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1.
The molecular weights of aquatic fulvic acids extracted from five rivers were determined by vapor pressure osmometry with water and tetrahydrofuran as solvents. The values obtained ranged from 500 to 950 dallons, indicating that the molecular weights of aquatic fulvic acids are not as great as has been suggested in some other molecular weight studies. The samples were shown to be relatively monodisperse from radii of gyration measurements determined by small angle x-ray scattering. THF affords greater precision and accuracy than H2O in VPO measurements, and was found to be a suitable solvent for the determination of molecular weight of aquatic fulvic acid because it obviates the dissociation problem. An inverse correlation was observed with these samples between the concentration of Ca++ and Mg++ in the river water and the radii of gyration and molecular weights of the corresponding fulvic acid samples.  相似文献   

2.
Humic matter fractions from modern sediments of Lake Huron and Lake Michigan have been compared. Large yields of saccharinic acids from alkaline hydrolysis suggest that these fractions contain large portions of carbohydrate materials. Evidence for contributions of aquatic lipid (C-16 fatty acids) and of liginin (phenolic acids) to these sediments is also present in the hydrolysis products. Qualitative differences among fulvic acid, humic acid and humin from the same lake are minor, suggesting common (or similar) organic sources for these fractions. The lability of sedimentary humic matter to alkaline hydrolysis is inversely related to its degree of exposure to oxidative weathering. Lability may also be related to diagenetic state as fulvic acids generally yield greater quantities of hydrolysis components than humic acids which in turn yield more than humin.  相似文献   

3.
The reactivity of iron(III) oxyhydroxides as reflected by their tendency to dissolve is of great importance in the redox cycling of iron and the bioavailability of iron to phytoplankton in natural waters. In this study, various iron(III) oxyhydroxides were produced by oxygenation of iron(II) in the presence of solutes, such as phosphate, sulfate, bicarbonate, valeric acid, TRIS, humic and fulvic acids, and in the presence of minerals, such as bentonite and δ-Al2O3 under conditions encountered in aquatic systems. The reactivity of the different iron(III) oxyhydroxides was subsequently assessed by means of a reductive dissolution using ascorbate and non-reductive dissolution using HQS (8-hydroxyquinoline-5-sulfonic acid) or oxalate. The experimental results show that the iron(III) oxyhydroxides with a low degree of polymerization exhibit higher reactivity than those with a high degree of polymerization or with high crystallinity. The quantity of active surface sites and the coordination arrangement of the functional groups at the surface of the iron(III) oxyhydroxides, especially the extent of the endstanding -OH groups per iron(III) ion determine the reactivity of iron(III) oxyhydroxides toward dissolution.Surfaces, such as clay and aluminum oxides, not only accelerate the oxygenation reaction of iron(II), but also induce the formation of iron(III) oxyhydroxides which are more active toward the dissolution reactions. Polymerization of iron(III) oxyhydroxides on the surfaces occurs predominantly in two dimensions rather than in three dimensions.In a laboratory experiment, the iron(III) oxyhydroxide formed in the presence of TRIS can be reduced by fulvic acid in a closed system under the following conditions: Fe(OH)3(s) 0.01 g/l, fulvic acid 5 mg/l, pH 7.5, 20°C. The kinetics of the reaction depend on the reactivity of iron(III) oxyhydroxide and reducing power of fulvic acid. Although reductants other than fulvic acid may be of importance in antural waters, this result provides the laboratory evidence that the >FeIII-OH/Fe(II) is able to act as an electron transfer mediator for the oxidation of natural organic substances, such as fulvic acid, by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.  相似文献   

4.
Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.  相似文献   

5.
A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin.  相似文献   

6.
Thermal decomposition, temperatures of four organic Zn complexes were evaluated experimentally by determining the change in sphalerite solubility with temperature in aqueous solutions containing organic compounds. The results show that decomposition takes place at 180°±5°C for lactic acid-Zn complex, 200°±5°C for EDTA-Zn, 240°±5°C for quinone-Zn and 190°±5°C for fulvic acid-Zn. It is also shown that at 190°–200°C sphalerite solubility is 4 to 7 times higher in NaCl solution containing organic compounds than that in NaCl solution without organic compounds. Studies were also conducted on the contents of Pb and Zn complexed by fulvic acid and humic acid in aqueous solutions the infrared spectra of fulvic acid-Zn and humic acid-Zn complexes, the differential thermal analysis of fulvic acid, humic acid and quinone and EDTA, and the variation in fulvic acid solubility in the seawater with temperature.  相似文献   

7.
Five surface sediment samples (0–3 cm), two suspended sediment samples and a zooplankton sample from Lake Ontario were analysed for nitrogen-containing compounds. Amino acids, amino sugars, ethanolamine and urea were separated and characterized by ion-exchange chromatography. Free amino acids and soluble combined amino acids and amino sugars accounted for less than 0–25 per cent of the total nitrogen in the sediments. Insoluble combined amino acids and amino sugars were the most abundant nitrogen fraction in the sediments, making up from 49 to 55 per cent of the total nitrogen. Evidence is presented that asparagine, glutamine and citrulline are present in the interstitial waters and may make up part of the sediment organic nitrogen that was not characterized.The free amino acids released by the proteolytic enzyme, pronase, from the interstitial waters and sediment humic and fulvic acid extracts were determined. Pronase released 65 per cent of the soluble combined amino acids and 34 per cent of the fulvic acid amino acids as free amino acids. Enzyme activity was inhibited in the presence of the humic acid extract. The results indicate that the combined amino acids in the interstitial waters and fulvic acid extracts are intermediates between the primary aquatic detritus and the sediment humic acids. The enzyme experiments and infra-red data indicate that part of the sediment amino acids are combined through peptide linkages.  相似文献   

8.
Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.  相似文献   

9.
The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS 15N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by 15N NMR. Liquid state 15N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (1H–15N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.  相似文献   

10.
Aquatic fulvic acid, isolated from a North Carolina bay lake, was reacted with ozone, an alternative oxidant in drinking water treatment. Ozonated samples were acidified, extracted with ether, dried, concentrated, and methylated prior to GC-MS analysis. Identified reaation products include mono-, di- and tribasic aliphatic acids and benzene tricarboxylic acids. The products with the highest relative concentrations were succinic and malonic acid, although all products were at relatively low concentration levels. Many of the products identified in this study have also been seen among the reaction products of fulvic acid and other oxidants, such as Cl2, CIO2 and KMnO4.  相似文献   

11.
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.  相似文献   

12.
After the May 18, 1980, eruption of Mount St Helens, the concentration of dissolved organic material in surface waters near the volcano increased significantly as a result of the destruction of the surrounding conifer forest. Low molecular weight organic compounds identified in the blast zone surface waters were derived from pyrolysis of plant and soil organic materials incorporated into pyroclastic flow, mud flow and debris avalanche deposits. A major fraction of the dissolved organic material consisted of high molecular weight, colored, organic acids that are similar in their general properties to aquatic fulvic acids found in more typical surface waters except for greater sulfur contents. The other major fraction of the dissolved organic material consisted of hydrophilic acids, which may include compounds capable of supporting heterotrophic microorganisms, and precursors in the formation of aquatic fulvic acids. The organic chemistry of blast zone surface waters will probably be greatly influenced by the May 18, 1980, eruption for many years.  相似文献   

13.
《Organic Geochemistry》1987,11(2):91-101
Nuclear magnetic resonance (NMR) techniques have been applied to the structural characterization of humic substances isolated from an organic-rich sediment in Loch Thurnaig, northwest Scotland. Both the sedimentary humic acid (SHA) and sedimentary fulvic acid (SFA) fractions from Loch Thurnaig contained substantial quantities of carboxylic and alkyl carbon with a small contribution (26 and 22% respectively) of aromatic/olefinic carbon atoms. The latter structures were shown by dipolar dephasing 13C NMR to be largely non-protonated. Differences in the alkyl structures of the two fractions were noted, with the SHA containing a larger amount of branched chain aliphatic material. As branched chain compounds are more resistant to microbial degradation than straight chain compounds, this may indicate that SHA is the older, more refractory fraction of the sedimentary organic matter, although it is possible that the results reflect different algal precursor material. The fraction of aromatic carbon was higher in the SHA than in the SFA as is generally found for humic and fulvic acids isolated from the same source. The low aromaticities and highly branched aliphatic structures show that the sedimentary humic substances from the loch resemble dissolved marine humic substances rather than their terrestrial counterparts.  相似文献   

14.
The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH3COO−) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).  相似文献   

15.
Adsorption experiments using fulvic acid with calcite and quartz demonstrate that carbonate surfaces are able to selectively adsorb aspartic acid-rich organic matter. Quartz does not have this ability, instead exhibiting a preference for the aspartic acid-poor fraction. The relative abundance of aspartic acid in the fraction adsorbed onto calcite is highly dependent on the ratio of fulvic acid to calcite. At high ratios, fulvic acid is adsorbed with a relative abundance of aspartic acid that is more than twice that in the original fulvic acid. With decreasing ratios, there is a concomitant decrease in the relative abundance of aspartic acid in the adsorbed fraction. Selective adsorption may be the most likely mechanism by which aspartic acid-rich organic matter is included in non-biogenic car- bonates such as ooids. This process may be a factor influencing the distribution of amino acids within ooids, their rate of growth, and may ultimately be a factor in limiting their size.  相似文献   

16.
《Organic Geochemistry》1999,30(8):901-909
Deuterium nuclear magnetic resonance spectroscopy (2H-NMR) spin–lattice relaxation (T1) experiments were used to measure noncovalent interactions between deuterated monoaromatic compounds (phenol-d5, pyridine-d5, benzene-d6) and fulvic acids isolated from the Suwannee River and Big Soda Lake. Noncovalent interactions, in aqueous solution, were examined as a function of monoaromatic hydrocarbon functional groups, fulvic acid concentration and identity, and solution pH. Phenol did not exhibit noncovalent interactions with either fulvic acid at any pH. Pyridine, in a pH range from 3 to 8, interacted with Suwannee River fulvic acid, forming a bond involving the lone pair of electrons on nitrogen. Conversely, no interactions were observed between pyridine and Big Soda Lake fulvic acid; the difference in noncovalent interactions is attributed to the structural and chemical differences of the two fulvic acids. The translational and rotational molecular motion of benzene increased in the presence of both fulvic acids, indicating that in aqueous solution, fulvic acids solubilize benzene rather than forming discrete bonds as with pyridine. The results of this study demonstrate that monoaromatic functional groups, solution pH, and identity and concentration of fulvic acid can influence the type and degree of noncovalent interactions with dissolved organic matter.  相似文献   

17.
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.  相似文献   

18.
《Applied Geochemistry》1996,11(4):555-565
Organic material is present at low concentrations, typically 1–2 mg/l in terms of dissolved organic carbon (DOC), in groundwaters deep in granitic rock. Hydrophobic and hydrophilic acids may complex inorganic contaminants and change their sorption behaviour on geological materials. This report describes a series of experiments performed under aerobic conditions to investigate the effects of fulvic acid over a concentration range of 0–5 mg/I DOC on the sorption of85Sr,137Cs,233U,238Pu and241'Am by crushed granite, biotite, goethite, montmorillonite and quartz. In addition, similar solutions were used to study the effects of dissolved fulvic acid on the sorption of99Tc and125I on each of the above solids except quartz. The fulvic acid was extracted from groundwater collected at a depth of 240 m in the granitic rock of the Underground Research Laboratory near Lac du Bonnet, Manitoba.In all experiments, the sorption of the fulvic acid by the geological materials was in the order goethite montmorillonite > biotite > granite > quartz. No sorption of Tc was observed from any of the solutions on any of the solids. Low sorption of I on montmorillonite occurred in the presence of the dissolved organic material. No sorption of I was observed with the other solids used. Only montmorillonite sorbed any appreciable amount of Sr in this study with the fulvic acid having no effect on this sorption. All the solids except quartz sorbed substantial amounts of Cs, but sorption was not affected by the organic material in solution. Each of the solids sorbed U with no difference in sorption observed due to the dissolved organic. In general, Pu sorption decreased as the concentration of dissolved fulvic acid increased. However, sorption of Pu on quartz remained at approximately the same levels regardless of the concentration of organic in solution. Generally high sorption of Am was found. Lowest sorption of Am on all solids occurred from the solution with the highest concentration of fulvic acid. Sorption of Am on granite decreased as the concentration of the organic in solution increased.This study indicated that, under aerobic conditions, the effect of dissolved organic material on sorption of radioisotopes depends on the radioisotope in question and the concentration of the organic in solution.  相似文献   

19.
Water samples from Narragansett Bay and the Providence River, and fulvic acid/ saline water solutions were examined for their ability to solubilize n-alkane (n-C16 and n-C20), isoprenoid (pristane) and aromatic (phenanthrene and anthracene) hydrocarbons and dibutyl phthalate. Removal of the dissolved organic matter (D.O.M.) from the natural samples by activated charcoal and by ultra-violet oxidation resulted in a 50–99 per cent decrease in the amounts of n-alkanes and isoprenoid hydrocarbons solubilized. This decrease was directly related to the amount of D.O.M. removed. The solubilities of the aromatic hydrocarbons were unaffected by the D.O.M. Fulvic acid from a marine sediment, surface active organic material isolated at a chloroform/sea water interface, organic material extracted from a marine sediment by sea water, and organic matter contributed by a municipal sewage effluent, promote n-alkane solubility when added to NaCl solutions and re-enhance solubility when added to organic depleted sea water. The solubility of No. 2 fuel oil increased 2.5 times in the presence of fulvic acid (3.7 mg C/l.) with most of the increase seen in the alkane and isoprenoid components.N-Alkane solubility increases in fulvic acid/saline water solutions with increasing pH and reaches a maximum with respect to ionic strength at I = 0.3. There is evidence to suggest that the mode of solubilization of the hydrocarbons is by incorporation into micelles formed by intermolecular association of the surface active humic-type monomers. The presence of ionic species is a prerequisite for micelle formation.  相似文献   

20.
Peptides were released from organic matter fractions of three Italian soils (humin, humic and fulvic acids), when the samples were hydrolyzed in Ba(ON)2-saturated solution at 105°C for 2 hr. The peptides obtained were separated using electrophoresis and paper chromatography. The presence of polypeptides in the soil organic matter was indicated by: (1) their hydrolysis by pronase; (2) the amino acids released by 6 N HCl hydrolysis; (3) The comparison of i.r. spectra of humic fractions before and after hydrolysis with 6 N HCl.Attempts at isolating the native proteinaceous compounds using electrophoresis in polyacrylamide gel failed; additionally, our attempts to hydrolyze proteinaceous components enzymatically in unfractionated soil organic matter, as well as in its fractions, before and after methylation, with pepsin, papain and pronase, were unsuccessful. Pronase demonstrated a weak proteolytic activity only at very low substrate-enzyme ratios (20 : 1) in humic and fulvic fractions and in whole phyrophosphate extract. Deproteinated substrates treated with pronase also released free amino acids, suggesting autodigestion.In humin, humic and fulvic fractions we found a total amino acid content of 40–45%, 12–24% or 1–85, respectively. Amino acid recovery from single fractions was about 70–80% of the total content in the unfractionated soil.  相似文献   

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