高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.     

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.     

Dicyandiamide sorption-desorption behavoir on soils and peat humus

The sorption-desorption behavior of dicyandiamide (DCD) is an important chemical process that affects DCD fate and mobility in soils. Therefore, this study quantified DCD sorption-desorption on a phaeozem (Mollisol), a burozem (Alfisol), a soil with organic matter-removed and peat humus using the batch-equilibration procedure, and identified soil properties that influenced DCD sorption. The sorption on peat humus was higher than that on the phaeozem and the burozem, with much lower sorption observed on the soil with organic matter-removed, indicating that soil organic matter was the main carrier of DCD sorption. Due to its amphipathic property the DCD molecule sorption on the phaeozem and the burozem decreased as pH increased from about 2 to 5, but a further increase in pH led to a rise in DCD sorption.The DCD desorption hysteretic effect for peat humus was greater than that for the phaeozem and the burozem using 0.01 mol L^-1 CaCl2 as the background electrolyte, suggesting that the hydrophobic domains of organic matter may play an important role in DCD sorption.     

不同年代的埃特纳火山土壤上用甘油萃取有机质的特性

We characterized humic acids (HAs) and glycerol-extractable organic fractions (GEOFs) extracted from four Andisols, taken from comparable soil-climate conditions on the east side of Mount Etna. The soils were formed on old lava (about 9 000 years ago), old tephra (about 8 700 years ago), recent lava (about 2 600 years ago) and recent tephra (about 3 600 years ago). A part of the organic matter of the soils, deprived of HAs and fulvic acids (FAs), was isolated by glycerol extraction. The GEOF can not be extracted with alkaline solutions, probably because it is closely bound to the mineral component of the soil. The characterization of the extracted organic fraction was carried out using elementary and functional group analysis and Fourier transform infrared (FT-IR) spectroscopy. About 20 extractions were necessary to extract the HA and FA from the older soils and about 10 extractions to extract them from the younger soils. Data showed that the GEOFs had a greater ash content and a smaller N content, as well as a greater presence of aliphatic compounds and carboxylic groups as compared to the HA extracted from the same soil. The GEOFs extracted from younger soils also had a lower yield, ash and COOH-group content, and were more aliphatic than the GEOF extracted from older soils. Finally, the GEOFs were more closely bound to the amorphous component of the soil (‘short-range’ minerals) and consequently less subject to biodegradation.     

重金属污染对典型湿润富铁土上钾素行为的影响

Difference of montmorillonite(Mt),illite(It) and kaolinite(Kt) in lead sorption characteristics and the effects of amorphous Fe and Al oxide coatings on the characteristics were experimentally sutdied with logistic model.The sorption curves had sigmoid feature due to use of acetate-type buffer solution.With the model the sorption process could be divided into four stages and the sorption characteristics at the stages were discussed.The results showed that,after Mt,It and Kt were coated by amorphous Fe oxide,their maximum sorption capacity(MSC) and percentage of high-SSC concentration scope(HCS) of Pb^2 increased markedly,but the specific sorption capacity(SSC) decreased.with regard to effects of amorphous Al oxide coating,except for It Al,the SSC of other samples showed a downtrend,despite that their MSC remained unchanged.Eventually,the gray correlation degrees to Pb^2 sorption for different physicochemical characteristics of the clay minerals were indicated to be higher for hydronium,zero point of surface charge and hydroxy,but lower for specific surface area.density of surface charge and amount of surface charges.     

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.     

土壤中磷、钾、钙、镁的同时提取以及对巴西南部作物的钾肥推荐

Simultaneous multi-element extraction has been increasing worldwide to improve soil laboratory testing quality and effciency. This study sought to investigate the applicability of the Mehlich-1, Mehlich-3, and resin methods for simultaneous extraction of soil available P, K, Ca, and Mg as well as the effect of using conversion equations on nutrient recommendations for crops. Topsoil (0-20 cm) samples were taken from the most representative soil types used for crop production in southern Brazil with a wide range of chemical, physical, and mineralogical properties. Soil P, K, Ca, and Mg were simultaneously extracted using 1.0 mol L-1 KCl, Mehlich-1 and Mehlich-3 solutions, and membrane resin. The amounts of P extracted with the Mehlich-1 method were, on average, 50% lower than those extracted with the resin and Mehlich-3 methods. However, the resin method extracted the lowest amounts of K, Ca, and Mg. The use of conversion equations was suitable and it did not a?ect negatively the K recommendations for crops grown on soils of southern Brazil.     

乙炔浓度对厌氧培养的土壤悬浊液反硝化作用及相关的微生物过程的影响

Potentiometric experiments were carried out on the proton binding equilibria of FA extracted from a weathered coal and HA and Fa extracted from a dark loessial soil.The affinity spectrum model was employed to treat the experimental data.The affinity spectrum model technique could“magnify” the heterogeneity of the proton binding equilibria.so it was useful for comparing and studying the characteristics of humic substances with similar properties.According to the affinity spectra,we also found that the direction of the titration could affect the properties of the equilibria of FA from the weathered coal,and the acidic functional groups contained in FA from the weathered coal were larger in quantity than those contained in HA and FA from the dark loessial soil.     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

溶液体系中非生物因素对胡敏酸还原汞的影响

As a global pollutant process,the reduction of mercury(Hg)is especially important.One pathway is through an abiotic reduction with humic acids(HAs),which is controlled by different factors,including initial Hg and HA concentrations,pH,temperature and light.In this study,three humic acids were selected to illustrate the Hg~(2+)abiotic reduction mechanisms by HAs,and to identify the key limiting factors for reduction rates and amounts.In addition,the initial status of the HAs as a solid or in an aqueous solution were also compared,to help explain why HAs show different dominant characteristics(e.g.complexation or reduction)in the reaction process with Hg.Results indicated that HAs were able to reduce Hg abiotically.Higher initial Hg,higher HA concentrations and either high(8.1)or low(3.6)solution pH decreased the HA reduction capacity.In addition,Hg°production rates increased with increasing temperature,and the same trend was observed with light exposure.Humic acids added as an aqueous solution resulted in significantly greater Hg°production than addition as a bulk solid.Finally,the Hg reduction rate and capacity varied significantly(P0.05)with HAs from different sources.These findings helped to explain why HAs showed different dominant characteristics(e.g.complexation or reduction)in the reaction process with Hg,and evidentially demonstrated the existence of a possible pathway of Hg~(2+)reduction,which indicated that humic substances in natural environments,especially in water bodies,could act either as a sink or a source for Hg.     

Influence of fertilizers applied to a paddy-upland rotation on characteristics of soil organic carbon and humic acids

The qualitative and quantitative characteristics of soil organic carbon (SOC) and related humic acids (HAs) extracted from the soils of field plots were investigated after 8 years of annual paddy (Oryza sativa L.) and upland maize (Zea mays L.) rotation with various fertilizations. Seven fertilization treatments were selected: Ck (no inputs); Chem (chemical fertilizer of NPK); Comp (swine compost); Comp + 33% of Chem N rate; Comp + 67% of Chem N rate; GM (legume green manure) + 33% of Chem N rate; and peat + 33% of Chem N rate. Organic and inorganic nitrogen inputs of six treatments were equivalent with respect of nitrogen content, but Comp, GM, and peat treatments were complemented with various amounts of inorganic N. After harvest of the eighth paddy crop, surface soil samples collected from the plots were subjected to soil characterizations and extraction of humic substances, which were used for chemical, spectroscopic (FTIR, 13C NMR, ESR, X-ray diffractometry), delta13C, and 14C dating analyses. The yields of HAs extracted from the seven treatments were significantly different. Treatment containing persistent organic compound such as the peat + 33% N treatment increased the humification process in topsoils and produced higher yield of HA. Spectroscopic analyses revealed that fertilization treatments changed the functional groups, alkyl C, crystalline characteristics, and delta13C ratios of HAs and turnover rate of SOC considerably. The SOC of the peat + 33% N treatment had the highest mean residence time of 3100 years. Various fertilizer treatments are correlated with turnover rate of SOC and related HAs, which are associated with concerned carbon sequestration as well as mitigation of CO2 emission in the soil environment.     

Phenanthrene sorption by compost humic acids

Nonlinear isotherms were observed for sorption of polycyclic aromatic hydrocarbons (PAHs) to humic materials, but the exact sorption mechanism is not clearly understood. This study aimed to investigate the sorption of PAHs by compost humic materials. Humic acids (HAs) were progressively extracted from two compost samples by a 0.1-M sodium pyrophosphate solution. Sorption of phenanthrene by the extracted HAs was studied with a batch equilibration technique. Competitive sorption between pyrene and phenanthrene in the HAs was also examined. Elemental analysis and solid-state ¹³C NMR were used to characterize HAs. All sorption isotherms were nonlinear although these samples contained little black carbons if any. Isotherm linearity increased with increasing number of extractions. Isotherm nonlinearity was negatively related to HA aliphaticity. Addition of pyrene to the phenanthrene-HA system increased isotherm linearity. Competition between phenanthrene and pyrene sorption was more pronounced in the first fraction of HAs with a higher content of aromatic moieties. This study showed that humic materials alone could lead to nonideal sorption for PAHs.     

Effect of pH on binding of mutagenic heterocyclic amines by the natural biopolymer poly(gamma-glutamic acid)

Poly(gamma-glutamic acid) (gamma-PGA), a nontoxic and biodegradable macropolymer, was evaluated for its efficiency in binding three mutagenic heterocyclic amines (HAs), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-p-2), as affected by pH in a batch mode. The maximum HA sorption was attained for pH 3-7 and decreased sharply for pH less than 3. Binding isotherms obtained at pH 2.5 and 5.5 showed different isotherm shapes that belong to S and L types, respectively. The isotherm data at pH 2.5 were well described by a linear form of the Langmuir equation, while at pH 5.5 it showed two distinct curves, which were precisely fitted as multiple Langmuir curves. The deviation of linearity in Scatchard plot proved the multisite HA sorption. The Brunauer-Emmett-Teller equation also fitted better to isotherm data at pH 5.5, suggesting a multisite sorption caused by multimolecular HA layers on gamma-PGA. High HA sorption levels of 1250, 667, and 1429 mg/g at pH 2.5 and 1429, 909, and 1667 mg/g at pH 5.5 were observed for MeIQ, 4,8-DiMeIQx, and Trp-p-2, respectively. Among the HAs studied, the sorption capacity correlated directly with hydrophobicity of HAs and inversely with the number of methyl groups in HA molecules. The plausible binding mechanism of HAs on gamma-PGA may include a combination of hydrophobic, hydrogen-bonding, ionic, and dipole-dipole interactions.     

Nitric Acid Oxidation for Improvement of a Chinese Lignite as Soil Conditioner

Oxidation is known commonly to enhance humic acid (HAs) contents of coal, but in China, most humic substances are used directly as soil conditioners or applied in combination with fertilizers without oxidation. Therefore, we investigated the impact of nitric acid (HNO₃) oxidation on the characteristics of HAs derived from a Chinese lignite. The results showed that total HA content was increased by HNO₃ oxidation, thus consequently increasing its cation exchange capacity and moderate humification. Besides, HAs extracted from oxidized lignite were richer in oxygen-containing functional groups with smaller molecular size than natural lignite. Compared with natural lignite, retention capacities of nitrogen and potassium by oxidized lignite were significantly greater. However, phosphorus-retention capacity was decreased to near zero, which might enhance the availability of phosphorus in soil. In general, optimum HNO₃ oxidation had favorable effects on lignite and improved its characteristics for use as a soil conditioner.     

Anticlastogenic, antitoxic and sorption effects of humic substances on the mutagen maleic hydrazide tested in leguminous plants

The potential anticlastogenic and antitoxic effects of a soil humic acid (HA), a peat HA and a peat fulvic acid (FA) on the mutagen maleic hydrazide (MH) have been investigated in two legume species, Vicia faba and Pisum sativum. Both HAs and FA were tested at two different concentrations, 20 and 200 mg l^?1, either alone or after 24‐hour interaction with 10 mg l^?1 of MH before addition to the legume seeds. Anticlastogenicity, i.e. an antimutagenic action defined as the capacity for minimizing chromosome breakages, was evaluated by counting both micronuclei (MN) and aberrant anatelophases (AAT) in root‐tip cells. Length and dry weight of the seedling primary root were measured to test the antitoxic activity of HA and FA on MH. The possible occurrence and extent of adsorption or desorption of MH onto or from HA were also investigated. The two species responded differently to the anticlastogenic tests, with V. faba showing a greater number of MN and AAT anomalies than P. sativum. Peat HA and FA exhibited anticlastogenic and antitoxic activities of similar intensity and greater than those of soil HA. The adsorption capacity of both HAs for MH was small, thus suggesting that adsorption is not a major mechanism responsible for the reduction of clastogenicity and antitoxicity of MH by HA.     

Complexation of mercury(II) ions with humic acids in tundra soils

The interaction mechanisms of mercury(II) ions with preparations of humic acids (HAs) isolated from organic horizons of surface-gleyed soils (Haplic Stagnosol (Gelic, Siltic)) of shrub tundra and hydromorphic peat gley soils (Histic Cryosol (Reductaquic, Siltic)) of moss-lichen tundra have been studied. The particular features of the interactions between the mercury(II) ions and the HAs are related to the molecular structure of the HAs, the mercury concentration range, and the environmental parameters. The fixation of mercury(II) ions into stable coordination compounds is most efficient in the pH range of 2.5–3.5. At the element concentrations below 0.50 μmol/dm³, the main complexing sites of HAs are their peripheral aminoacid functional groups. Pyrocatechol, salicylate, and phenolic groups from the nuclear moiety of molecules interact in the concentration range of 0.0005–0.50 mmol/dm³; the physical sorption of mercury hydroxo complexes by the surface of HAs is the main process occurring in the system.     

Paramagnetic Properties of Humic Substances in Taiga and Tundra Soils of the European Northeast of Russia

The study of paramagnetic activity of humic substances in taiga and tundra soils of the Komi Republic and the assessment of the influence of soil hydromorphism on concentrations of free radicals in the structure of humic acids (HAs) and fulvic acids (FAs) have been performed. The concentration of free radicals in HA specimens was up to 11 times higher than that in FA specimens due to a higher content of aromatic and other condensed structures in HA molecules. This fact attests to the high capacity of HAs to polymerization and complexation reactions with participation of radicals. The average value of g-factor is higher for FA specimens than for HA specimens, which attests to a greater electron density shift of unpaired electron to oxygen atom in the structure of FAs because of its spin-orbital interaction with oxygen-containing functional groups, the concentrations of which are significantly higher in FAs than in HAs. An increase in the concentration of free radicals in the molecular structure of HAs is observed in taiga soils with an increase in the degree of their hydromorphism (from automorphic to semihydromorphic soils), which is related to the biohydrothermal conditions of humus formation in bog-podzolic soils with retarded biochemical processes and low degree of plant litter humification. As a result, HAs with the high content of free radicals in their structure are formed. An opposite situation is observed for HAs in tundra soils with a decrease in the content of unpaired electrons under conditions of the increased hydromorphism. The difference in the character of changes in the paramagnetic activity of HAs in taiga and tundra soils with different degrees of hydromorphism may be related to different natures of plant residues participating in humification processes. A tendency for a decrease in the paramagnetic activity in both HAs and FAs from the south to the north is observed, which may be related to a general decrease in the content of poly-conjugated systems in the structure of humic substances in tundra soils.     

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.