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.     

A liquid chromatographic/mass spectrometric method to evaluate <Superscript>13</Superscript>C and <Superscript>15</Superscript>N incorporation into soil amino acids

Purpose  

Amino acids are highly associated with biogeochemical cycling and represent an important potential source and sink of carbon (C) and nitrogen (N) in terrestrial ecosystems. Tracing the isotope dynamics of amino acids can improve the understanding of the origin and transformation of amino acids in soil matrix at process-levels; hence, the liquid chromatographic/mass spectrometric (LC/MS) method to evaluate ¹³C or ¹⁵N enrichment in amino acids is necessary to be established.     

Purification and isotopic signatures (<Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C, <Emphasis Type="Italic">δ</Emphasis><Superscript>15</Superscript>N, Δ<Superscript>14</Superscript>C) of soil extracellular DNA

The aim of this work was to obtain pure extracellular DNA molecules so as to estimate their longevity in soil by an isotope-based approach. Extracellular DNA molecules were extracted from all horizons of a forest soil and purified by the procedure of Davis (Purification and precipitation of genomic DNA with phenol–chloroform and ethanol. In: Davis LG, Dibner MD, Battey JF (eds) Basic methods in molecular biology. Appleton & Lange, Norwalk, 16–22, 1986) without (DNA1) or with (DNA2) a successive treatment with binding resins followed by elution. The two differently purified DNA samples were compared for their A₂₆₀/A₂₈₀ ratio, polymerase chain reaction (PCR) amplification and natural abundance of stable (¹³C and ¹⁵N) and radioactive (¹⁴C) isotopes. The purity index and the PCR amplification did not differentiate the efficiency of the two purification procedures. The isotopic signature of DNA was more sensitive and was strongly affected by the purification procedures. The isotopic measurements showed that the major contaminant of extracellular DNA1 was the soil organic matter (SOM), even if it is not possible to exclude that the similar δ ¹³C, δ ¹⁵N and Δ¹⁴C values of DNA and SOM could be due to the use of SOM-deriving C and N atoms for the microbial synthesis of DNA. For extracellular DNA2, extremely low values of Δ¹⁴C were obtained, and this was ascribed to the presence of fossil fuel-derived substances used during the purification, although in amounts not revealed by gas chromatography-mass spectrometry analysis. The fact that it is not possible to obtain contaminant-free DNA molecules and the potential use of soil native organic compounds during the microbial synthesis of DNA make it not achievable to estimate the age of soil extracellular DNA by radiocarbon dating.     

近红外光谱法在土壤有机质研究中的应用

近红外光谱技术(Near Infrared Reflectance Spectroscopy,NIRS)具有快速、低成本、无损等优点。目前利用NIRS获取土壤信息已成为国内外学者研究的重点,但是在我国利用NIRS对土壤成分进行定量分析才刚刚起步。本文简要介绍了近红外光谱分析的基本原理、模型的建立及评价,详细论述了该技术在预测土壤有机质及其组分方面的应用,并对NIRS在我国土壤有机质定量研究方面的应用前景进行了展望。     

林火对土壤有机质的影响研究综述

火干扰被认为地球化学循环和土壤碳循环的主要干扰因素,主要包括森林火灾和计划烧除。就火干扰对土壤有机质的影响进行归纳总结,火干扰对土壤有机质的影响差异很大,主要取决于火灾类型、火强度、火干扰持续时间、可燃物特性、土壤类型、土壤含水率等,高强度火灾后土壤有机质显著减少、腐殖质急剧转化成溶解性物质,火干扰土壤中各粒度级碳含量增加、游离脂肪链的长度有选择性降低、土壤芳香烃和烷基大量增加、土壤腐殖酸与富里酸中的胡敏素数量增加,更高温度下胡敏素是残留在土壤中的主要有机成分,森林可燃物不完全燃烧后经过冷凝形成黑碳;森林火灾直接杀死部分菌类,改变土壤微生物结构和营养成分,通过核磁共振光谱比较腐殖质中的有机化合物,发现火干扰土壤的腐殖质羧基缺位。根据归纳现有研究现状,并提出今后的研究重点与方向。建立火干扰后土壤有机质连续跟踪调查研究机制,土壤有机质变异数据库,加强火干扰对土壤有机质影响机理的模拟研究。     

Use of a double radioactive label (<Superscript>54</Superscript>Mn and <Superscript>14</Superscript>C) in the study of organomineral manganese compounds

A fundamentally new approach to the study of natural organomineral materials was proposed. A procedure was developed for using a double carbon-metal label in the systemic study of organomineral complexes of soils and conjugated landscape objects. A significant effect of water-soluble organic ligands on the migration of manganese in soils was shown. It was found that mineral manganese compounds were transformed into organomineral ones differing in composition, solubility, and stability, and the complex of humus substances in podzolic soil was a peculiar matrix on which a complex system of organomineral compounds was developed. The input mechanism of organomineral complexes with different molecular weights (MWs) into plants was studied. Pot experiments using a root exudates sampling procedure and a double radioactive label (⁵⁴Mn and ¹⁴C) showed that the organomineral complexes of Mn with the fulvic acid fraction (MW > 10000) came intact to corn roots. The fulvic acid fraction (MW 380) and manganese ions independently passed from the soil solution into the young plants.     

Selective effects of forest fires on the structural domains of soil humic acids as shown by dipolar dephasing <Superscript>13</Superscript>C NMR and graphical-statistical analysis of pyrolysis compounds

Purpose

Data management strategies of pyrolysis results and NMR acquisition modes were examined in humic acids (HAs) from control soils and fire-affected soils. The information supplied by dipolar dephasing (DD) ¹³C NMR spectroscopy and Curie-point pyrolysis were used to assess chemical structures hardly recognizable and measurable, or of unclear interpretation, when using ¹³C NMR under standard acquisition pulses (cross-polarization/magic angle spinning, CPMAS).

Materials and methods

The HAs were isolated from two forest soils under Pinus halepensis and Pinus sylvestris in control and burned sites affected by medium or severe-intensity wildfires. For NMR analyses, during DD acquisition conditions, a 180° ¹³C pulse was inserted to minimize phase shifts. Curie-Point pyrolysis was carried out at 510 °C for 5 s, and the pyrolysis fragments were analyzed by GC/MS. The total abundances of the major pyrolysis products were compared by an update of the classical Van Krevelen’s graphical-statistical approach, i.e., as surface density values in the space defined by the compound-specific H/C and O/C atomic ratios.

Results and discussion

The DD ¹³C NMR experiments displayed significant differences in the HA spectral profiles as regards to the standard CPMAS ¹³C NMR acquisition conditions, mainly in the chemical shift region of alkyl structures as well as for tannin- or carbohydrate-like O-alkyl structures. In fact, the comparison between DD and CPMAS solid-state NMR suggested shortening of alkyl chains and generation of carbohydrate-derived, unsaturated structures—viz. furans—which adds to the aromatic domain. Pyrolytic results showed fire-induced specific changes in HAs chemical structure and its molecular diversity. The changes were evident in the location and sizes of the different clusters of pyrolysis compounds defined by their atomic ratios.

Conclusions

The DD ¹³C NMR provided specific information on the fate of aliphatic structures and the origin of unsaturated HA structures, which could be helpful in differentiating “inherited” from “pyrogenic” aromatic structures. This is further confirmed by the analysis of the molecular assemblages of pyrolytic products, which showed accumulation of condensed polyaromatic domains in the HAs after the high-intensity fire, accompanied by a recalcitrant alkyl hydrocarbon domain. Medium-intensity fire led to aromaticity increase due to a selective accumulation of lignin-derived phenols concomitant to the depletion of aliphatic hydrocarbon constituents.

     

Radioactive Contamination of Alluvial Soils in the Taiga Landscapes of Yakutia with <Superscript>137</Superscript>Cs, <Superscript>226</Superscript>Ra,and <Superscript>238</Superscript>U

The concentrations and distribution of ¹³⁷Cs in alluvial soils (Fluvisols) of the upper and middle reaches of the Markha River in the northwest of Yakutia and ²²⁶Ra and ²³⁸U in alluvial soils within the El’kon uranium ore deposit in the south of Yakutia have been studied. It is shown that the migration of radiocesium in the permafrost-affected soils of Yakutia owing to alluviation processes extends to more than 600 km from the source of the radioactive contamination. The migration of ¹³⁷Cs with water flows is accompanied by its deposition in the buried horizons of alluvial soils during extremely high floods caused by ice jams. In the technogenic landscapes of southern Yakutia, active water migration of ²³⁸U and ²²⁶Ra from radioactive dump rocks. The leaching of ²³⁸U with surface waters from the rocks is more intense than the leaching of ²²⁶Ra. The vertical distribution patterns of ²³⁸U and ²²⁶Ra in the profiles of alluvial soils are complex. Uranium tends to accumulate in the surface humus horizon and in the buried soil horizons, whereas radium does not display any definite regularities of its distribution in the soil profiles. At present, the migration of ²³⁸U and ²²⁶Ra with river water and their accumulation in the alluvial soils extend to about 30 km from the source.     

Organophosphates in agrogray soils with periodic water logging according to the data of <Superscript>31</Superscript>P NMR spectroscopy

The composition of organic phosphorus compounds was studied using the ³¹P NMR spectroscopy method in agrogray soils with periodic water logging. The phosphorus content was determined by the specific difference between the hydrological and the redox regimes of these soils. The phosphorus of the organic compounds in the agrogray soils with contrasting water regimes is composed mostly of phosphoric monoesters and diesters, including nucleic and teichoic acids. The relative distribution of the monoesters and inorganic orthophosphates is shown depending on the climate and the soil’s position in the relief. The area of the monoester peaks increases by two times and that of the mineral orthophosphate decreases by six times in the agro-gray soils of Bryansk opolie with an optimal regime of moistening and evaporation in comparison with the agro-gray gleyed soils of Kolomna opolie. As the degree of the soil hydromorphism in the sequence of deeply gleyed soils and gleyic soils increased, the portion of monoesters decreased. Favorable conditions for the microbial activity are formed in soils with a contrasting redox regime, and this is expressed in the accumulation of labile diesters. Inverse relationships were found between the distributions of the mono- and diesters in iron-manganic nodules and in the soils enclosing them; this was caused by the different mechanisms of the stabilization of the stable and labile phosphorus containing compounds. A high percentage of mineral orthophosphate in the nodules allows assuming the presence of chemisorbed orthophosphate ions in organomineral phosphate-metal-humus complexes. The transformation of iron-manganic nodules under the influence of drying demonstrates the more direct participation of microorganisms in the nodules’ formation than the contribution of the physicochemical processes.     

Effect of nitrogen fertilization on the fate of rice residue-C in paddy soil depending on depth: <Superscript>13</Superscript>C amino sugar analysis

A 100-day incubation experiment was conducted to (i) trace the fate of rice residue-derived ¹³C in the amino sugar (AS) pool in 0–1-cm (oxic) and 1–5-cm (anoxic) layers of paddy soil and (ii) evaluate the effects of inorganic N ((NH₄)₂SO₄) fertilization on the formation of AS at early and late incubation times (5 and 100 days, respectively). The accumulation of rice residue-derived AS occurred at 5 and 100 days in both soil layers as a result of AS stabilization. Inorganic N addition increased the contents of rice residue-derived muramic acid, glucosamine, and galactosamine in the 0–1-cm soil layer for both incubation times by average on 14.7–20.8%, 23.7–31.8%, and 11.6–23.3%, respectively. In contrast, no effects of N fertilization on AS content in the 1–5-cm soil layer were found. The amount of rice residue-derived AS was higher in the 1–5-cm than in the 0–1-cm soil layer at early incubation time, probably due to the higher contents of ammonium here compared to the upmost oxic layer where nitrate was the dominated N form. Thus, the preferential uptake of ammonium but not nitrate by microorganisms led to the higher formation of rice residue-derived AS in the anoxic soil layer. The ratio of fungal to bacterial residues (fungal glucosamine/muramic acid) ranged between 1.0 and 1.7 for rice residue-derived AS and was 12.5–14.6 for total AS, indicating that fungi and bacteria have similar contributions to the decomposition of fresh rice residue whereas native soil organic matter (SOM) is a fungi-predominated process. This study emphasized that coupling of C and N cycles in paddy soils is different in oxic and anoxic layers, resulting in variation of plant residue decomposition and formation of SOM.     

The exchangeable fraction of selectively sorbed <Superscript>137</Superscript>Cs in soils and natural sorbents as a function of the K<Superscript>+</Superscript> and NH<Stack><Subscript>4</Subscript><Superscript>+</Superscript></Stack> concentrations

The exchangeable portion of the selectively sorbed ¹³⁷Cs extractable by a 1 M ammonium acetate solution (α _Ex ) for soils, illite, bentonite, and tripolite was found to increase with the increasing concentration of the competitive cation M⁺ (K⁺ or NH₄⁺) and can be approximated by a logarithmic relationship. For clinoptilolite, the values of α _Ex did not depend on the concentration of M⁺. The expression 1 − α _Ex (C _M=n )/α _Ex (C _M = 16) as a function of the M⁺ concentration (where α _Ex (C _M=n ) is the α _Ex value at the competitive cation concentration equal to 16 mmol/dm³) was proposed to compare the dependence of α _Ex on the concentration of K⁺ or NH₄⁺in different sorbents. For soils and illite, these dependences almost coincided, which indicated that the selective sorption of ¹³⁷Cs in soils is determined by the presence of illite-group minerals.     

农艺措施对土壤可溶性有机质的影响研究进展

土壤可溶性有机质(DOM)是土壤有机物中的高活性组分，在土壤养分的生物地球化学循环、重金属和有机污染物的迁移转化、土壤矿物质的活化及土壤肥力的保持等过程中发挥着重要作用。农艺措施可通过内外源同步作用显著影响土壤DOM的含量、组分及性质，本文综述了近年来相关研究中不同农艺措施下土壤DOM的变化，总结了不同耕作管理、种植制度、施肥措施以及新型土壤改良剂等对土壤DOM的影响。分析表明，免耕加秸秆覆盖方式可显著提高土壤DOM含量，与单一耕作相比轮作可提升土壤DOM含量，绿肥配施有机肥较单一化肥施用可显著改善土壤DOM的组成和结构，合理调控热解炭和水热炭等土壤调理剂的施用时间、施用量、C/N等性质可优化土壤DOM结构和性能。本综述分析了农艺措施对土壤DOM的影响效果及作用途径，指出了当前的研究热点和难点，并对未来研究方向进行了展望，可为今后合理的农艺措施管理和土壤健康调控提供科学指导。     

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。     

Contamination of terrestrial ecosystem components with <Superscript>90</Superscript>Sr, <Superscript>137</Superscript>Cs,and <Superscript>226</Superscript>Ra caused by the deterioration of the multibarrier protection of radioactive waste storages

The spatial-temporal features of the radioactive contamination of terrestrial ecosystem components caused by the deterioration of the multibarrier protection of regional radioactive waste storages of the State Research Center of the Russian Federation-Leipunskii Institute of Physics and Power Engineering at the input of radionuclides into the soil and ground water were studied. The composition of the radioactive contamination was determined, and the hydrological and geochemical processes resulting in the formation of large radioactive sources were described. The natural features of the radioactive waste storage areas favoring the entry of ⁹⁰Sr, ¹³⁷Cs, and ²²⁶Ra into the soils and their inclusion in the biological turnover were characterized. The directions of the horizontal migration of ⁹⁰Sr, ¹³⁷Cs, and ²²⁶Ra and the sites of their accumulation within the superaquatic and aquatic landscapes of a near-terrace depression were studied; the factors of the ⁹⁰Sr accumulation in plants and cockles were calculated. The results of the studies expand the theoretical concepts of the mechanisms, processes, and factors controlling the behavior of radionuclides at the deterioration of the multibarrier protection of radioactive waste storages. The presented experimental data can be used for solving practical problems related to environmental protection in the areas of industrial nuclear complexes.     

Role of plants in the spatial differentiation of <Superscript>137</Superscript>Cs and <Superscript>90</Superscript>Sr statuses on the aggregate level

The increased concentration of an element in plant biomass compared to the soil mass is an essential condition for the differentiated spatial distribution and status of the element on the aggregate level. Two forms of this differentiation have been revealed for ¹³⁷Cs and ⁹⁰Sr. Transfer of ¹³⁷Cs from plant roots and concentration on the surface of soil aggregates have been established experimentally. Indirect data also point to the potential localization of ¹³⁷Cs on the surface of intraaggregate pores. The effect of radionuclide concentrating on the outer and inner surfaces of aggregates is due to the rapid and strong fixation of cesium microamounts by mineral soil components. ¹³⁷Cs from the surface of aggregates is more available for the repeated uptake by plant roots than from the intraped mass. The distortion of this spatial differentiation mainly occurs during the reaggregation of soil mass, which in turn decreases the availability of the radionuclide to plants. For ⁹⁰Sr, its elevated concentration in the form of organic residues has been revealed in the inter- and intraaggregate pore space. However, due to the high diffusion rate, ⁹⁰Sr is relatively rapidly (during several months under pot experimental conditions) redistributed throughout the entire volume of soil aggregates and its major part gradually passes into the phase of humic compounds, to which the radionuclide is bound by exchange sorption. The high level of the next root uptake (higher than for ¹³⁷Cs by one to two orders of magnitude) favors the permanent renewal of loci with increased ⁹⁰Sr concentrations in the inter- and intraaggregate pore space in the form of plant residues.     

国际土壤有机质研究概况和趋势——基于文献计量学分析

土壤有机质对土壤生态系统的健康发展有至关重要的作用。为厘清全球土壤有机质研究的脉络,作者利用WOS数据库结合Citespace软件分析了国际土壤有机质研究的相关概况,并对未来土壤有机质可能的研究方向提供参考意见。结果显示:全球土壤有机质研究正处在快速发展阶段,发文量最多、H指数最高和篇均被引最多的国家均是美国;发文量最多的研究机构是中国科学院,总被引频次最多的机构是美国农业部,H指数最高的是美国加州大学;发文量最多、总被均被引频次和H指数最高的科研学者均是Lal,篇均被引最高的学者是Six;从发文量和总被引频次以及H指数来看,《Soil Biology and Biochemistry》是最权威的期刊;全球土壤有机质研究的最新热点集中在土地利用方式、生物多样性、农业土壤、土壤污染和土壤呼吸作用等方向。未来全球土壤有机质研究可能会集中在土壤有机质对农业生态系统的影响、土壤有机质对环境污染的影响和土壤有机质结构及性质的分析三个方向。     

三维荧光光谱法在土壤溶解性有机质组分解析中的应用

土壤溶解性有机质是具有较高化学和微生物活性的土壤有机质组分,其周转在维持土壤肥力和调节生态系统碳循环中发挥着核心作用,正确解析可溶性有机质的化学组分对深刻理解其生态环境效应具有重要意义。 论文旨在概述常见的土壤可溶性有机质组分分析方法,简要比较了常见的可溶性有机质化学组分分析技术,包括紫外－可见吸收光谱法、傅里叶红外光谱法、核磁共振法、傅里叶回旋共振质谱法和三维荧光光谱法的基本原理及技术优缺点,并着重对三维荧光光谱法在土壤可溶性有机质组分解析应用过程中的重要影响因素、常用荧光指标和数据处理方法进行了综述。三维荧光光谱法具有操作简便、仪器可及性高、成本低、通量高等特点,通过荧光指数、腐殖化指数及生物源指数等表征指标追溯土壤可溶性有机质的来源,结合平行因子分析法解析可溶性有机质化学组分及其对土地利用方式、耕种制度、全球变化因子的响应。但是,三维荧光光谱法也存在易受环境影响、解谱困难等局限性。未来研究亟需定量分析环境因素对可溶性有机质荧光特性的影响,并加强与其它分析技术和方法的联用,有助于更准确和全面地解析可溶性有机质,继而深入理解其生态环境效应。     

Carbon turnover in the rhizosphere under continuous plant labeling with <Superscript>13</Superscript>CO<Subscript>2</Subscript>: Partitioning of root,microbial, and rhizomicrobial respiration

The input of labeled C into the pool of soil organic matter, the CO₂ fluxes from the soil, and the contribution of root and microbial respiration to the CO₂ emission were studied in a greenhouse experiment with continuous labeling of oat plants with ¹³CO₂ using the method of the natural ¹³C abundance in the air. The carbon of the microbial biomass composed 56 and 39% of the total amounts of ¹³C photoassimilates in the rhizosphere and in the bulk soil, respectively. The contribution of root respiration to the CO₂ emission from the soil reached 61–92%, including 4–23% of the rhizomicrobial respiration. The contribution of the microbial respiration to the total CO₂ emission from the soil varied from 8 to 39%. The soil organic matter served as the major carbon-containing substrate for microorganisms in the bulk soil and in the rhizosphere: 81–91% of the total amount of carbon involved in the microbial metabolism was derived from the soil organic matter.     

土壤细颗粒对有机质的保护能力研究

本文主要综述了土壤细颗粒(<20μm或<50μm)对土壤有机质的保护能力,详细阐述了土壤储存细颗粒态有机质的能力模型及其意义,探讨了影响土壤细颗粒对有机质的保护能力的主要因素。     

土壤压实及有机质对其影响的研究进展

压实导致土壤板结的发生、与土壤团聚体的形成和破坏直接相关,而土壤的孔隙状况和水、气、热等条件改变在影响作物生长的同时,也会带来水土流失、碳氮温室气体排放等环境问题。在当今农业现代化进程加快、机械化水平提高的背景下,压实所引发的土壤板结问题愈益引起人们关注。本文在对土壤压实过程及其压缩曲线、表征参数等进行介绍的基础上,对近年来土壤压实过程及其影响因素方面的研究进展进行梳理,从提高土壤肥力、防治土壤板结的角度重点阐述了有机质改良土壤压实性状的效果及其作用机制,并对这一研究领域今后的发展趋势做了展望;研究认为在减少农业机械作业对农田压实次数和压实强度的前提下,提高土壤有机质含量、实行合理耕作仍然是我国今后改良土壤机械物理性质、培肥土壤和防止土壤板结的主要途径。