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 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.     

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.     

Cobalt,copper, and manganese adsorption by aluminium and iron oxides and humic acid

Abstract

Adsorption of cobalt (Co), copper (Cu), and manganese (Mn) by synthetic aluminium oxide, ferrihydrite, goethite, extracted humic acid, and a sandy soil sample were determined as a function of metals concentration (0–1.2 mM) and pH (3.8–8.2). For each pH and adsorbent, the Langmuir adsorption maximum (adsorption capacity) was calculated. The position of the adsorption curves for Co, Cu, and Mn as a function of pH has been shown to be related to the first hydrolysis constant of the cations in solution (pK₁). The sequence of preference of the three metals to the studied adsorbents decreased in order Cu >> Co > Mn. The results obtained from this study showed that the Co, Cu, and Mn adsorption characteristics of soils are probably controlled to large extent by their organic matter and oxides contents.     

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 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     

Phosphate adsorption on uncoated and humic acid-coated iron oxides

Purpose

The phosphate adsorption on natural adsorbents is of particular importance in regulating the transport and bioavailability of phosphates in environmental system. In soils, oxides are often associated with organic matter and form mineral-organic complexes. The aim of the present paper was to investigate the mechanisms of phosphate adsorption on these complexes.

Materials and methods

Phosphate adsorption on uncoated and humic acid (HA)-coated iron oxide complexes was investigated at different ionic strengths and pH by isotherm experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.

Results and discussion

Results showed that HA-coated iron oxide complexes caused a decrease in the specific surface area (SSA) and the isoelectric point (IEP) of oxides. Phosphate adsorption on iron oxides was insensitive to changes of ionic strength, while it increased on the complexes with increasing ionic strength. The presence of HA decreased the maximum adsorption and the affinity of phosphate on the complexes. The zeta potential of phosphate-bound iron oxides linearly reduced with the increment of phosphate surface coverage, while the zeta potential of complexes with adsorbed phosphate kept at the same level. ATR-FTIR analysis suggested the formation of phosphate-metal complexation. The presence of HA promotes the formation of the monodentate phosphate complexes at pH 4.5 and significantly influenced phosphate species at pH 8.5.

Conclusions

The amount of phosphate adsorbed was reduced, and the phosphate speciation was also influenced when phosphate was adsorbed on HA-coated iron oxide complexes compared with phosphate adsorption on pure goethite and hematite.

     

Adsorption mechanisms of nicotine on humic acid and clay humic acid complex

The adsorption isotherm of nicotine on humic acid - surface was found to be multiphase according to the applied concentrations of nicotine. Each phase was characterized by its own change in free energy and represented a mechanism of interaction. At low concentrations, the isotherm showed a H-curve of high affinity between both reactants as a result of protonation of the pyrrolidine nitrogen atom of nicotine, the second phase was that of flat adsorption in which the nitrogen atoms of nicotine acted as electron donor. The third phase was that of the rearrangement of the nicotine from flat to side adsorption on the humic surface, after which the phase of multilayer formation followed. The adsorption on the surface of the humic acid-clay complex showed no distinct phases but an isotherm looks like the L-type, although it could not verify Langmuir's equation. Probably the isotherm was the resultant of two mechanisms one due to the adsorption of the humic acid part and the other due to the clay part in the complex. Comparison of the constants of Freundlich's equation showed that the capacity of the adsorption humic surface was greater than that of the complex.     

Poorly ordered hydrous Fe oxides, colloidal dispersion and soil aggregation. I. Effect of humic macromolecules on surface and colloidal properties of Fe (III) polycations

Model humic macromolecules, obtained by auto-oxidation of the catechol-glycine system, were adsorbed on poorly ordered hydrous iron oxides, Fe(OH)_2.8. The pH was nearly constant at c. 6 in order to simulate natural soil and river environments. When the amount of organic carbon adsorbed on 1 g of poorly ordered ferrihydrite increased from 0 to 70 mg, the ligand OH exchange was very small, but the zero point of charge of suspensions progressively shifted from 7.3 to 5.6, and net surface charge, which was initially positive, progressively became negative, suggesting an adsorption mechanism with positive charge neutralization. Consequently, colloidal stability changed from rapid to slow flocculation. The ferrihydrite-haematite exothermic reaction partially shifted from 400°C to higher temperatures as a function of adsorbed organic matter, and ferrihydrite solubility progressively increased by formation of soluble iron-organic complexes. These results were explained more satisfactorily by the concept of colloidal organ- mineral association than by organic coatings on surfaces.     

硫酸铵与腐植酸及改性腐植酸配施对氨挥发的影响

通过室内连续培养试验,研究了石灰性褐土中硫酸铵与不同用量及改性腐植酸（HA）配施对氨挥发及氮素形态转化的影响。试验设置6个腐植酸用量处理,分别为CKⅠ、ASNⅠ（硫酸铵Ⅰ）、ASNⅠ+5%HA、ASNⅠ+10%HA、ASNⅠ+15%HA、ASNⅠ+20%HA(5%、10%、15%、20%为腐植酸占硫酸铵施用量的百分比)和6个改性腐植酸处理,分别为CKⅡ、ASNⅡ（硫酸铵Ⅱ）、ASNⅡ+W0、ASNⅡ+W400、ASNⅡ+W600、ASNⅡ+OHA(W0、W400、W600分别为含水量0%、400%、600%的改性腐植酸,OHA为干燥+过氧化氢氧化处理的改性腐植酸)。结果表明：培养32 d后,与单施硫酸铵处理（ASNⅠ）相比,ASNⅠ+10%HA～ASNⅠ+20%HA处理可以抑制氨挥发,其中ASNⅠ+20%HA处理抑制效果最佳,日平均氨挥发速率降幅为5.07%。腐植酸经不同改性处理后,按硫酸铵用量的20%与硫酸铵配施培养32 d后,与单施硫酸铵处理（ASNⅡ）相比,ASNⅡ+W400与ASNⅡ+W600处理加剧了土壤氨挥发,土壤氨挥发总量分别增加了50.69%和57.64%;ASNⅡ+O...     

Sorption of 2,2′-bipyridine on clays and oxides

The sorption of 2,2′-bipyridine onto some clays and oxides was studied as a function of concentration, pH, time and the exchangeable cation of the clays. The reaction was found to include both physical, cation exchange, and chemisorption, was irreversible and multilayered at high concentrations. The sorption was also pH dependent attaining a maximum in the pH range 4.5 to 5.5 depending on the sorbent; this dependence was attributed to chemisorption. The maximum in sorption was observed to take place above the pH value where the molecular form is the only bipyridine species present in solution thus indicating its preference by the sorbents over the positive species. Chemisorption, ion exchange against metalic cations and molecular aggregation on the surface are the factors thought to be responsible for the desorption of bipyridine at pH values beyond that at the maximum sorption.     

Poorly ordered hydrous Fe oxides, colloidal dispersion and soil aggregation. II. Modification of silty soil aggregation with Fe(III) polycations and model humic macromolecules

Poorly ordered ferrihydrites, more or less associated with synthetic humic macro-molecules, were added to a poorly structured temperate silty soil. Manipulation of the net soil charge through these additions was measured by potentiometric titration and cation exchange capacity. The consequences of anchoring positively charged Fe hydrous oxides on negative permanent clay surface charges were studied. Both cementation and aggregate water-stability increased with increase in adsorbed iron. The aggregation process was studied by using micromorphology and ultramicromorphology, water retention curves, mercury porosimetry and a fractal approach. Aggregate water-stability was studied when the soils were air-dried, with some irreversible aggregation, and oven-dried or wetted from – 1.5 MPa to – 1 kPa thereafter. Soils with added Fe(III) polycation–humic macro-molecule associations were less positively charged, less cemented and less stable than soils amended with Fe(III) polycations alone. The effect of these treatments on slaking is discussed.     

Sorption of 2,4,6-trichlorophenol in model humic acid-clay systems

Humic acids and clays are important soil components that influence the sorption and desorption of organic contaminants; however, it is unclear how humic acids influence the sorption of organic contaminants onto clays and their subsequent desorption. Sorption and desorption of 2,4,6-trichlorophenol (2,4,6-TCP) by and from humic acid-modified K(+)- and Ca(2+)-montmorillonite and -illite were compared with unmodified clays using batch equilibration methods. Commercial humic acid and the humic acid extracted from forest soil were employed in this experiment. The adsorbed amount of 2,4,6-TCP by commercial humic acid was almost twice as large as that adsorbed by the extracted soil humic acid. More 2,4,6-TCP was sorbed onto K(+)- and Ca(2+)-illite than onto K(+)- and Ca(2+)-montmorillonite. K(+) clays were more effective in adsorbing 2,4,6-TCP than Ca(2+) clays. Sorption of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite and -illite increased as compared with unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-illite increased remarkably as compared with the unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite increased slightly in contrast to unmodified montmorillonites. By comparing sorption and desorption results, we observed hysteresis for all sorbents including humic acids, clays, and humic acid-modified clays. Sorption nonlinearity and hysteresis were dependent on the structure of humic acids. Higher aromaticity of humic acids resulted in greater sorption nonlinearity and desorption hysteresis. In addition, sorption capacity (K(f)') was positively correlated with the humic acid content of the sorbents. These results show that modification of humic acids on clays can not only increase the adsorption ability of clays but also affect the sorption nonlinearity of 2,4,6-TCP, and the desorption hysteresis was probably due to the structural characteristics of humic acids.     

Effects of humic acids on the growth of bacteria

The influence of humic acids of different origins on the growth of bacterial cultures of different taxa isolated from the soil and the digestive tracts of earthworms (Aporrectodea caliginosa)—habitats with contrasting conditions—was studied. More than half of the soil and intestinal isolates from the 170 tested strains grew on the humic acid of brown coal as the only carbon source. The specific growth rate of the bacteria isolated from the intestines of the earthworms was higher than that of the soil bacteria. The use of humic acids by intestinal bacteria confirms the possibility of symbiotic digestion by earthworms with the participation of bacterial symbionts. Humic acids at a concentration of 0.1 g/l stimulated the growth of the soil and intestinal bacteria strains (66 strains out of 161) on Czapek’s medium with glucose (1 g/l), probably, acting as a regulator of the cell metabolism. On the medium with the humic acid, the intestinal bacteria grew faster than the soil isolates did. The most active growth of the intestinal isolates was observed by Paenibacillus sp., Pseudomonas putida, Delftia acidovorans, Microbacterium terregens, and Aeromonas sp.; among the soil ones were the representatives of the Pseudomonas genus. A response of the bacteria to the influence of humic acids was shown at the strain level using the example of Pseudomonas representatives. The Flexom humin preparation stimulated the growth of the hydrocarbon-oxidizing Acinetobacter sp. bacteria. This effect can be used for creating a new compound with the elevated activity of bacteria that are destroyers of oil and oil products.     

矿物源腐植酸肥料中可溶性腐植酸快速检测方法研究

采用分光光度法检测矿物源腐植酸肥料中可溶性腐植酸含量,讨论在检测过程中样品的称取质量、离心条件、重铬酸钾浓度以及氧化时间对检测结果的影响.进行了方法验证,计算出方法检出限为4.27％,相对标准偏差为2.1％～11.6％,加标回收率为95％～106％.     

Deformation of humic acid by acid treatment

In our previous report (1) we had proposed the method to fractionate humic acid into three parts using organic solvents, and had advocated the new theory on the process of humification in volcanic ash soils from the results of the fractionation.     

Viscosimetric characteristics of humic acid

One of the authors, KUMADA (I), has proposed a new classification of humic acids based on their colour and spectral characteristics in the visible and ultra-violet regions. Humic acids can be grouped into four major types by this procedure (A, B, Rp and P types) and evidence for a classification diagram based on the values ΔlogK and RF has recently been presented (2). It is clearly important that the usefulness of this new classification should be investigated by considering other chemical and physical properties of humic acids.     

Studies on the physiological effect of humic acid

Many investigations have been reported on the physiological mechanisms of iron chlorosis induced by manganese. And several hypotheses such as “Oxidation reduction potential theory” (1) or “Chelation theory” (2) have been proposed concerning the interference of manganese on the absorption and translocation of iron in plants. However, from a comparative check of experimental results which had been done on various kinds of heavy metals inducing iron chlorosis, the authors have found that the degree of iron chlorosis did not strictly coincide with the order of oxidation reduction potential or stability constant of these chelate compounds. Also, CHINO et al. (3,4) reported that iron chlorosis induced by heavy metals did not coincide with the order of stability constant of these metal chelate compounds, but depended upon their inhibiting action on plant growth and iron absorption. But ASO et al. (5) reported previously that using root separating method they obtained higher iron absorption and better recovery of iron chlorosis of barley plants when iron and nitro-humic acid or EDTA were added simultaneously than when iron only was added. From these results, it was considered that the distribution and chemical form of iron in plants were affected by chelating action of nitro-humic acid or EDTA.     

Some aspects on the nature of humic acid

For the extraction of humic acid from soils, solutions of sodium hydroxide or neutral sodium salts of inorganic and organic acids such as sodium fluoride, sodium oxalate and sodium pyrophosphate have been used most generally.