Sorption of antimony species by humic acid

The retention of antimony (a potential toxin) in polluted soils or waterway sediments can involve interaction with several component phases. One of these, humic acid, has been found to adsorb antimony (III) from solutions of Sb(OH)₃ or potassium antimonyl tartrate (C₈H₄K₂Sb₂O₁₂) in accordance with Langmuir type isotherms. Using Sb(OH)₃ solutions (initial Sb levels < 10 μM) the bonding constant value (at pH 4) was 6 × 10⁵, with a calculated saturation capacity of 23 μmol g^?1. In the antimonyl tartrate systems (initial Sb levels 0.5 to 75 μM) the bonding constant value for the sorbed species was 1.6 × 10⁵ and the saturation capacity 53 μmol g^?1. Addition of small amounts of HCl or NaOH (to vary the pH between 3.1 and 5.4) had little effect on the amount sorbed from KSbT solutions but with Sb(OH)₃ solutions uptake was reduced (by about 15%). In the presence of NaCl (0.5 or 0.05M) Sb uptake increased (by about 15%). Antimony (V) (introduced as KSb (OH)₆) was not sorbed from solutions < 10 μM in this salt. Using more concentrated solutions, uptake gradually increased, reaching a plateau value of around 8 μmol g^?1 with solutions initially 50 or 75 μM.     

Sorption of L-methionine-sulphoximine on humic acids and clay minerals

 The sorption of L-methionine-sulphoximine (MSX) on soil-extracted humic fractions (MW>20,000 Da), and mined clays (kaolinite and montmorillonite) was studied by a reversed-phase high-performance liquid chromatography method. The molecule, acting as an inhibitor of glutamine synthetase activity, was recently used in soil incubation assays for the determination of gross rates of N mineralization. Equilibrium data of MSX adsorbed on humic fractions and clay minerals were described by both the Freundlich and Langmuir sorption isotherms. It was observed that humic fractions were more effective than mined clay minerals in removing MSX from water. Most isotherms were of Langmuir type, indicating a higher affinity of MSX for sorbing sites which become increasingly saturated at higher equilibrium concentrations. Analysis of Langmuir empirical constants revealed that different adsorbing mechanisms took place. Results showed that when MSX is applied in soil incubation assays, sorption of MSX on soil colloids considerably reduces the availability of the inhibitor to target microorganisms, and renders the method unsuitable for the determination of the gross rate of N mineralization, especially when high levels of both organic matter and clay minerals are present in the soil. Received: 19 April 1999     

Sorption of cadmium by complexes of kaolinite with humic acid

Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.     

Sorption of chlorpyrifos to selected minerals and the effect of humic acid

Sorption of chlorpyrifos (CPF) from 2.85 microM (1 mg/L) aqueous solutions in 0.01 M NaCl to montmorillonite, kaolinite, and gibbsite was investigated at 25 degrees C. Uptake of CPF by kaolinite and gibbsite was generally <10%, with pH having at most a small effect. Sorption to montmorillonite was significantly greater, with approximately 50% of the initial CPF being removed from solution below pH 5. Above pH 5 the sorption decreased to about 30%. About 70% of CPF was sorbed to kaolinite and gibbsite after 30 min, whereas on montmorillonite only 50% sorbed in an initial rapid uptake (approximately 30 min) followed by slower sorption, with a maximum achieved by 24 h. Although CPF desorbed completely from kaolinite in methanol, only about two-thirds was desorbed from montmorillonite. CPF has only a weak affinity for the surfaces of kaolinite and gibbsite. In the case of montmorillonite, sorption is significantly stronger and may involve a combination of sorption to external surfaces and diffusion into microporous regions. At pH >6 increased negative surface charge results in a lower affinity of CPF for the external surface. In the presence of 50 mg/L humic acid (HA) the amount of CPF sorbed on gibbsite and kaolinite was 3-4 times greater than that in the binary systems. The HA forms an organic coating on the mineral surface, providing a more hydrophobic environment, leading to enhanced CPF uptake. The HA coating on montmorillonite may reduce access of CPF to microporous regions, with CPF tending to accumulate within the HA coating.     

Sorption of humic acid on Fe oxides,bacteria, and Fe oxide-bacteria composites

Purpose

Sorption of humic substances on other soil components plays an important role in controlling their function and fate in soil. Sorption of humic substances by individual soil components has been studied extensively. However, few studies reported the sorption characteristic of humic substances on composites of soil components. This study aimed to investigate the sorption characteristics of humic acid on Fe oxide-bacteria composites and improve the understanding on the interaction among humic substance Fe oxide bacteria in soil.

Materials and methods

Humic acid was purchased from Sigma-Aldrich and was purified. Hematite and ferrihydrite were synthesized in the lab. Bacillus subtilis and Pseudomonas putida were cultivated in Luria-Broth medium and harvested at stationary growth phase. Batch sorption experiments were carried out at pH 5.0. Various amounts of humic acid were mixed with 20 mg of Fe oxide, bacteria, or Fe oxide-bacteria composite (oxide to bacteria of 1:1) in 10 mL of KCl (0.02 mol L^?1) to construct sorption isotherms. The effects of phosphate concentration and addition order among humic acid, Fe oxide, bacteria on the sorption of humic acid were also studied. The sorption of humic acid was calculated by the difference between the amount of humic acid added initially and that remained in the supernatant.

Results and discussion

The maximum sorption of humic acid on hematite, ferrihydrite, B. subtilis and P. putida was 73.2, 153.5, 69.1, and 56.7 mg C g^?1, respectively. The maximum sorption of humic acid on examined Fe oxide-bacteria composite was 28.2–57.2 % less than the predicted values, implying that the sorption of humic acid was reduced by the interaction between Fe oxides and bacteria. The presence of phosphate exerted negligible influence on the sorption of humic acid on bacteria while it inhibited the sorption of humic acid on Fe oxides. On Fe oxide-bacteria composites, inhibiting influences followed by promoting or weak inhibiting effects of phosphate with increasing concentration on the sorption of humic acid were found.

Conclusions

The interaction between Fe oxides and bacteria reduced the sorption of humic acid; moreover, the reduction was greater by the interaction of bacteria with ferrihydrite than that with hematite. Phosphate exerted negligible and inhibiting influence on the sorption of humic acid by bacteria and Fe oxides, respectively. On Fe oxide-bacteria composites, humic acid sorption was initially inhibited and then promoted or weakly inhibited by phosphate with increasing concentration.     

Bound amino acids in humic acids from arable cropping systems

We investigated the varying concentrations of bound amino acids in humic acids (HA) extracted from soils under both crop rotation and continuous cropping of rye. The experiment was created in 1957. Since then, winter rye had been grown continuously and also the sequence of the 7 yr rotation had been started: potato, spring barley, alfalfa, alfalfa, oil seed rape, winter rye, and winter rye. Soils were fertilized with NPK and manure. Continuous cropping of rye increased total acidity of soils and the contents of carboxylic and phenolic groups in HA. The total amounts of the bound amino acids in HA from soils under crop rotation were higher than from continuous cropping of rye. Fertilization with NPK increased the contents of bound amino acids more than manure. Neutral amino acids dominated in all samples of HA, and basic amino acids had the lowest concentrations. In both types of cultivation, glutamic acids, glycine, alanine, valine, and lysine dominated. The proline contents in HA from continuous rye cropping were higher than in HA from soils under crop rotation. The concentrations of β‐alanine and lysine were higher in HA from crop rotation indicating a higher microbial biomass since these compounds are typical constituents of bacteria cell walls.     

Caesium sorption—desorption in clay—humic acid systems

Soaking for 7 d with 0.05 M NaCl resulted in less caesium being sorbed by bentonite and kaolinite, but more by illite, compared to soaking for 2 d prior to addition of Cs. Overall the amount of Cs sorbed by the three clays was in the order bentonite > illite > kaolinite. Addition of humic acid to the clays depressed the sorption of Cs by all three clays, with illite showing the greatest effect. Desorption of added Cs was not totally reversible. The presence of humic acid resulted in an enhanced desorption of Cs from bentonite and to a lesser extent kaolinite. This enhanced desorption in the presence of humic acid was not seen for illite. The order of Cs retention following desorption for both clay and clay/ humic-acid mixtures was illite > bentonite > kaolinite. A single K_d value could not describe the whole isotherm, but individual values were calculated at different Cs concentrations to cover the range of the isotherm. K_d values for desorption were higher than the corresponding K_d for sorption. For both sorption and desorption, the presence of humic acid resulted in lower K_d values than in its absence.     

A model for a type humic acid

In the preceding papers (1,2,3,4), the author studied some chemical properties of soil humic acids, and compared various so-called artificial humic acids with soil humic acids in respect to their absorption spectra and stabilities. According to these experimental results, it is Presumed that soil humic acids, especially A type, must contain not only benzene ring, but also condensed aromatic rings as their structural units.     

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.     

Preparation and characterization of model humic polymers containing organic phosphorus

The nature of organic P in soil organic matter was studied by evaluating the incorporation of serine, phosphoserine, ethanolamine, phosphoethanolamine and glycerophosphate into model humic polymers prepared by chemical oxidation of polyphenols. Elemental and functional group analysis indicated that the composition of model humic polymers ranged as follows: organic C, 50.6–56.8%; total acidity, 7.86–11.87m-equiv g^?1; carboxyl, 1.42–2.00 m-equiv g^?1; total hydroxyl, 6.79-10.0 m-equiv g^?1; ash, 6.4–13.9%; E₄/E₆ ratio, 5.34–6.19; organic N, 0.70–1.65% and organic P, 0.254–0.942%. These values are within the ranges reported for soil humic substances. The only non-phenolic compounds incorporated into model humic polymers were those containing free amino groups. The P content of model polymers was not increased by the presence of KH₂PO₄, glycerophosphate, serine or ethanolamine whereas phosphoserine and phosphoethanolamine resulted in model polymers containing 0.254 and 0.942% P, respectively. Further characterization studies of the model polymer containing phosphoethanolamine (HA-PE) showed that most of the C (83.2%), N (79.8%) and P (75.3%) was in the humic acid fraction. Gel filtration of HA-PE showed that 0.5% of the polymer was present in high molecular weight (mol. wt) components (mol. wt > 100,000) and 74.8% of the polymer was in two components of mol. wt 10,000–50,000. The majority of the organic P in HA-PE was associated with the medium molecular weight fractions (79.2%) while 16.8% of the P was associated with materials possessing mol. wt < 10,000. Attempts to demonstrate the presence of organic P functional groups contained in HA-PE by infrared spectroscopy was limited by the relatively small amounts of organic P incorporated into the model humic polymers. The results obtained show that a portion of the unidentified organic P in soil humic substances may arise from the incorporation of organic compounds containing both amino and phosphate ester functional groups during oxidative polymerization of polyphenols.     

Stability and mineralization of organic phosphorus incorporated into model humic polymers

The stability of the phosphate ester linkage in phosphoserine (PS) and phosphoethanolamine (PE) was evaluated after incorporation of these compounds into model humic polymers. Humic polymers prepared by oxidation of a mixture of substituted phenols in the presence of either PS or PE resulted in model humic materials containing from 0.25 to 0.94% P, values within the range found for organic P in natural soil humic materials. The organic P contained in model humic polymers was resistant to hydrolysis with 1 n HC1 and 1 n NaOH and resistance of the P ester to hydrolysis with 6 n HCl was increased through incorporation into model humic polymers. Organic P in model humic polymers was also stabilized towards hydrolysis with acid and alkaline phosphomonoesterases. Less than 11% of the organic P in polymers containing PS and PE was hydrolyzed by acid or alkaline phosphatase. The incorporation of PE into a model humic polymer markedly reduced the amount of P mineralized during incubation in soil when compared to P mineralized in soils treated with PE. For all environmental conditions imposed during soil incubations (i.e. pH, aeration, temperature), only 20% of the P in model humic polymer containing PE was released during a 16-week period. In contrast, > 60% of the P in either PS and PE added individually to soils or PS and PE intimately mixed with preformed model humic polymer and then added to soils was released during the initial 7 days of soil incubation. The results suggest that a portion of the unidentified organic P in soils may arise from the incorporation of organic compounds containing both amine and phosphate ester functional groups into humic materials and that the organic P thus formed is resistant to both chemical and enzymatic hydrolysis.     

A normal distribution model for the titration curves of humic acids

Titration curves of humic acids extracted from different sources were fitted using a continuous distribution model. The mean pK values and distribution variances were calculated in the fitting procedure and they proved to be useful in differentiation of the humic acids under examination.     

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.     

Sorption and desorption of triadimefon by soils and model soil colloids

Sorption-desorption of the azole fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2, 4-triazol-1-yl)-2-butanone] on eight soils and a series of single, binary, and ternary model soil colloids was determined using the batch equilibration technique. Regression analysis between Freundlich sorption coefficients (K(f)) and soil properties suggested that both clay and organic C (OC) were important in triadimefon sorption by soils, with increasing importance of clay for soils with high clay and relatively low OC contents. Triadimefon sorption coefficients on soil were not significantly affected by the concentration of electrolyte or the presence of soluble soil material in solution, but they were highly dependent on the soil:solution ratio due to the nonlinearity of triadimefon sorption on soil. Freundlich sorption isotherms slopes were very similar for all soils (0.75 +/- 0.02). Desorption did not greatly depend on the concentration at which it was determined and showed higher hysteresis for more sorptive soils. Results of triadimefon sorption on model sorbents supported that both humic acid and montmorillonite-type clay constituents contribute to triadimefon retention by soil colloids.     

Photochemistry of imidacloprid in model systems

The photochemical behavior of the neonicotinoid insecticide imidacloprid was studied with regard to different chemical environments. Different model solvents simulated the structure moieties mainly occurring in waxes and cutin of the plant cuticle. Cyclohexane and cyclohexene substituted saturated and unsaturated hydrocarbon chains, whereas ethanol and 2-propanol were models for primary and secondary alcohol groups of cuticular components. After 5 h of irradiation, imidacloprid was completely degraded in all solvents. With 88-96 mol% 1-[(6-chloropyridin-3-yl)methyl]imidazolidin-2-imine was formed as the main product, whereas 1-[(6-chloropyridin-3-yl)methyl]imidazolidin-2-one was identified as minor product in the range 4-6 mol%. By contrast, besides the photoproducts formed in organic solvents, irradiation of the solid imidacloprid on a glass surface delivered a complex variety of unidentified photoproducts. The nucleophilic addition reaction of the main photoproduct, 1-[(6-chloropyridin-3-yl)methyl]imidazolidin-2-imine, with both cyclohexene oxide and methyl 9,10-epoxystearate as model compounds indicates that epoxidized cutin acids are possible reaction partners for the formation of plant cuticle bound residues of imidacloprid, which could explain the reported findings of nonextractable residues of imidacloprid in plants.     

Quantitative aspects of solid-state C-NMR spectra of humic substances from soils of volcanic systems

Cross-Polarisation Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance spectroscopy (CPMAS ¹³C-NMR) represents one of the most powerful tools to investigate soil organic matter (SOM) mainly because of its inherent capacity to provide a semi-quantitative evaluation of carbon distribution. A critical parameter during acquisition of CPMAS ¹³C-NMR spectra is the contact time required to obtain the cross-polarisation between proton and carbon nuclei. The procedure to evaluate the best contact time for the acquisition of a quantitative CPMAS ¹³C-NMR spectrum is to perform Variable Contact Time (VCT) experiments. In this work the structural features of a number of purified humic substances from Italian and Costarican volcanic soils were investigated by CPMAS ¹³C-NMR spectroscopy after having performed preliminary VCT experiments. The VCT experiments showed that the average contact times vary according to the origin and chemical structure of the humic material. The optimal contact times (OCT) for nine humic samples were between 250 and 800 μs These values were different from the time of 1000 μs that is commonly applied as the best average contact time for humic materials. Moreover, by comparing the NMR data to those obtained by elemental analysis (C/H ratio), it appeared that the efficiency of the cross-polarisation between protons and carbons, and hence the contact time, is affected not only by the number of protons, but also by their distribution over the molecules. The evaluation of errors in quantitative estimation of the different carbons revealed that the use of OCT generally reduced by half the loss of signals occurring when the average contact time of 1000 μs is used in CPMAS ¹³C-NMR spectra of humic substances.     

Fate of humic acids isolated from natural humic substances

Composition of humic acids (HA) is a function of plant-derived inputs, degradation processes regulated by microorganisms, organo-mineral interactions and age. Characterization of different origin humic substances is important for evaluation of their contribution to stabile and labile carbon pool in the environment. The relative abundance of chemical components in HA isolated from soils, compost, commercial lignohumates, alginite, acadiane and lignite was studied with aim to quantify content of important biomarkers such as amino acid, lipids and polyphenols. HA were considered as a heterogeneous complex and high concentration of peptides, polyphenols and lipids was determined in acadian-HA to compare with soil-HA. Compost-HA contained much more amino acids to compare with soil-HA samples. Alginite-HA and lignite-HA were similar in biomarkers content to soil-HA. Fourier transform infrared spectroscopy confirmed that chemical composition and functional groups content differs with the origin, humification degree and the age of studied samples. Soil-HA are typically composed of a variety of ?OH, COOH?, C–O, C–H₂, (aliphatic and aromatic) groups, quinines, lignin fragments, polysaccharide, monosaccharide and proteins fragments, which are linked together by ?O?, ?NH?, ?H=, >C=O, metal ions and –S? groups. ¹³C NMR spectroscopy showed that aromatic carbon content was the highest in lignite-HA and soil-HA.     

Haze formation in model beer systems

The interaction of a haze-active protein (gliadin) and a haze-active polyphenol (tannic acid) was studied in a model beer system in order to investigate the principle mechanisms of haze formation at low temperatures. Low concentrations (g/L) of tannic acid, high concentrations of gliadin, and comparatively high temperatures lead to maximum haze values. When considered on a molar basis, the greatest haze levels are displayed at an approximate 1:1 equivalence of polyphenol and protein. The greater part of haze formation was completed within 0.5 h, irrespective of the concentration of gliadin, the concentration of tannic acid, and the temperature of the model solution.