可溶性有机物对土壤中绿麦隆吸附与解吸的影响

A batch equilibrium techniques was used to examine the effect of dissolved organic matter （DOM） extracted from both non-treated sludge （NTS） and heat-expanded sludge （HES） on the sorption and desorption of chlorotoluron （3-（3-chloro-p-tolyl）-1,1-dimethylurea） in two types of soils, a yellow fluvo-aquic and a red soil from China. Without DOM,sorption of chlorotoluron was significantly greater （P 〈 0.05） in the red soil than in the yellow fluvo-aquic soil. However,with DOM the effect was dependent on the soil type and nature of DOM. Chlorotoluron sorption was lower in the yellow fluvo-aquic soil than in the red soil, suggesting that with the same DOM levels the yellow fluvo-aquic soil had a lower sorption capacity for this herbicide. Application of DOM from both NTS and HES led to a general decrease in sorption to the soils and an increase in desorption from the soils. Desorption of chlorotoluron also significantly increased （P 〈 0.05） with an increase in the DOM concentration. Additionally, for sorption and desorption, at each DOM treatment level the NTS treatments were significantly lower （P 〈 0.05） than the HES treatments. This implied that non-treated sludge had a greater effect on the sorption and desorption of chlorotoluron than heat-expanded sludge.     

Liming effect on dissolved organic matter leaching

The main agrochemical treatment applied in agriculture to lower harmful soil acidity is liming. Long term studies showed that application of calcium carbonate fertilizer brought about higher leaching of dissolved organic matter (DOM) in pot, lysdmetric and field experiments. Outflows obtained from limed soils contained 44.8% more DOM in comparison with nonlimed soils. During four years of lysimetric experiments it was found that the amounts of DOM from limed soils were increased by 52.7%. In the field experiments the amounts leached from one hectare of limed and nonlimed soil ranged 25.6 kg and 19.2 kg per year, respectively. DOM leached from limed soils was characterized by higher (45.4%) contents of carboxylic groups and humic substances (19.7%). Dissolved organic substances particularly humus rich in functional groups, due their complexing properties bound plant nutrients leached from soils and modify geochemical mobility of metals and anions. Therefore, DOM can play a significant role in the migration of chemical substances in agriculture landscape.     

长期定位施肥对土壤有机无机复合体中有机质和微量元素含量的影响

长期施用有机肥或有机无机肥配施显著提高潮土各组复合体中的有机质含量,但只能提高旱地红壤和红壤性水稻土G2组复合体中的有机质含量,增加的有机质主要累积于G2和G1组复合体中。长期单施化肥降低潮土各组复合体中的有机质含量,对旱地红壤和红壤性水稻土各组复合体中的有机质含量影响不大。长期施肥对土壤有机无机复合体中微量元素的影响,在不同土壤和不同施肥处理中不完全相同。相关分析表明,复合体中的有机质、微量元素含量与作物产量之间的相关性不高,因此,不宜用复合体中的有机质含量或微量元素含量来判断土壤肥力高低。     

Biochemical properties and biodegradation of dissolved organic matter from soils

Various biologically mediated processes are involved in the turnover of dissolved organic matter (DOM) in soil; however, relatively little is known about the dynamics of either the microbial community or the individual classes of organic molecules during the decomposition of DOM. We examined the net loss of DOC, the mineralisation of C to CO₂ and the degradation of DOC from six different soils by soil microorganisms. We also quantified the changes in the concentrations of protein, carbohydrate and amino acid C during microbial biodegradation. Over a 70-day incubation period at 20°C, the mineralisation of DOC to CO₂ was described by a double exponential model with a labile pool (half-life, 3–8 days) and a stable pool (half-life, 0.4–6 years). However, in nearly all cases, the mass loss of DOC exceeded the C released as CO₂ with significant deviations from the double exponential model. Comparison of mass DOC loss, CO₂ production and microbial cell counts, determined by epifluorescence microscopy, showed that a proportion of the lost DOC mass could be accounted for by microbial assimilation. Carbohydrate and protein C concentrations fluctuated throughout the incubation with a net change of between 3 to 13 and −30 to 22.4% initial DOC, respectively. No amino acid C was detected during the incubation period (level of detection, 0.01 mg C l⁻¹).     

黄土丘陵区不同植被下土壤可溶性有机物的荧光特征研究

【目的】土壤水溶性有机质的组成和结构是土壤质量的重要判别指标,具有重要的生态意义。研究黄土丘陵地区不同植被下土壤水溶性有机物的数量和荧光结构特征,可以为该地的植被修复及土壤质量评价提供科学依据。【方法】利用传统荧光和三维荧光技术,选取激发发射荧光光谱、 同步荧光光谱得到的腐殖化指标对土壤水溶性有机物的来源和结构进行评估,通过三维荧光技术探究不同植被下土壤水溶性有机物之间组分的差异。【结果】辽东栎(Quercus liaotungensis)和油松林(Pinus tabulaeformia)地具有较高的水溶性有机物含量,含量均为0.16 mg/g; 而荒坡地和农地的水溶性有机物较低,分别为0.04和0.05 mg/g,灌木荆条(Vitex negundo var. heterophylla )和狼牙刺(Sophora viciifolia)林地的含量介于两者之间。发射激发荧光光谱、 同步荧光光谱以及三维荧光光谱表明土壤水溶性有机物大多来源于植物和微生物的混合作用; 油松林地的水溶性有机物结构较简单、 腐殖化程度较低; 而灌木林地的水溶性有机物结构较为复杂、 腐殖化程度较高。从不同植被下土壤水溶性有机物的组成来看,蛋白类的物质差异不明显; 油松和辽东栎林地土壤水溶性有机物的类酪氨酸蛋白质、 类色氨酸蛋白质、 类溶解性微生物代谢产物含量较高,灌木林地较低。最主要的差异是富里酸类和胡敏酸类物质,油松林地的水溶性小分子量的富里酸类物质占主导地位,而灌木林地的水溶性有机物芳香化程度较高,农地和抛荒地类富里酸物质和类胡敏酸类物质含量的比值最低,其水溶性腐殖质的缩聚度高。油松、 辽东栎林地水溶性有机物由于植物残体分解形成的富里酸较易被氧化,同时阴坡林地较高的含水量使得这些产物较难缩合; 而灌木林地和农田及荒地较为干旱,枯枝落叶少,腐殖酸有充分时间进行缩合,导致了水溶性有机物的高芳香化和腐殖化。【结论】不同植被下的土壤水溶性有机物的组成和结构是存在差异的,同时说明荧光技术可用于揭示水溶性有机物的组成和缩合特性研究。     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Quantification of long‐chain fatty acids in dissolved organic matter and soils

The objective was to develop and adapt a versatile analytical method for the quantification of solvent extractable, saturated long‐chain fatty acids in aquatic and terrestrial environments. Fulvic (FA) and humic (HA) acids, dissolved organic matter (DOM) in water, as well as organic matter in whole soils (SOM) of different horizons were investigated. The proposed methodology comprised extraction by dichloromethane/acetone and derivatization with tetramethylammonium hydroxide (TMAH) followed by gas chromatography/mass spectrometry (GC/MS) and library searches. The C_10:0 to C_34:0 methyl esters of n‐alkyl fatty acids were used as external standards for calibration. The total concentrations of C_14:0 to C_28:0 n‐alkyl fatty acids were determined in DOM obtained by reverse‐osmosis of Suwannee river water (309.3 μg g^—1), in freeze‐dried brown lake water (180.6 μg g^—1), its DOM concentrate (93.0 μg g^—1), humic acid (43.1 μg g^—1), and fulvic acid (42.5 μg g^—1). The concentrations of the methylated fatty acids (n‐C_16:0 to n‐C_28:0) were significantly (r² = 0.9999) correlated with the proportions of marker signals (% total ion intensity (TII), m/z 256 to m/z 508) in the corresponding pyrolysis‐field ionization (FI) mass spectra. The concentrations of terrestrial C_10:0 to C_34:0 n‐alkyl fatty acids from four soil samples ranged from 0.02 μg g^—1 to 11 μg g^—1. The total concentrations of the extractable fatty acids were quantified from a Podzol Bh horizon (26.2 μg g^—1), Phaeozem Ap unfertilized (48.1 μg g^—1), Phaeozem Ap fertilized (57.7 μg g^—1), and Gleysol Ap (66.7 μg g^—1). Our results demonstrate that the method is well suited to investigate the role of long‐chain fatty acids in humic fractions, whole soils and their particle‐size fractions and can be serve for the differentiation of plant growth and soil management.     

秸秆施用后土壤溶解性有机质的动态变化

采用室内培养方法研究了水稻秸秆腐解对土壤溶解性有机质（Dissolved Organic Matter,DOM）含量及其化学组成的动态影响。结果表明,秸秆腐解的前7 d显著增加了土壤溶解性有机碳（DOC）含量,7 d后则无明显影响;同时,秸秆腐解增加了土壤中溶解性糖（DS）、溶解性酚酸（DP）以及芳香族化合物含量。随着腐解时间的延长,溶解性糖在DOC中所占比例下降,而芳香族化合物逐渐上升,表明秸秆腐解不同阶段DOM的化学组成发生了变化。溶解性总氮（TDN）的变化表明,秸秆腐解增加土壤氮素的固定。     

Contribution of dissolved organic matter to carbon storage in forest mineral soils

Dissolved organic matter (DOM) is often considered the most labile portion of organic matter in soil and to be negligible with respect to the accumulation of soil C. In this short review, we present recent evidence that this view is invalid. The stability of DOM from forest floor horizons, peats, and topsoils against microbial degradation increases with advanced decomposition of the parent organic matter (OM). Aromatic compounds, deriving from lignin, likely are the most stable components of DOM while plant‐derived carbohydrates seem easily degradable. Carbohydrates and N‐rich compounds of microbial origin produced during the degradation of DOM can be relatively stable. Such components contribute much to DOM in the mineral subsoil. Sorption of DOM to soil minerals and (co‐)precipitation with Al (and probably also with Fe), especially of the inherently stable aromatic moieties, result in distinct stabilization. In laboratory incubation experiments, the mean residence time of DOM from the Oa horizon of a Haplic Podzol increased from <30 y in solution to >90 y after sorption to a subsoil. We combined DOM fluxes and mineralization rate constants for DOM sorbed to minerals and a subsoil horizon, and (co‐)precipitated with Al to estimate the potential contribution of DOM to total C in the mineral soil of a Haplic Podzol in Germany. The contribution of roots to DOM was not considered because of lack of data. The DOM‐derived soil C ranges from 20 to 55 Mg ha^–1 in the mineral soil, which represents 19%–50% of the total soil C. The variation of the estimate reflects the variation in mineralization rate constants obtained for sorbed and (co‐)precipitated DOM. Nevertheless, the estimates indicate that DOM contributes significantly to the accumulation of stable OM in soil. A more precise estimation of DOM‐derived C in soils requires mineralization rate constants for DOM sorbed to all relevant minerals or (co‐)precipitated with Fe. Additionally, we need information on the contribution of sorption to distinct minerals as well as of (co‐)precipitation with Al and Fe to DOM retention.     

长期不同施肥潮土对可溶性有机碳的吸附特征

可溶性有机碳(DOC)吸附影响土壤元素化学行为。为此,本研究采用批处理法研究了DOC在长期不同施肥处理(对照CK、氮N、氮磷NP、氮磷钾NPK、化肥+秸秆还田NPKS、化肥+有机肥NPKM)潮土上的吸附动力学和等温吸附特征。结果表明,猪粪源DOC易于分解,需要添加0.025 mmol(1 mL 25 mmol/L)Na N3抑制其分解,抑制率超过90%。DOC吸附符合准二级动力学方程(R~2≥0.99)。不同施肥处理下,吸附速率常数k及初始速率常数h与平衡吸附Qe都没有显著差异,平均值分别为0.208 kg/(g·h)、1.60 g/(kg·h)和2.77g/kg。吸附等温式可用Langmuir方程很好拟合(R~2≥0.96),吸附容量(最大吸附量)Q_(max)在不同施肥处理下也没有显著差异(平均7.05 g/kg),但在N和NP等非平衡施肥下却保持高的亲合力,半饱和吸附浓度k_d分别为50.2和57.6 mg/L,吸附亲合常数K则分别为0.02和0.017 4 L/mg;相反,在NPKM处理下,显著低的亲合性发生,k_d和K分别为72.94 mg/L和0.013 8 L/mg。研究证明粘粉粒含量控制了不同施肥处理潮土对DOC的吸附;土壤有机碳水平不影响Q_(max),而且高土壤有机碳还降低其吸附亲合性。     

以水稻为主的种植系统对土壤有机质状况的影响

A long-term simulation experiment was carried out to study the effect of rice-based cropping system, green manure and ground-water level on soil organic matter. Soil organic matter content increased when upland soil was puddled and cropped under submerged conditions. Among all treatments, soil organic matter contents in the treatments of rice-rice-flooded fallow in winter (WF) were the highest, those in the treatments of rice-rice-astragalus (WG) came the second, and those in the treatments of rice-rice-rape (WR) were the lowest. At the same rate of green manure application, the degrees of organo-mineral complexing in soils of treatments WG and WR were higher than those of treatment WF. After 9-year rice cultivation, the state of combination of humus in heavy fraction varied with treatments. The relative content of loosely bonded humus decreased in the order of WR > WG > WF, and it correlated significantly with Se availability.     

The quality of exogenous organic matter: short-term effects on soil physical properties and soil organic matter fractions

We examined the short-term effect of five organic amendments and compared them to plots fertilized with inorganic fertilizer and unfertilized plots on aggregate stability and hydraulic conductivity, and on the OC and ON distribution in physically separated SOM fractions. After less than 1 year, the addition of organic amendments significantly increased ( P  <   0.01) the aggregate stability and hydraulic conductivity. The stability index ranged between 0.97 and 1.76 and the hydraulic conductivity between 1.23 and 2.80 × 10⁻³ m/s for the plots receiving organic amendments, compared with 0.34–0.43, and 0.42–0.64 × 10⁻³ m/s, respectively, for the unamended plots. There were significant differences between the organic amendments (P <  0.01), although these results were not unequivocal for both soil physical parameters. The total OC and ON content were significantly increased ( P  <   0.05) by only two applications of organic fertilizers: between 1.10 and 1.51% OC for the amended plots versus 0.98–1.08% for the unamended and between 0.092 and 0.131% ON versus 0.092–0.098% respectively. The amount of OC and ON in the free particulate organic matter fraction was also significantly increased ( P  <   0.05), but there were no significant differences ( P  <   0.05) in the OC and ON content in the POM occluded in micro-aggregates and in the silt + clay-sized organic matter fraction. The results showed that even in less than 1 year pronounced effects on soil physical properties and on the distribution of OC and ON in the SOM fractions occurred.     

动物粪液中可溶性磷在土壤中的吸附和迁移特性研究

农田土壤施用动物粪肥引入了大量的可溶性有机物、有机磷和无机磷,了解这些可溶性物质在土壤中的相对移动性及它们之间的相互作用有助于指导农田养分管理。本研究从粪液中分离获得含水溶性无机磷、有机磷和有机物（碳）的溶液,选择了具不同质地和有机质含量的4个土壤（含高量有机质的黄筋泥、含低量有机质的黄筋泥、淡涂泥和清水沙）,应用等温吸附和土柱模拟淋洗方法研究了可溶性有机碳、无机磷和有机磷共存条件下,粪液中可溶性有机态磷和无机态磷在土壤中的吸附和迁移特性。吸附试验表明,可溶性有机物（碳）的存在大大降低了土壤对有机态磷和无机态磷的吸附,表明施用液态有机肥比施用化肥具有更大的磷流失风险。供试土壤对无机态磷的吸附强度高于有机态磷,但对二者的吸附量大小为:黄筋泥>淡涂泥>清水沙;并与粘粒含量、氧化铁含量呈正相关。有机质较高的土壤对有机磷的吸附明显低于有机质低的土壤。淋洗试验表明,在供试土壤中,这3种可溶性物质在土壤中吸持(包括生物吸持)的顺序为:可溶性无机磷>可溶性有机碳>可溶性有机磷;有机态磷比无机态磷更易在土壤中迁移。     

基于三维荧光光谱的土壤溶解性有机质的提取

Soil dissolved organic matter(DOM) consists of many organic compounds and plays an important role in contaminant transport in the ecosystem. However, the effects of different extraction conditions on contents of different DOM components are poorly understood.We extracted DOM from three soils using different extraction times, solid to liquid ratios(SLR), and extraction solution(KCl)concentrations, and evaluated the extractions using three-dimensional excitation-emission matrix(EEM) fluorescence spectroscopy.The sum of the contents of the main DOM components(protein-, fulvic-, and humic-like compounds) increased by 0.6–3.5, 2.5–3.9,and 0.11–0.37 times(P 0.05) when SLR decreased from 1:2 to 1:10, the extraction solution concentration increased from 0.01 to 1.5 mol L~(-1), and extraction time increased from 10 to 300 min, respectively. The three-dimensional EEM fluorescence spectroscopy is a useful tool to characterize the components of DOM and evaluate DOM extraction in soils.     

Studies on the properties of organic matter in buried humic horizon derived from volcanic ash

Abstract

Humic acids were extracted from the surface horizon Yu 1 and buried humic horizons (Yu 2, 800-864 AD; Yu 4, ca. 4,000 years B.P.; Yu 6, 7,000 years B.P.; Yu 7, ca. 10,000 years B.P.). The humic acids were filtered with ultramembranes with 20, 10, 5, 1 or 0.1 × 10' M.W. in this order and separated into five fractions; (>20), (20-10), (10-5), (5-1) and (1-0.1) × 10⁴ M.W. fractions. The elementary composition, functional groups, optical properties, and hydrolyzable total- and sugar-carbon contents of each humic acid fraction were determined, and the changes in properties of the humic acid with age after burial were discussed.

In horizons Yu 1 to Yu 6, the patterns of M.W. distribution of the >20 × 10⁴ to (1- 0.1) × 10⁴ fractions were rather similar. In contrast, Yu 7 was characterized by the predominance of (1-0.1) x 10' M.W. fraction and the presence of a small amount of <0.1 × 10⁴ M.W. fraction.

The chemical properties of humic acid (HA) fractions of each humic horizon and their changes with age after burial were as folIows:

1) Elementary composition of HA fractions of each humic horizon was rather similar to each other. The C% and C/N ratio increased, and the H%, N% and H/C ratio decreased in all HA fractions with age.

2) Total acidity and carboxyl contents of HA fractions of Yu 1 were higher in the lower M.W. fractions. These values increased with age up to Yu 4 or Yu 6 horizons, then decreased in the Yu 6 or Yu 7 horizon. The contents of carbonyl groups in all the HA fractions which were very low in Yu 1, showed a wide range of variations in Yu 2, intermediate values from Yu 4 to Yu 6 horizons then decreased in the HA fractions of Yu 7, except for the (>20) fraction.

3) The degree of humification of the HA fractions of Yu 1 judging from the RF and \sDlogK values, tended to be higher in higher M.W. fractions, and increased in all the HA fractions with age after burial.

4) Hydrolyzable total- and sugar-carbon contents were high in the HA fractions of Yu 1 and decreased with age.

5) Changes of elementary composition, degree of humification and hydrolyzable total- and sugar-carbon contents were conspicuous from the Yu 1 to Yu 2 horizons, and less significant afterwards.

6) The 0%, C/O ratio and phenolic OH content did not show any consistent change with age after burial.     

不同生物有机肥用量对土壤活性有机质和酶活性的影响

通过盆栽试验研究了不同有机质含量的土壤中,不同用量生物有机肥对棉花苗期土壤活性有机质和5种酶活性的影响。结果表明,不同土壤随着生物有机肥施用量的增加,其活性有机质及碳库管理指数(CMI)均显著增加。其中高有机质含量土壤施用生物有机肥20 g/kg效果显著,中等有机质含量土壤和低有机质含量土壤施用生物有机肥30、40 g/kg效果显著。5种土壤酶活性施肥处理均高于对照(CK),并且土壤酶活性与施用量成正比。脲酶、蔗糖酶、多酚氧化酶在施用生物有机肥10、20 g/kg与其它处理相比变化显著,过氧化氢酶、蛋白酶变化不显著。相关分析表明,有机质与活性有机质和CMI在棉花出苗0 d相关系数分别为0.831**、0.542*;在出苗后60 d相关系数分别为0.928**、0.635**,其中有机质与活性有机质相关性最高。而CMI与有机质和活性有机质在棉花出苗0 d相关系数分别为0.542*、0.896**,在出苗后60 d分别为0.635**、0.842**,说明活性有机质相对于有机质与CMI关系更为密切。蔗糖酶、过氧化氢酶、多酚氧化酶与土壤有机质和活性有机质在棉花出苗0 d和出苗后60 d存在显著相关,表明活性有机质与土壤酶活性能够较好的反映肥力水平。     

平菇栽培废料等有机肥对土壤活性有机质和土壤酶活性的影响

通过大田试验研究了不施有机肥(CK)、施用平菇栽培废料(T1)、施用干腐熟牛粪(T2)和烘干鸡粪(T3)在种植黄瓜01～50.d内土壤中活性有机质和4种土壤酶活性的变化。结果表明:施入不同有机肥对土壤总有机质含量的影响为烘干鸡粪平菇栽培废料干腐熟牛粪对照;对活性有机质含量的影响为平菇栽培废料烘干鸡粪干腐熟牛粪对照;施用平菇栽培废料的土壤中脲酶、转化酶和脱氢酶活性最高,施用干腐熟牛粪的土壤中过氧化氢酶活性最高。相关性分析显示,脲酶、转化酶和脱氢酶活性与土壤活性有机质显著相关。用平菇栽培废料做有机肥能有效提高土壤活性有机质含量和土壤酶活性。     

Precipitation of enzymes and organic matter by aluminum—Impacts on carbon mineralization

The precipitation of dissolved organic matter (DOM) by aluminum (Al) results in a stable soil organic matter (OM) fraction. Extracellular enzymes can also be removed from soil solution by sorption or precipitation, but whether this affects their activity and their importance for carbon (C) mineralization is largely unknown. We studied the activity of eight extracellular enzymes, precipitated by Al together with DOM, in relation to C mineralization of the precipitated OM. Dissolved OM was obtained from the Oi and Oa horizon of two forest soils and precipitated at different Al : C ratios and pH values to achieve a large variation in composition and C mineralization of precipitated OM. All eight enzymes were present in a functional state in precipitated OM. On average 53% of DOM was precipitated, containing on average 17%–41% of the enzyme activity (EA) involved in C degradation (chitinase, cellobiohydrolase, β‐glucosidase, glucuronidase, lacasse, and xylosidase) previously present in soil solution. In contrast, on average only 4%–7% of leucine‐aminopeptidase and acid‐phosphatase activity was found in precipitated OM. The EA found in precipitates significantly increased the percentage of C mineralized of precipitated OM, with a stronger influence of C‐degrading enzymes than enzymes involved in N and P cycling. However, after 8 weeks of incubation the correlations between EA and C mineralization disappeared, despite substantial EA being still present and only 0.5%–7.7% of C mineralized. Thus, degradation of precipitated OM seems to be governed by EA during the first degradation phase, but the long‐term stability of precipitated OM is probably related to its chemical properties.