Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Metal distribution and nature of some Cu,Mn and V complexes in humic and fulvic acid fractions of soil organic matter

Organic matter from an arable soil derived from base rich parent material was extracted by alkali and fractionated on the basis of solubility in 0.1 N HCl, hot water and hot 6 N HCl and by selective adsorption on charcoal. The distribution of associated metals was determined and Cu had the largest proportion, 15%, associated with the organic matter. Moderate proportions of the total Al, Co, Ni, and V (3–8%) but only small amounts (?1%) of the Mn, Fe, Ti, Cr, Ba and Sr were extracted from the soil by alkali. The Fe and Ti were concentrated mainly in the humic fraction whereas Mn and V were both found largely in the fulvic acid.Electron paramagnetic resonance spectra of the various fractions were examined and attempts made to relate the spectra to the forms of some of the metals present. In the humic acid fraction Cu was present partly as a copper porphyrin-type complex but in the fulvic acid it was in some other complexed form. VO²⁺ occurred in complexed forms in the fulvic acid which were more covalent than VO²⁺ humic acid complexes, whereas the Mn²⁺ components of the humic and fulvic acids all had a high degree of ionicity.     

Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter

The acid-base properties of 14 standard and reference materials from the International Humic Substances Society (IHSS) were investigated by potentiometric titration. Titrations were conducted in 0.1 M NaCl under a nitrogen atmosphere, averaging 30 min from start to finish. Concentrations of carboxyl groups and phenolic groups were estimated directly from titration curves. Titration data were also fit to a modified Henderson-Hasselbalch model for two classes of proton-binding sites to obtain “best fit” parameters that describe proton-binding curves for the samples. The model was chosen for its simplicity, its ease of implementation in computer spreadsheets, and its excellent ability to describe the shapes of the titration curves. The carboxyl contents of the IHSS samples are in the general order: terrestrial fulvic acids > aquatic fulvic acids > Suwannee River natural organic matter (NOM) > aquatic humic acids > terrestrial humic acids. Overall, fulvic acids and humic acids have similar phenolic contents; however, all of the aquatically derived samples have higher phenolic contents than the terrestrially derived samples. The acid-base properties of reference Suwannee River NOM are surprisingly similar to those of standard Suwannee River humic acid. Results from titrations in this study were compared with other published results from both direct and indirect titrations. Typically, carboxyl contents for the IHSS samples were in agreement with the results from both methods of titration. Phenolic contents for the IHSS samples were comparable to those determined by direct titrations, but were significantly less than estimates of phenolic content that were based on indirect titrations with Ba(OH)₂ and Ca(OAc)₂. The average phenolic-to-carboxylic ratio of the IHSS samples is approximately 1:4. Models that assume a 1:2 ratio of phenolic-to-carboxylic groups may overestimate the relative contribution of phenolic groups to the acid-base chemistry of humic substances.     

Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon

In this paper the groundwater in-situ generation of dissolved organic carbon (DOC) is discussed based on the origin of groundwaters, their physico-chemical and isotopic properties, chemical composition and the dissolved inorganic carbon (DIC) concentration and its ¹³C content. Three aquifer systems are investigated. Two of these have relatively well defined hydrological and geochemical conditions (Fuhrberg and Munich) and are used as reference systems. The third aquifer (Gorleben) is a complex system containing DOC concentrations up to 200 mg C/L in deep groundwaters. From this aquifer system 19 groundwaters from different hydrogeochemical conditions are analyzed. The in-situ generation of DOC is found to occur in conjunction with the microbiologically mediated mineralization of sedimentary organic carbon (SOC). Thereby, SO₄ is reduced and phosphate is released into the groundwater. Where SO₄ is depleted, the mineralization of SOC occurs via fermentation, resulting in CH₄ generation.     

An EPR spectroscopic examination of heavy metals in humic and fulvic acid soil fractions

Electron paramagnetic spectra of humic acid and various fractions of fulvic acid from a deep peat soil were studied and related to some of the metals present. In fulvic acid, VO²⁺ occurred in complexed form. The Mn²⁺ components all had a high degree of ionicity. In the humic acid fraction Cu²⁺ was present as a copper porphyrin-type complex.     

Aquathermolysis of humic and fulvic acids: Simulation of organic matter maturation in hot thermal waters

Dissolved aromatic compounds in Hungarian thermal waters were first reported more than 10 years ago. Among the identified compounds were alkylbenzene, polyaromatic hydrocarbon and heteroaromatic homologue series. The appearance of dissolved organic compounds has been bound to a threshold temperature of ∼80 °C, and their distribution is controlled by the water temperature. Relative demethylation and aromatisation were observed with increasing temperature. The origin of these compounds is not proved. Among precursor candidates are humic substances.Simulation experiments were carried out on humic and fulvic acid and on their mixture to gain information on aromatic compounds formed. The samples were heated and products were measured with GC-MS.In the presence of oxygen, increasing concentration of benzene can be observed as a function of temperature. Toluene and thiophene can be identified, other alkylbenzenes are missing. Under reductive conditions the concentration of benzene, toluene and the ratio of short to long chained aromatics generally increases in every sample as a function of temperature. Main compounds are toluene and benzene. The amount of heteroaromatic compounds increases with temperature, but their relative concentration compared to aromatic hydrocarbons decreases. At higher temperatures the proportion of pyrroles drops and S and O containing ones become dominant.The different processes (formation, aromatisation, polycondensation, relative demethylation, decomposition) occur in parallel but their relative intensities vary as a function of temperature. The effects of duration and increasing temperature are similar but not equal: both demethylation and aromatisation can be observed.     

Preparation and characterization of humic acid cross-linked with organic bridging groups

Cross-linking of humic substances with organic bridging groups is thought to contribute to the humification of soil organic matter. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid, applying procedures established for cross-linking of polymers and textile fabrics. Products of the cross-linking reactions were analyzed by FTIR and ¹³C CPMAS NMR. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and ¹³C CPMAS NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. The reactions investigated in this study can be regarded as models for reactions occurring in natural soils to test the significance of cross-linking reactions in the humification process of soil organic matter and the physico-chemical properties and ecological function of organic matter in geosolids.     

Comparison of soil humic and fulvic acids of similar molecular weight

Soil fulvic acids were compared with humic acid of similar molecular weight. The elementary composition, total carbohydrate content and ¹³C-NMR spectral features differentiate these fractions and leads to consideration of fulvic acid as a separate chemical entity.     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

The lignin component of humic substances: Distribution among soil and sedimentary humic,fulvic, and base-insoluble fractions

Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.     

1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

¹H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH₂)_n - CH₃ (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.     

Effects of age on the chemical structure of paleosol humic acids and fulvic acids

Humic acids and fulvic acids were extracted from six paleosols in Southern Italy. Humic acids (HAs) constituted between 96.5 and 99.2% of the total extracts; the remaining materials consisted of fulvic acids (FAs). Radiocarbon ages of the HAs ranged from about 6,000 to close to 29,000 years B.P., δ¹³C values averaged $\text{?25.6 ± 0.3‰}$ The HAs were characterized by chemical (elemental and functional group analyses) and spectroscopic (IR, ESR, ¹³CNMR, E₄/E₆ ratios) methods. FAs were characterized by chemical methods, E₄/E₆ ratios and IR spectra.The chemical and spectroscopic analyses showed practically no differences in the chemical structure and composition of the six HAs and FAs, so that age appeared to have little effect on these parameters. The paleosols were found to be closed systems with low polysaccharide and protein contents, thus providing unfavorable substrates for microbial activity. The preservation of the humic materials in the paleosols may have been due to low biological activity and/or to retention by amorphous minerals. The HAs did not appear to be affected by temperatures higher than 170–200°C over the 23,000 year period which we observed.     

Differences in properties and Cm(III) complexation behavior of isolated humic and fulvic acid derived from Opalinus clay and Callovo-Oxfordian argillite

Fulvic acids from deep clay formations have been isolated by the International Humic Substances Society (IHSS) standard protocol and analyzed. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy reveals, that the basic structural features relating to the origin of the clay organic matter (i.e., terrestrial or marine) are preserved even after the around 150 Ma since deposition (Jurassic sediment). Analysis by asymmetrical flow field flow fractionation (AFFFF) shows the size distribution peak found for typical fulvic acids. In addition, a second larger size peak is found for the fulvic acids influenced by marine deposition. These fulvic acids also have a considerable content of organic material which does not absorb in the visible range. The Cm(III) complexation behavior has been studied by time-resolved laser fluorescence spectroscopy (TRLFS). Despite considerable fluorescence quenching, the complexation constant is shown to be in the same range as published values found for different typical fulvic acids.     

Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

Copper dissociation from estuarine humic materials

Dissolved humic material from three locations on the Ogeechee River Estuary near Savannah, GA, was ultrafiltered into three size fractions and used for kinetic experiments with Cu(II). A Cu(II)-humic mixture was reacted with a colorimetric reagent for Cu(II) and absorbance observed from 50 msec to at least 1835 sec corresponding to rate constants from 0.001–40 sec^?1. The apparent dissociation rate constants were distributed over a wide range, with most bound Cu(II) having k > 1 sec^?1 ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 0.7 sec}$). Nearly all the variation seen in the kinetic distribution was among size fractions; as size fraction decreased, the distribution of bound Cu(II) shifted to larger rate constants. Location of sampling stations on the estuary had little effect on results.     

Molecular weight distribution of humic and fulvic acids of sediments from a north Florida estuary

The molecular weight distribution of the humic and fulvic acid fractions of two sediments was determined using Amicon ultrafiltrat ion techniques. All fractions of humic substances had a molecular weight range of less than 500 to greater than 300,000. The largest component of humic acids was in the greater than 300,000 molecular weight range, whereas, the largest percentages of fulvic acids were in the less than 500 molecular weight range and the 100,000–300,000 molecular weight range. From this preliminary investigation there appears to be a qualitative relationship between the molecular weight composition of the humic substances in the sediment and the salinity of the overlying water within an estuarine environment.     

Ultrafiltration of fulvic and humic acids,a comparison of stirred cell and hollow fiber techniques

The ultrafiltration of solutions of well characterized samples of fulvic and humic acids or their salts, using two different techniques, show that these materials are retained by commercial ultrafiltration membranes with molecular weight cut-off values far higher than the reported molecular weights of fulvic or humic acid. The lower molecular weight fulvic acid or its Na⁺ -salt is retained even better than the higher molecular weight Na⁺-salt of humic acid. Both stirred cell and hollow fiber techniques can be employed to concentrate or desalt solutions of these humic materials, with relatively small solute losses. Very high simple electrolyte backgrounds (above 1 M) lower the performance of a given membrane considerably, moderate concentrations of simple electrolyte do not influence the ultrafiltration efficiency.     

Effect of monochloramine on isolated fulvic acid

Monochloramine is interesting both as a selective oxidant of fulvic acid and as a drinking water disinfectant. In this study, the controlled reaction of aquatic fulvic acid with monochloramine did not result in products detectable by ether extraction-gas chromatography-flame ionization detection techniques. Evidence of a reaction was shown by bleaching of the fulvic acid solution (decreased absorbance at 465 nm) and chlorine substitution. Chlorine-containing products were quantified by the total carbon adsorbable organic halide (TOX) parameter. Bleaching and organic chlorine formation were much less extensive than in the reaction of free chlorine with fulvic acid. Monochloramine was shown to produce an organic chlorine fraction more hydrophilic and with higher molecular size than that produced by chlorine and fulvic acid. Results suggest that monochloramine may be useful tool for the investigation of certain humic functionalities because it reacts rather selectively and to a small extent with aquatic fulvic acid.     

Sterols as source indicators of organic materials in sediments

The sterol contents of plankton and sediment samples have been determined. Cholesterol, 22-dehydrocholesterol, brassicasterol, campesterol, 24-methylenecholesterol, stigmasterol, and β-sitosterol are the major sterols in these samples. Systematic variations have been observed in the compositions of the sterols from bay and Gulf of Mexico plankton and from sediments collected in the mouth of the Aransas River, Capano Bay, Aransas Bay, Corpus Christi Bay and the Gulf near Port Aransas. The concentration of cholesterol increases as the concentration of β-sitosterol decreases in the sample sequence of river inlet sediments-bay sediments-Gulf sediments-bay and Gulf plankton. Calculations based on either the cholesterol or the β-sitosterol contents of the sterol fractions of the fresh water sediments and the Gulf plankton and sediments suggest that 34% of the sterols in the Gulf sediments are derived from terrigenous sources.