从高山火山灰中提取铝, 铁和有机碳的可供选择的方法

Montane volcanic ash soils contain disproportionate amounts of soil organic carbon and thereby play an often underestimated role in the global carbon cycle.Given the central role of Al and Fe in stabilizing organic matter in volcanic ash soils,we assessed various extraction methods of Al,Fe,and C fractions from montane volcanic ash soils in northern Ecuador,aiming at elucidating the role of Al and Fe in stabilizing soil organic matter(SOM).We found extractions with cold sodium hydroxide,ammonium oxalate/oxalic acid,sodium pyrophosphate,and sodium tetraborate to be particularly useful.Combination of these methods yielded information about the role of the mineral phase in stabilizing organic matter and the differences in type and degree of complexation of organic matter with Al and Fe in the various horizons and soil profiles.Sodium tetraborate extraction proved the only soft extraction method that yielded simultaneous information about the Al,Fe,and C fractions extracted.It also appeared to differentiate between SOM fractions of different stability.The fractions of copper chloride-and potassium chloride-extractable Al were useful in assessing the total reactive and toxic Al fractions,respectively.The classical subdivision of organic matter into humic acids,fulvic acids,and humin added little useful information.The use of fulvic acids as a proxy for mobile organic matter as done in several model-based approaches seems invalid in the soils studied.     

中国黑土上腐殖酸和腐殖物质的提取及其描述

Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC even after 23 successive HA extractions. In addition, the atomic C/H ratio decreased during the course of extraction while C/O increased; the E4/E6 ratio from the UV analysis decreased with further extraction while E~/E3 increased; the band assigned to aliphatic carbon (2 930 cm-1) in the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) spectra gradually increased with progressive extraction; the calculated ratio of the sum of aromatic carbon peak heights to that of aliphatic carbon peak heights from DRIFTS spectra declined with extractions; and nuclear magnetic resonance (NMR) data suggested that HA aliphatic carbons increased with extractions while aromatic carbons decreased. Thus, hydrophobicity and aliphaticity of HAs increased with extractions while polarity and aromaticity decreased. These data showed substantial chemical, structural, and molecular differences among the 23 HAs and two humin fractions. Therefore, these results may help explain why soil and sediment humin fractions have high sorption capacity for organic contaminants.     

Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).     

Effect of Organic Manure Application on Physical Properties andHumus Characteristics of Paddy Soil

Long-term field experiment was established in 1978 on a coastal paddy soil to determine the effect of application of pig manure, rice straw and chemical N fertilizer on the physical property and humus characteristics of soil. Results showed that the porosity, the microstructural coefficient, the reactivities of organic C and N, the OlogK value, the degree of oxidation stability, the contents of o-alkyl C and alkyl C, and the ratio of aliphatic C to aromatic C of humic acid from soils received organic manure increased; whereas, the ratio of<10μm to >10μm of microaggregates, the humification degree of humus, the degree of organo-mineral complexation, the number-average molecular weight, the C/H ratio, the contents of carboxyl and aromatic C of HAs in them decreased. These results indicated that the application of organic manure not only improved the physical property of the paddy soil but also made the HA more aliphatic in structure and younger in origin.     

Effects of Water Regime and Reaction of Soil on Properties of Newly—Formed Humic Substances

The effects of soil water regime and soil reaction on nitrogen distribution and fractional composition of newly-formed humus (decayed products) and the structural characteristics of the newly-formed humic acids(HAs) were studied in an incubation experiment,with the following results obtained: 1.The humus newly formed under submerged conditions was higher in the relative content of α-amino acid-N and the humic acid/fulvic acid (HA/FA) ratio than that under upland conditions.The HAs extracted from the former were also higher in C/O ratio,aromaticity and the contents of methoxyl groups and lignin-like components,but lower in the content of carboxyl groups than the HAs from the latter. 2.Under upland conditions,the C/ organic N ratio and the relative content of mobile HA of newly-formed humus were lower,but the HA/FA ratio was higher in the CaCO2-amended treatment than in non-amended treatment.The presence of CaCO3 also resulted in a decrease of C/N ratio of HA and a slight increase of its carboxyl group content.On the other hand,there was no significant change in the composition and properties of the newly-formed humus with the addition of CaCO3 under submerged conditions. 3.Compared with soil HAs,the newly-formed HAs contained more carbohydrates,polypeptides and lignin-like components,and were in lower degrees of oxidation and humification.     

半干旱土添加有机改良剂后有机质的化学结构变化

A 9-month incubation experiment using composted and non-composted amendments derived from vine pruning waste and sewage sludge was carried out to study the effects of the nature and stability of organic amendments on the structural composition of organic matter (OM) in a semi-arid soil.The changes of soil OM,both in the whole soil and in the extractable carbon with pyrophosphate,were evaluated by pyrolysis-gas chromatography and chemical analyses.By the end of the experiment,the soils amended with pruning waste exhibited less organic carbon loss than those receiving sewage sludge.The non-composted residues increased the aliphatic-pyrolytic products of the OM,both in the whole soil and also in the pyrophosphate extract,with the products derived from peptides and proteins being significantly higher.After 9 months,in the soils amended with pruning waste the relative abundance of phenolic-pyrolytic products derived from phenolic compounds,lignin and proteins in the whole soil tended to increase more than those in the soils amended with sewage sludge.However,the extractable OM with pyrophosphate in the soils amended with composted residues tended to have higher contents of these phenolic-pyrolytic products than that in non-composted ones.Thus,despite the stability of pruning waste,the composting of this material promoted the incorporation of phenolic compounds to the soil OM.The pyrolytic indices (furfural/pyrrole and aliphatic/aromatic ratios) showed the diminution of aliphatic compounds and the increase of aromatic compounds,indicating the stabilization of the OM in the amended soils after 9 months.In conclusion,the changes of soil OM depend on the nature and stability of the organic amendments,with composted vine pruning waste favouring humification.     

Analysis of the microbial communities in soils of different ages following volcanic eruptions

Volcanism is a primary process of land formation.It provides a model for understanding soil-forming processes and the role of pioneer bacteria and/or archaea as early colonizers in those new environments.The objective of this study was to identify the microbial communities involved in soil formation.DNA was extracted from soil samples from the Llaima volcano in Chile at sites destroyed by lava in different centuries(1640,1751,and 1957).Bacterial and archaeal 16 S r RNA genes were analyzed using quantitative polymerase chain reaction(q PCR)and Illumina Mi Seq sequencing.Results showed that microbial diversity increased with soil age,particularly between the 1751 and 1640 soils.For archaeal communities,Thaumarchaeota was detected in similar abundances in all soils,but Euryarchaeota was rare in the older soils.The analysis of bacterial 16 S r RNA genes showed high abundances of Chloroflexi(37%),Planctomycetes(18%),and Verrucomicrobia(10%)in the youngest soil.Proteobacteria and Acidobacteria were highly abundant in the older soils(16%in 1640 and 15%in 1751 for Acidobacteria;38%in 1640 and 27%in 1751 for Proteobacteria).The microbial profiles in the youngest soils were unusual,with a high abundance of bacteria belonging to the order Ktedonobacterales(Chloroflexi)in the 1957 soil(37%)compared with the 1751(18%)and 1640(7%)soils.In this study,we show that there is a gradual establishment of the microbial community in volcanic soils following an eruption and that specific microbial groups can colonize during the early stages of recovery.     

Evaluation of Soil Labile Phosphorus Using a Double—Labeling （^32P and ^33P） Technique

Isotopic exchangeability of phosphorus in four Chinese soils with and without P application was studied by ^32P and ^33P double-labeling technique in relation to routine chemical extractions.The results showed that Bray-I and Bray-Ⅱ reagents could extract most of the fast exchangeable P.Not all of the Olsen-P belonged to fast exchangeable P,but it was about the same quantity of fast exchangeable P in a calcareous soil and a neutral soil without P application.Sequential fractionation of the soil phosphorus showed that most of the added radioisotopes in high P fixation red soils were tightly held by iron and aluminium oxides,which could be totally extracted only by 0.1M NaOH solution.In the neutral and calcareous soils most of the radioisotopes added were loosely held on the surface of soil particles and could be extracted by anion exchange resin.Phosphate application increased the resin-P fraction significantly for all the soils studied.     

Titratable Acidity and Alkalinity of Red Soil Surfaces

The surfaces of red soils have an apparent amphotenc character, carrying titratable acidity and titratable alkalinity simultaneously. The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter, while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces. The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils. The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution, free iron ox-ide(Fed) extracted with sodium dithionite-citrate-bicarbonate (DCB) and clays, but also with the zero point of charge (ZPC) of the samples. Organic matter made an important contribution to the titratable acidity.     

土地利用方式对田间植物残体中C、N矿化的影响

Four kinds of plant materials(astragalus,azolla,rice straw and water hyacinth) were allowed to decom-pose for 10 years in two soils with different mineralogical characteristics in fields under upland and submerged conditions.Greater amounts of C and N from azolla were retained in soils throughout the 10-year experi-mental period compared to those from the other plant materials.The residual C of all the plant materials in the two soils under upland conditions mineralized at rates corresponding to half-lives between 4.4-6.6 years,while the corresponding figures for those under submerge conditions were between 6.5-13.1 years,Minera-liztion of residual organic N followed the same pattern as residual C.Compared to residual C,however,the mineralization rates of residual organic N in most cases were significantly lower and the percentages of added N retained in soils were higher.More N from plant materials was retained in the yellow-brown soil than in the red soil,but no consistent differences in the amounts of C from plant materials and in the mineraliztion rates of both residual C and residual organic N between the wto soils could be folund.     

Aerobic short-term microbial utilization and degradation of humic acids extracted from soils of long-term field experiments

A humic acid (HA) fraction of the soil organic matter (SOM) was extracted with alkali from soil samples originated in non-fertilized and fertilized (NPK + organic manure) plots of long-term (45 years) field experiments. The HA preparations served as supplemental sources of nutrients or as sole source of either C or N for soil micro-organisms indigenous to the same soils. Under aerobic conditions (shake cultures) between 15% and 45% of HA were degraded in 21 days. The degradation was minimum if HAs were added supplementary, although the biomass formation was strongly enhanced. Preparations of HA from long-term fertilized soils appeared somewhat less susceptible to microbial degradation but they were capable of supporting microbial growth. Under copious nutritional conditions some novel HA-like substances were formed. The HA preparations re-isolated from individual cultures exhibited differences in elemental and structural characteristics. The FTIR spectra indicated an increasing proportion of aromatic structures that appeared as associated with mineral moieties. Conclusively, HAs from long-term fertilized and manured soils could be considered as more resistant to microbial activities than those from control soil, but under limited nutrient conditions their aliphatic constituents appear utilizable by micro-organisms.     

Long term effects of a brown coal-based amendment on the properties of soil humic acids

In this study a typical grey-brown podzolic soil was amended with different doses of a brown coal-based preparation called Rekulter (R) largely used in Poland. After seven years, soils were analyzed and humic acids (HAs) were extracted both from the control soil and from the amended soils. All HAs were characterized by Fourier transform infrared spectroscopy and fluorescence spectroscopy both in emission, excitation and synchronous-scan mode and as Excitation-Emission-Matrix (EEM) contour maps. A higher carbon content was observed in the amended soils whereas significant differences were highlighted between the unamended and the amended soil HAs. HAs from amended soils showed a higher content of carboxyl groups and a more aromatic character, particularly HA extracted from the soil amended with the highest dose of R.     

Effects of pig slurry application on soils and soil humic acids

The effect of three annually consecutive additions of pig slurry at two rates (90 and 150 m3 x ha(-1) x year(-1) on soils and soil humic acids (HAs) was investigated in a field experiment under semiarid conditions. Soils and pig slurries were analyzed by standard methods. The HAs were isolated from soils and pig slurry by a conventional procedure based on alkaline extraction, acidic precipitation to pH 1, purification by repeated alkaline dissolutions and acidic precipitations, water washing, dialysis, and final freeze-drying. The HAs obtained were analyzed for elemental (C, H, N, S, and O) and acidic functional group (carboxylic and phenolic) composition, and by UV-vis, FT-IR, fluorescence, and ESR spectroscopies. With respect to the control soil, the pig slurry amended soils had greater pH and electrical conductivity, slightly larger total N content, and smaller values of C/N ratio. A decrease of total organic C was observed only in soils amended for 2 and 3 years at the higher slurry rate. With respect to control soil HA, pig slurry HA was characterized by larger contents of S- and N-containing groups, smaller acidic functional group and organic free radical contents, a prevalent aliphatic character, extended molecular heterogeneity, and smaller aromatic polycondensation and humification degrees. Amendment with pig slurry HA determines a number of modifications in soil HAs, including increase of C, S, and COOH contents, C/N ratios, and aliphaticity and decrease of extraction yields and N, O, phenolic OH, and organic free radical contents. These effects are generally more evident after the first year of slurry application and tend to disappear with increasing number of treatments. Most probably, over the years the slightly humified slurry HA is mineralized through extended microbial oxidation, whereas only the most recalcitrant components, such as S-containing, phenolic, and aliphatic structures, are partially accumulated by incorporation into soil HA.     

Chemical and spectroscopic characterization of Humic acids from a soil toposequence in venezuela

Abstract

An investigation was conducted on physico‐chemical properties of humic acids (HAs) in Venezuelan soils. The HAs were extracted by the NaOH method from a Banco‐Bajio‐Estero soil toposequence (local names for soils located at high, intermediate and low topographic levels), in the Venezuelan plains (Mantecal, Apure State). The extracted HAs were analyzed for elemental composition and characterized by fluorescence, Fourier transform infrared (FT‐IR) and electron spin resonance (ESR) spectroscopies. The results showed that free radical concentration of HAs increased from soils at the highest to soils at the lowest topographic position. High carbon (C), nitrogen (N), and carboxyl group contents, E₄/E₆ ratio, aliphatic character and concentration of free radicals, and low oxygen (O) and phenolic hydroxyl group contents and total acidity were typical of HA from soils at the lower relief position. The FT‐IR spectra indicated that the HA from the soil at the lowest topographic position tended to have a slightly higher content of carboxyl groups than the HAs from soils at higher topographic levels. The observed fluorescence was attributed to the presence of condensed aromatic moieties and/or conjugated unsaturated systems of various complexity in the HA macromolecules.     

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.     

Changes in humic fraction characteristics and humus-enzyme complexes formation in semiarid degraded soils restored with fresh and composted urban wastes. A 5-year field experiment

Purpose

The aim of this study was to evaluate in the medium term (5 years) the effect of two organic amendments, which were spiked to a degraded soil as a strategy for bioremediation, on the amount and characteristics of soil humic acids (HAs) and their ability to associate with certain extracellular enzymes.

Materials and methods

Soil samples were collected in an experimental field where 5 years earlier, a mixture of the organic fraction of household waste and sewage sludge (2:1 ratio), both composted (composted residue, CR) and non-composted (fresh residue, FR), had been added in triplicate at rates equivalent to 1 % (D1) and 3 % of organic carbon (D2) to 30-m² plots as a strategy for degraded soil restoration. Humic substances (HSs) and HAs were extracted from the collected soil samples and submitted to chemical, biochemical, spectroscopic (FTIR), and chemical-structural (CPMAS ¹³C NMR) analyses.

Results and discussion

After 5 years, the amended soils showed significantly higher HS and HA content than did the control soil, and the differences with respect to the control were greater with compost addition than with FR addition. The HA from the amended soils had higher H, N, and S contents than the HA from the non-amended soil in addition to a lower oxygen content and lower O/C ratio values. Furthermore, the FTIR spectra of the HA from the amended soils showed a higher absorption intensity in bands corresponding to aliphatic and amide-carboxylic groups and polysaccharide structures and a lower absorption intensity in bands corresponding to carbonyls and carboxylic groups than the HA from the control. These results were confirmed by ¹³C-NMR spectra, which showed a clear increase of aliphatic compounds in the HA from the amended soils with respect to the HA from the control. HA spectra were not greatly influenced by the maturity of the amendment or by the application dose.

Conclusions

In general, the addition of organic amendments increased the quantity of enzymes immobilized in the humic colloid. Furthermore, the addition of the composted residues favored to a greater extent the immobilization of the abovementioned enzymes, which represent a biological reservoir in the soil. This is of great importance since these enzymes possess functional capacity even when the soils are under conditions that are stressful or unfavorable for microbial life. An increase in the quantity of immobilized enzymes such as that observed in amended soils supposes an important improvement in soil quality.

     

Compositional and functional features of humic acids from organic amendments and amended soils in Minnesota, USA

The use of organic amendments requires an adequate control of the chemical quality of their humic acid (HA)-like fractions and of the effects that these materials may have on the status, quality, chemistry and functions of native soil HAs. In this work, the compositional, functional and structural properties of the HA-like fractions isolated from a liquid swine manure (LSM), a municipal sewage sludge (SS), and two municipal solid waste composts (MSWCs) were evaluated in comparison to those of HAs isolated from three unamended soils and from the corresponding soils amended with LSW, SS, and MSWC at various rates in three field plot experiments conducted in Minnesota, USA. With respect to the unamended soil HAs, the HA-like fractions of the three amendments featured a greater aliphatic character, a marked presence of proteinaceous, S-containing and polysaccharides-like structures, an extended molecular heterogeneity, small organic free radical contents and a small degree of humification. The MSWC-HAs featured a larger degree of humification than LSM-HA and SS-HA. The three amendments affected in different ways and by various extents the compositional, structural and functional properties of soil HAs depending upon the nature, origin and application rate of the amendment. In general, the data obtained suggested that proteinaceous, S-containing and aliphatic structures contained in HA-like fractions of organic amendments were partially incorporated into native soil HAs.     

Chemical structure of humic acids in biosolids-amended soils as revealed by NMR spectroscopy

We used NMR spectroscopy to characterize humid acids extracted from soils that had received long-term application of 2 levels of biosolids to evaluate the soil organic matter (SOM) stability in biosolids-amended soils. The study also quantified fulvic acids (FAs), humic acids (HAs) and Fe/Al oxides. The soils were collected in 2004 from 7 fields, in Fulton County, southwestern Illinois, which received biosolids at a cumulative rate of 0 (control), 554 (low biosolids) and 1,066 (high biosolids) Mg ha⁻¹. The application of biosolids increased both FA and HA contents, but biosolids-amended soil and control soil did not differ in FA/HA ratio. Biosolids application had no effect on water-soluble organic carbon content. Biosolids application increased the presence of Fe/Al in the SOM complex and lowered its C/Fe and C/Al ratios. ¹³C NMR spectra showed increased alkyl C and decreased aromatic C content in soil HAs with the application of biosolids, and the extent of such changes was higher with high than low biosolids treatment. Under biosolids application, the soil HAs’ C structure shifts from O-alkyl-dominant to alkyl-dominant. Biosolids application does not decrease SOM stability but rather increases the stability of soil humic substances.     

Chemical and physical characteristics of humic substances extracted from greek soils varying in classification order and natural drainage

Abstract

Humic and fulvic acids were extracted from the surface horizons of Alfisols, Vertisols, and Entisols with good and impeded natural drainage. These profiles are located in the temperate subhumid zone. The extracted humic substances were characterized by elementary and functional group analyses, IR‐spectroscopy, differential thermal analysis (DTA) and electron spin resonance spectroscopy (ESR). Some differences in the humic substances seem to be associated with differences in the natural drainage of the soils. When data from samples of the same soil order are compared, indicate that humic (HAs) and fulvic acids (FAs) extracted from soils with impeded drainage, have higher contents of carbon and spin concentration, but less total acidity and fewer carboxylic groups (COOH), than the respective humic substances extracted from well drained soils. The IR‐spectra of the HAs extracted from soils with impeded drainage showed more aliphatic groups than those of the well drained soils. No essential differences, which could be related to the drainage conditions of the studied soils, were observed in the IR‐spectra of FAs. DTA‐diagrams shows that the thermal stability of the HAs and the FAs are related to their carbon and ash contents. Iron was the dominant element in the ash of the humic acids, aluminum and silicon were the most abundant elements in the ash of the fulvic acids.