Depending on the amendment, the C signal visibility was weakened by a factor of 2–4 for the clay‐associated OC. This estimation was rendered possible by combining mineral specific surface area (SSA) measurements with the N₂ gas adsorption method (BET method) and determination of TOC and iron concentrations. This approach contributes to the quantitative evaluation of the CPMAS ¹³C‐NMR detection.     

Partitioning of organic carbon, aluminium and cadmium between solid and solution in soils: application of a mineral–humic particle additivity model

The partitioning of chemical elements between the solid and solution phases in soil is fundamental in understanding processes such as leaching and bioavailability. Here I present a model in which the partitioning of Cd, Al and carbon in both mineral and organic soils can be simulated in the pH range 2–8. A two‐phase additivity approach simulates ion adsorption by the soils using a hydrous ferric oxide and humic type surface. A model for the partitioning of soil humic matter has also been developed in which the NICA–Donnan model calculates humic surface charge. Other key processes represented include mineral solubilization and solution speciation. Methods for deriving model input parameters either from analytical data or by parameter optimization were used. Acid ammonium‐oxalate‐extractable Fe was used to estimate the amount of hydrous ferric oxide, and reactive humic substances were estimated by a scaled down version of the International Humic Substances Society method for the extraction of humic and fulvic acid. For initial calculation the 0.1 m HCl‐extractable Al was used to estimate reactive Al. Optimization of reactive Al improved the fit of both the total dissolved Al data and the adsorbed Cd. The model for the solid–solution partitioning of humic substances could simulate reasonably well the release of carbon in the pH range 4–8 for both the organic and mineral soils.     

The fate of catechol in soil as affected by earthworms and clay

The effect of endogeic earthworms (Octolasion tyrtaeum) and the availability of clay (Montmorillonite) on the mobilization and stabilization of uniformly ¹⁴C-labelled catechol mixed into arable and forest soil was investigated in a short- and a long-term microcosm experiment. By using arable and forest soil the effect of earthworms and clay in soils differing in the saturation of the mineral matrix with organic matter was investigated. In the short-term experiment microcosms were destructively sampled when the soil had been transformed into casts. In the long-term experiment earthworm casts produced during 7 days and non-processed soil were incubated for three further months. Production of CO₂ and ¹⁴CO₂ were measured at regular intervals. Accumulation of ¹⁴C in humic fractions (DOM, fulvic acids, humic acids and humin) of the casts and the non-processed soil and incorporation of ¹⁴C into earthworm tissue were determined.Incorporation of ¹⁴C into earthworm tissue was low, with 0.1 and 0.44% recovered in the short- and long-term experiment, respectively, suggesting that endogeic earthworms preferentially assimilate non-phenolic soil carbon. Cumulative production of CO₂-C was significantly increased in casts produced from the arable soil, but lower in casts produced from the forest soil; generally, the production of CO₂-C was higher in forest than in arable soil. Both soils differed in the pattern of ¹⁴CO₂-C production; initially it was higher in the forest soil than in the arable soil, whereas later the opposite was true. Octolasion tyrtaeum did not affect ¹⁴CO₂-C production in the forest soil, but increased it in the arable soil early in the experiment; clay counteracted this effect. Clay and O. tyrtaeum did not affect integration of ¹⁴C into humic fractions of the forest soil. In contrast, in the arable soil O. tyrtaeum increased the amount of ¹⁴C in the labile fractions, whereas clay increased it in the humin fraction.The results indicate that endogeic earthworms increase microbial activity and thus mineralization of phenolic compounds, whereas clay decreases it presumably by binding phenolic compounds to clay particles when passing through the earthworm gut. Endogeic earthworms and clay are only of minor importance for the fate of catechol in soils with high organic matter, clay and microbial biomass concentrations, but in contrast affect the fate of phenolic compounds in low clay soils.