Kinetic aspects of the reduction of mercury ions by humic substances

A combination of a computer controlled titration device with a cold vapour atomic absorption spectrometer was set up to examine the kinetics of the reaction between humic substances and Hg(II). Subsequent injections of Hg(II) into an excess of humic acid produce data about short and long term changes in the reaction velocity of humic substances. This experimental design is suitable for the examination of the effects of pH, reaction time, light and interfering substances like chloride on the formation of elemental mercury. The obtained data agree with data from the literature. With the accumulation of the produced elemental mercury on a gold net it is possible to enhance the sensitivity of the method. This enables examinations at environmental concentrations.     

Flocculation of humic substances with metal ions as followed by capillary zone electrophoresis

Humic and fulvic acids from various sources have been shown to give different electropherograms by capillary zone electrophoresis (CZE), depending on the pH of the electrolyte. This CZE work is extended here through investigations involving the titration of humic and fulvic acids with Fe(III) and Cu(II) cations. As increasing amounts of these cations were added to the humic substances (HUS), flocculation of metal-humic complexes occurred. This is believed to be caused by binding of the metal cations with negative carboxyl and phenolic sites on the HUS, resulting in a decrease of the repulsive forces that keep the HUS in a conformation more suitable for water solubility. The flocculated complexes were separated from the supernatant by centrifugation, and the supernatants were characterized as to total organic carbon (TOC) content, molecular weight (MW) using gel permeation chromatography, and average electrophoretic mobility (AEM) using CZE. The extent of flocculation correlated with both TOC and quantitative CZE measurements. The MW of the HUS remaining in solution actually decreased, presumably because of precipitation of larger molecules as they became insoluble because of reactions with the metals. Humic acids showed total precipitation of TOC with both metals at a concentration equivalent to their measured acidity. CZE demonstrated that certain fulvic acid fractions (low molecular weight phenolic acids) remained in solution even at high metal concentrations. In summary, changes in electrophoretic behavior of the soluble HUS could be related to changes in charge-to-mass ratios (charge densities) of both humic and fulvic acids with increasing metal cation concentration (neutralization). The copper treated HUS showed changes in their electrophoretic behavior even at low metal concentrations before flocculation, whereas the iron treated HUS flocculated uniformally over the range of added iron without significant changes in AEM. Thus these changes in CZE patterns illustrate different specific binding sites of the HUS for each metal.     

Flocculation of humic substances with metal ions as followed by capillary zone electrophoresis

Humic and fulvic acids from various sources have been shown to give different electropherograms by capillary zone electrophoresis (CZE), depending on the pH of the electrolyte. This CZE work is extended here through investigations involving the titration of humic and fulvic acids with Fe(III) and Cu(II) cations. As increasing amounts of these cations were added to the humic substances (HUS), flocculation of metal-humic complexes occurred. This is believed to be caused by binding of the metal cations with negative carboxyl and phenolic sites on the HUS, resulting in a decrease of the repulsive forces that keep the HUS in a conformation more suitable for water solubility. The flocculated complexes were separated from the supernatant by centrifugation, and the supernatants were characterized as to total organic carbon (TOC) content, molecular weight (MW) using gel permeation chromatography, and average electrophoretic mobility (AEM) using CZE. The extent of flocculation correlated with both TOC and quantitative CZE measurements. The MW of the HUS remaining in solution actually decreased, presumably because of precipitation of larger molecules as they became insoluble because of reactions with the metals. Humic acids showed total precipitation of TOC with both metals at a concentration equivalent to their measured acidity. CZE demonstrated that certain fulvic acid fractions (low molecular weight phenolic acids) remained in solution even at high metal concentrations. In summary, changes in electrophoretic behavior of the soluble HUS could be related to changes in charge-to-mass ratios (charge densities) of both humic and fulvic acids with increasing metal cation concentration (neutralization). The copper treated HUS showed changes in their electrophoretic behavior even at low metal concentrations before flocculation, whereas the iron treated HUS flocculated uniformally over the range of added iron without significant changes in AEM. Thus these changes in CZE patterns illustrate different specific binding sites of the HUS for each metal.     

Effect of humic substances on the electrochemical reduction of p -nitrophenol

p-Nitrophenol (PNP) is the main hydrolysis product of methylparathion (MP), one of the most commonly used organophosphate insecticides in the world. Such a product is very toxic for human and animals. Humic substances (HS) are natural recalcitrant organic matter found in soil and waters that have an ability to interact, immobilize, and degrade pesticides. This article presents electroanalytical and UV-Visible studies, conducted to understand the effect of the HS on the PNP reduction process and therefore to understand how the HS can influence PNP degradation in the environment. Electroanalytical results showed that the HS benefit the reduction of the nitro-group of PNP by electrocatalysis. UV-Visible spectra showed that the catalytic effect of HS occurs due to the interection between the PNP and the HS followed by a proton donor mechanism.     

Some theoretical and practical aspects in the separation of humic substances by combined liquid chromatography methods

Permanent need to understand nature, structure and properties of humic substances influences also separation methods that are in a wide scope used for fractionation, characterization and analysis of humic substances (HS). At the first glance techniques based on size-exclusion phenomena are the most useful and utilized for relating elution data to the molecular mass distribution of HS, however, with some limitations and exceptions, respectively, in the structural investigation of HS. The second most abundant separation mechanism is reversed-phase based on weak hydrophobic interactions beneficially combined with the step gradients inducing distinct features in rather featureless analytical signal of HS. Relatively great effort is invested to the developments of immobilized-metal affinity chromatography mimicking chelate-forming properties of HS as ligands in the environment. Surprisingly, relatively less attention is given to the ion-ion interactions based ion-exchange chromatography of HS. Chromatographic separation methods play also an important role in the examination of interactions of HS with pesticides. They allow us to determine binding constants and the other data necessary to predict the mobility of chemical pollutants in the environment. HS is frequently adversely acting in analytical procedures as interfering substance, so more detailed information is desired on manifestation of its numerous properties in analytical procedures. The article topic is covered by the review emphasizing advances in the field done in the period of last 10 years from 2000 till 2010.     

Characterization of humic substances by capillary electrophoresis

Capillary electrophoresis was used for the separation of humic acid (HA) from peat, soil, and vermicompost. The electropherograms show the presence of at least three peaks eluted between 6 and 11 min for all HA. The best analysis resolution was obtained with the use of borate buffers at pH 8.9. The HA analyzed have structural and charge similarity, which increases the difficulty of separation. Therefore, the shape of the peaks is broad and the CE profiles of all HA are similar. It is reasonable to assume that the broad band in the three regions is due to the acidic groups that have a similar structure. By comparing the results obtained for HA extracted from soil, peat, vermicompost, and the commercial sample, HA from peat had the major carbon content.     

Thermofractography of humic substances

Thermofractography (TF) has been applied to humic and fulvic acids from four different soil types. Among the thermal products, 3,5-dihydroxybenzoic acid, catechol, 5-hydroxymethylfurfural, vanillin, phenol, furfural, guaiacol and indole were identified. These are typical fragments from lignins, microbial polyphenols, polysaccharides and proteins.Thermofractography appears to be an effective method for study of humic molecule structures by thermal degradation. Furthermore, it seems promising to differentiate humic acids from distinct soil types and to distinguish between humic and fulvic fractions.

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Zusammenfassung Die Thermofraktographie (TF) wurde zur Analyse von Humin- und Fulvinsäuren aus vier verschiedenen Bodenarten eingesetzt. Unter den Produkten der Thermolyse wurden die 3,5-Dihydroxy-benzoesäure, Brenzkatechin, 5-Hydroxymethyl-furfurol, Vanillin, Phenol, Furfurol, Guaiakol und Indol identifiziert. Diese sind typische Fragmente aus Lignin, mikrobiellen Polyphenolen, Polysacchariden und Proteinen.Die Thermofraktoraphie scheint eine wirksame Methode zum Studium der Struktur des Huminmoleküls durch thermische Zersetzung zu sein. Außerdem scheint sie auch zur Unterscheidung von Huminsäuren aus bestimmten Bodentypen und zur Unterscheidung von Humin- und Fulvinfraktionen geeignet.

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Résumé La thermofractographie (TF) a été appliquée à l'analyse des acides humiques et fulviques de quatre types différents de sols. L'acide 3,5-dihydroxybenzoïque, le pyrocatéchol, le 5-hydroxyméthyl-furfural, la vanilline, le phénol, le furfural, le guaacol et l'indole ont été identifiés parmi les produits de la thermolyse. Tous sont des fragments typiques des lignines, des polyphénols microbiens, des polysaccharides et des protéines.La thermofractographie paraît être une méthode efficace pour l'étude par dégradation thermique de la structure moléculaire des substances humiques. En outre, elle semble intéressante pour différencier les acides humiques dans les types de sols particuliers et pour distinguer les fractions humiques et fulviques.

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F. J. G. V. thanks DAAD (Deutsche Akademischer Austauschdienst) for providing a grant.     

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - A possible process of the mercury cycle in Brazil

The evolution of elemental Hg from its environmental compounds has already been supposed to be an important process within the global mercury cycle. The present study characterizes the abiotic reduction of Hg(II) ions by typical river humic substances (HS) conventionally pre-isolated by the adsorbent XAD 8 from the "Rio Negro" near Manaus, Brazil. For the investigation of this reduction process a special reaction and Hg(0) trapping unit combined with cold-vapor atomic absorption spectrometry (CVAAS) was developed. Preconcentration of traces of mercury(II), if required, was obtained by a home-made FIA system using microcolumns filled with the Hg(II)-selective collector CheliteS(R) (Serva Company). The effect of environmentally relevant parameters such as the pH value, the Hg(II)/HS ratio and the HS concentration on the Hg(II) reduction process was studied as a function of the time. The Hg(0) production was highest at pH 8.0 and in the case of decreasing HS amounts (0.5 mg) when about 65% of initially 1.0 mug Hg(II) was reduced within 50 h. Moreover, the reduction efficiency of HS towards Hg(II) strongly depended on the HS concentration but hardly on the Hg(II)/HS ratio. The reduction kinetics followed a relatively slow two-step first-order mechanism with formal rate constants of about 0.1 and 0.02 h(-1), respectively. Based on these findings the possible relevance of the abiotic evolution of mercury in humic-rich aquatic environments is considered.     

HPLC of humic substances fractionated by Flow FFF

This communication reports a study of the effect of ionic strength and electrolyte composition on fractions, separately collected by flow FFF, of a mixture of humic substances. Reverse phase HPLC analysis of three early eluting fractions suggests that the components released by the column behave as organic acids. The baseline‐resolved peaks of the first two fractions, subject to higher retention in solutions of lower pH and/or higher polarity, substantiate this suggestion. The fraction with larger components, as measured by flow FFF, also appears to contain acidic species. Their retention level, however, may not be accurately modulated by varying the mobile phase properties as these species are either totally retained in acidic phases or released before the void peak at pH ≥ 4.2. Besides showing the effective separation achieved in the flow FFF channel, this study reveals the pronounced difference in the physicochemical properties of some components of a humic mixture even with very close particle size.     

Characterisation of humic substances by acid catalysed transesterification

The chemical composition of low molecular weight moieties linked to the core structures of humic substances (HS) are of substantial importance for the understanding of the chemical structures and mode of interactions of HS with other substances in the environment. In this study a novel approach to characterise certain low molecular weight compounds bound to HS is suggested. The method includes transesterification (TE) of ester and amide bound structures, and esterification (E) of free carboxylic groups using acid catalysed methanolysis followed by gas chromatography (GC)-mass spectrometry (MS) and GC-FID analysis. Methanolysis of five HS of different origin, demonstrated the presence of multifunctional hydroxy-substituted benzoic acids, hexoses, and long chain fatty acids. Based on GC-FID and addition of the internal standard before methanolysis, the total amounts of low molecular weight material could be estimated. In case of HS from the aqueous sources the yields were below 1%, whereas in case of the HS derived from lignite the yield was significantly higher. The hydrophobic long chain fatty acids constituted about one-third of this material. Principal component analysis (PCA), which was used for extended data evaluation, differentiated between the samples in terms of chemical composition.     

UVC-induced photodegradation of p-arsanilic acid assisted by humic substances

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Kinetic determination of selenium using the reduction of nile blue with sulfide ions

The catalytic effect of Se(IV) was first observed in the reaction of the reduction of Nile Blue with sulfide ions. Optimal conditions for the determination of selenium by this reaction were found. The dependence of the reaction rate on the concentration of Se(IV) was linear in the concentration range 0.008-0.16 μg/mL. Solvent extraction with dithiophosphoric acids was proposed for the separation of selenium from the interferents. A procedure for the extraction-kinetic determination of selenium with the detection limit 0.006 μg/mL was developed.     

Kinetic and dynamic aspects of lifetime oscillations in the predissociation of hydrogen chloride ions

The predissociation dynamics of hydrogen chloride ions (HCl+ and DCl+) in the electronic A 2Sigma+ state has been investigated by solving the time dependent Schr?dinger equation. The predissociation lifetime is shown to strongly depend on the vibrational and the rotational quantum number, with quasi-periodic oscillations. Rovibronic states, which exhibit lifetimes about 1 order of magnitude larger than those of neighboring states, are termed rotational islands of stability (RIS). These RIS can be correlated with characteristic reference energies, e.g., the difference between rovibronic eigenenergy and the energy of crossing of rotronic bound and repulsive potentials. The origin of these RIS is illustrated by model studies of the positions of the nuclear wave functions involved.     

Analytical chemistry of freshwater humic substances

Dissolved organic carbon (DOC) in aquatic environments represents one of the largest active organic carbon reservoirs in the biosphere. Current ideologies concerning the sources of DOC, how it is formed and utilized, and what determines the quality of DOC are examined. Humic substances can comprise a significant fraction of the DOC and developments in methods of analysis including the isolation and characterization of this fraction are reviewed.     

Molecular weight fractionation of humic substances by adsorption onto minerals

Molecular weight (MW) fractionation of Suwannee River fulvic acid (SRFA) and purified Aldrich humic acid (PAHA) by adsorption onto kaolinite and hematite was investigated in equilibrium and rate experiments with a size-exclusion chromatography system using ultraviolet (UV) light detection. The extent of adsorptive fractionation based on UV detection was positively correlated with the percent carbon adsorption for both humic substances (HS), although the specific fractionation pattern observed depended on the particular HS and mineral used. Higher MW fractions of SRFA, an aquatic HS, were preferentially adsorbed to both kaolinite and hematite whereas the fractionation trends for PAHA, a terrestrial peat HS, differed for the two minerals. The contrasting fractionation patterns for SRFA versus PAHA can be explained reasonably well by the different structural trends that occur in their respective MW fractions and the underlying adsorption processes. Rate studies of adsorptive fractionation revealed an initial rapid uptake of smaller HS molecules by the mineral surfaces, followed by their replacement at the surface by a much slower uptake of the larger HS molecules present in aqueous solution.     

Determination of the phenolic-group capacities of humic substances by non-aqueous titration technique

The phenolic-group capacities of five humic substances, such as, the Aldrich humic acid, the humic and fulvic acids extracted from a soil, the humic and fulvic acids extracted from a peat have been precisely determined by the non-aqueous potentiometric titration technique. The titration by KOH in the mixed solvent of DMSO:2-propanol:water = 80:19.3:0.7 at [K⁺] = 0.02 M enabled to measure the potential change in a wide range of pOH (=−log [OH⁻]), and thus to determine the capacities of phenolic groups which could not be precisely determined in the aqueous titration. The results of the titration revealed that the mean protonation constants of the phenolic groups were nearly the same for all humic substances and close to that of phenol in the same medium, indicating that each phenolic-group in the humic substances is rather isolated and is not electronically affected by other affecting groups in the humic macromolecule.     

Separation methods in the chemistry of humic substances

Separation methods are widely used to isolate humic substances (HSs), to fractionate them before further investigation, and to obtain information about their structure and properties. Among the chromatographic methods, techniques based on a size-exclusion effect appear to be most useful, as they allow us to relate elution data to the molecular mass distribution of HSs. The limitations of this approach are discussed in this review. Gas chromatography with mass spectrometric detection is typically used to identify the products of pyrolysis or thermochemolysis of HSs; this technique is considered most important in the structural investigation of HSs. Electrophoretic methods (especially capillary zone electrophoresis) provide detailed characterization of HSs, but it is very difficult to relate the electrophoretic data to any specific subfraction, structure or properties of HSs. The electrophoretic patterns are often called "fingerprints" and can potentially be used for the identification and classification of HSs. This is limited, however, by the great diversity of the procedures employed and by the low degree of harmonization--no data on reproducibility and between-laboratory comparability are available. The same holds true, to a certain degree, for most methods utilized for the characterization of HSs. Separation methods play an important role in the examination of the interactions of HSs with heavy metals and other chemical pollutants. They allow us to determine binding constants and other data necessary to predict the mobility of chemical pollutants in the environment.     

Adsorption of mercury ions by mercapto-functionalized amorphous silica

Amorphous silicas have been functionalized by two different methods. In the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the silica surface to give the chlorinated silica Cl-Sil. In a second reaction, multifunctionalized N,S donor compounds were incorporated to obtain the functionalized silicas, which are denoted as L-Sil-Het (where L=mercaptothiazoline, mercaptopyridine or mercaptobenzothiazole). In the homogeneous route, the functionalization was achieved through a one-step reaction between the silica and an organic ligand containing the chelating functions; this gave the modified silicas denoted as L-Sil-Hom. The functionalized silicas were characterized by elemental analysis, IR spectroscopy and thermogravimetry. These materials were employed as adsorbents for mercury cations from aqueous and acetone solutions at room temperature. The results indicate that, in all cases, mercury adsorption was higher in the modified silicas prepared by the homogeneous method. Figure     

Titrimetric analysis of total mercury ions including mercury(I) ions

A systematic analytical method is proposed and applied to directly determine the total concentration of Hg(II) and Hg(I) ions in water. Experimental results demonstrate that this method provides a low detection limit of 0.05 mM and small relative error within 1.5% in an ion concentration range of 0.2–50 mM. The technique is especially applicable for sample solutions that the traditional titration method like Volhard and EDTA complexation titrimetry could not analyze directly. This method could be employed to analyze solutions in any ratio of Hg(II) and Hg(I) ions including pure Hg(II) or pure Hg(I) ions, exhibiting several advantages, such as simple operation, good reproducibility, and low cost. Correspondence: Xin-Gui Li, Key Laboratory of Advanced Civil Engineering Materials, Institute of Materials Chemistry, College of Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China.     

Titrimetric analysis of total mercury ions including mercury(I) ions

A systematic analytical method is proposed and applied to directly determine the total concentration of Hg(II) and Hg(I) ions in water. Experimental results demonstrate that this method provides a low detection limit of 0.05 mM and small relative error within 1.5% in an ion concentration range of 0.2–50 mM. The technique is especially applicable for sample solutions that the traditional titration method like Volhard and EDTA complexation titrimetry could not analyze directly. This method could be employed to analyze solutions in any ratio of Hg(II) and Hg(I) ions including pure Hg(II) or pure Hg(I) ions, exhibiting several advantages, such as simple operation, good reproducibility, and low cost.