Showing papers on "Humic acid published in 2003"

Characterization and copper binding of humic and nonhumic organic matter isolated from the south platte river : evidence for the presence of nitrogenous binding site

Abstract: Humic substances typically constitute 40-60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg x L(-1), SUVA254 = 2.4 L/mg x m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM,were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction ("transphilic" meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.

Effects of natural organic matter and solution chemistry on the deposition and reentrainment of colloids in porous media.

Abstract: The role of humic acid in the transport of negatively charged colloids through porous media was examined. Adsorption of humic acid on latex colloids and silica collectors reduced the deposition of suspended particles and enhanced the reentrainment of deposited particles in porous media. These effects are considered to arise from additional electrostatic and steric contributions to the repulsive interaction energy due to the adsorption of negatively charged humic acid on both the suspended particles and the media collectors. At low ionic strength reversible deposition in shallow secondary minima is hypothesized to be the principal attachment mechanism, independent of the presence of humic acid. It is proposed that under these solution conditions, particle deposition and reentrainment are the result of a dynamic process, in which particles are continuously captured and released from secondary minima. At higher ionic strengths, deposition may be regarded as a combination of two mechanisms: capture in the primary well and capture in the secondary minimum. Theoretical calculations of the attachment efficiency were conducted using two existing mathematical models. The first model is based on deposition in the primary well (interaction force boundary layer, IFBL), and the second model is based on the Maxwell kinetic theory and deposition in the secondary minimum (Maxwell model). Simulations conducted with the Maxwell model provide significantly better fits of the experimental results than those conducted with the IFBL model.

Effects of physical-chemical characteristics on the sorption of selected endocrine disruptors by dissolved organic matter surrogates.

Abstract: Sorption coefficients (K(oc) values) of selected endocrine disruptors for a wide variety of dissolved organic matter (DOM) were measured using fluorescence quenching and solubility enhancement. 17beta-Estradiol, estriol, 17alpha-ethynylestradiol, p-nonylphenol, p-tert-octylphenol, and dibutylphthalate were selected as endocrine disruptors. Aldrich humic acid, Suwannee River humic and fulvic acids, Nordic fulvic acid, alginic acid, dextran, and tannic acid were selected as DOM surrogates. The resulting sorption coefficients (log K(oc)) were independent of octanol-water partitioning coefficients (log K(ow)) of the selected endocrine disruptors, indicating the hydrophobic interaction is not the predominant sorption mechanism. Moreover, the K(oc) values for the selected endocrine disruptors, especially the steroid estrogens, correlated much better with UV absorptivity at 272 nm (A272) and phenolic group concentration of the DOM than with either the H/O or the (O+N)/C atomic ratio of the DOM. This suggests that the sorption mechanism is closely related to the interaction between pi-electrons and the hydrogen bonds, i.e., the affinity between phenolic groups of the steroid estrogens and DOM is suggested to provide a relatively large contribution to the overall sorption and yield the K(oc) values of the steroid estrogens as high as those of the alkylphenols and dibutylphthalate, which are suggested to be dominated by nonspecific hydrophobic interaction.

Binding of mercury(II) to aquatic humic substances: influence of pH and source of humic substances.

Abstract: Conditional distribution coefficients (KDOM‘) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that KDOM‘ values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (1022.5±1.0−1023.5±1.0 L kg-1), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. KDOM‘ values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)−DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pKa = 10.3) and one other group (pKa = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)−DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol

Abstract: . Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from remaining inorganic salts and "most" hydrophilic organic matter (MHOM). This approach allowed ISOM, which constitutes the major fraction of WSOM, to be isolated from ambient aerosols and investigated in pure form. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 30% and 60% relative humidity (RH), and hygroscopic growth factors at 90% RH ranged from 1.08 to 1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. The hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75-85% and 85-95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular mass and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumed value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) ranging from +1% to -18%. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42-53 wt % of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80-62% of particulate water in the samples are associated with inorganic salts and about 20-38% with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.

Automated quantitative and isotopic (13C) analysis of dissolved inorganic carbon and dissolved organic carbon in continuous-flow using a total organic carbon analyser.

Abstract: A method for the automated (13)C analysis of dissolved inorganic and organic carbon species has been developed to operate on a continuous-flow isotope ratio mass spectrometer (CF-IRMS). For natural and anthropogenic carbon species, the (13)C stable isotope has proven to be an excellent environmental tracer. Analytical performance tests were carried out on various organic compounds from easily oxidisable (sugar) to difficult (humic acid). A set of natural samples was also analysed to confirm the flexibility of the system. Analytical precision (2sigma) is typically <0.20 per thousand with sample reproducibility from 0.10-0.35 per thousand depending on reactivity of material. We believe this to be the first successful use of a total organic carbon (TOC) analyser for both dissolved inorganic and, specifically, dissolved organic species for (13)C stable isotope analysis in an automated CF-IRMS system. Routine analysis is achieved fairly quickly, is relatively simple with little or no sample manipulation, and will allow new and exciting studies for stable isotope research in both natural abundance and organic tracer studies not easily achieved before.

Sorption and desorption of naphthalene by soil organic matter: importance of aromatic and aliphatic components.

Abstract: Nonlinear isotherm behavior has been reported for the sorption of hydrophobic organic compounds (HOCs) in soil organic matter (SOM), but the exact mechanisms are unknown. Our objective was to provide insight into the sorption mechanism of HOCs in SOM by studying the sorption-desorption processes of naphthalene in a mineral soil, its humic fractions, and lignin. Additionally, humin and lignin were used for studying the effects of temperature and cosolvent on HOC sorption. All isotherms were nonlinear. The humin and lignin isotherms became more linear at elevated temperatures and with the addition of methanol indicating a condensed to expanded structural phase transition. Isotherm nonlinearity and hysteresis increased in the following order: soil humic acid (HA) < soil < soil humin. Of the samples, aliphatic-rich humin exhibited the largest degree of nonlinearity and had the highest sorption capacity for naphthalene. High nonlinearity and hysteresis in humin were most likely caused by its condensed structure. A novel aliphatic, amorphous condensed conformation is proposed. This conformation can account for both high sorption capacities and increased nonlinearity observed for aliphatic-rich samples and can explain many sorption disparities discussed in the literature. This study clearly illustrates the importance of both aliphatic and aromatic moieties for HOC sorption in SOM.

Sources of carbon dioxide supersaturation in clearwater and humic lakes in northern Sweden

Abstract: Partial pressure (pCO(2)) and flux to the atmosphere of carbon dioxide (CO2) were studied in northern alpine and forest lakes along a gradient of dissolved organic carbon (DOC) content (0.4-9.9 mg ...

Molecular Weight Characteristics of Humic Substances from Different Environments As Determined by Size Exclusion Chromatography and Their Statistical Evaluation

Abstract: Recorded molecular weights (MWs) for humic substances (HS) range from a few hundred to millions of daltons. For purposes of defining HS as a specific class of chemical compounds, it is of particular importance to ascertain if this broad range of MWs can be attributed to actual variability in molecular properties or is simply an artifact of the analytical techniques used to characterize HS. The main objectives of this study were (1)to establish if a preferential range of MWs exists for HS and (2) to determine any consistent MW properties of HS. To reach the goal, we have undertaken an approach to measure under standardized conditions the MW characteristics of a large set of HS from different natural environments. Seventy-seven humic materials were isolated from freshwater, soil, peat, and coal, such that each possessed a different fractional composition: humic acid (HA), fulvic acid (FA), and a nonfractionated mixture of HA and FA (HF). Size exclusion chromatography (SEC) was used as the analytical technique to determine molecular weight characteristics. The MW distributions were characterized by number (Mn) and weight (Mw) average MW, and by polydispersity. The complete range of Mw values varied within 4.7-30.4 kDa. The maximum Mw values were observed for peat HF and soil HA, whereas the smallest weights were measured for river water HF. Maximum values of polydispersity (3.5-4.4) were seen for peat HF and soil HA, while much lower values (1.6-3.1) were found for all preparations isolated with XAD-resins. Statistical evaluation showed consistent Mw and Mn variations with the HS source, while polydispersity was mostly a function of the isolation procedure used. A conclusion was made that HS have a preferential range of MW values that could characterize them as a specific class of chemical compounds.

Separation and characterization of NOM by high-performance liquid chromatography and on-line three-dimensional excitation emission matrix fluorescence detection.

Abstract: By using high-performance size exclusion chromatography (HPSEC) and reversed-phase high-performance liquid chromatography with on-line three-dimensional excitation emission matrix fluorescence detection, we measured fluorescence properties of natural organic matter (NOM) as a function of molecular size (MS) and polarity. The work was carried out with Suwannee River Fulvic Acid, Aldrich Humic Acid, and a naturally occurring river NOM sample. Significant differences in fluorescence maximum pattern were found as NOM was separated chromatographically based on MS and polarity. There existed a strong relationship between MS, fluorescence pattern, and polarity. Humic-, fulvic-, and protein-like fluorescence fractions had distinct hydrophilic/hydrophobic nature. The results suggest that HPSEC may be better for characterizing major fulvic-like fluorescence and smaller MS fractions but not those having humic- and protein-like fluorescence and larger MS, which may be strongly adsorbed onto the HPSEC column because of their hydrophobic nature. This study has significant implications for further understanding the nature of NOM and its complexation with trace metals.

Disinfection of water containing natural organic matter by using ozone-initiated radical reactions.

Abstract: Ozone is widely used to disinfect drinking water and wastewater due to its strong biocidal oxidizing properties. Recently, it was reported that hydroxyl radicals ((.)OH), resulting from ozone decomposition, play a significant role in microbial inactivation when Bacillus subtilis endospores were used as the test microorganisms in pH controlled distilled water. However, it is not yet known how natural organic matter (NOM), which is ubiquitous in sources of drinking water, affects this process of disinfection by ozone-initiated radical reactions. Two types of water matrix were considered for this study. One is water containing humic acid, which is commercially available. The other is water from the Han River. This study reported that hydroxyl radicals, initiated by the ozone chain reaction, were significantly effective at B. subtilis endospore inactivation in water containing NOM, as well as in pH-controlled distilled water. The type of NOM and the pH have a considerable effect on the percentage of disinfection by hydroxyl radicals, which ranged from 20 to 50%. In addition, the theoretical T value of hydroxyl radicals for 2-log B. subtilis removal was estimated to be about 2.4 x 10(4) times smaller than that of ozone, assuming that there is no synergistic activity between ozone and hydroxyl radicals.

Natural organic matter as reductant for chlorinated aliphatic pollutants.

Abstract: Humic acids (HA) are ubiquitous redox-active compounds of natural aquatic and soil systems. Here we studied the potential of HA as reductants for chlorinated aliphatic pollutants. To avoid artifacts potentially involved when studying chemically reduced HA, we prepared electrochemi cally reduced soil, aquatic and synthetic HA, and anthrahydroquinone-2,6-disulfonic acid (AHQDS), a model compound for hydroquinone moieties in HA. Both reduced HA and AHQDS reduced hexachloroethane (HCE) at appreciable rates. Some reduction of HCE by HA, however, occurred even before electrochemical reduction of the humic acids. This indicates that a small fraction of reduced moieties in HA persists at oxic conditions for some time. The initial reaction followed pseudo-first-order reaction kinetics, and tetrachloroethylene was the only halogenated product. The relatively small variations in carbon-normalized rate constants, kDOC, found indicate that despite inherent variations in concentration, accessibility, and reactivity of redox-active groups in HA of various origins their overall dechlorination activity is fairly constant. However, HCE transformation rate constants and reducing capacities of different HA did not correlate. Rate constants normalized to both carbon content and reducing capacity of HA clearly indicate that reduced functional groups in different HA exhibit different reactivities. Our results together with the fact that reduced HA can be formed by a variety of microbiological and chemical processes suggest that HA could play a significant role as reductants in the reductive transformation of subsurface contaminants and that such a process could potentially be enhanced at contaminated sites by addition of reducible natural organic matter.

Sorption and desorption of pesticides by clay minerals and humic acid-clay complexes

Abstract: In soils, organic matter and minerals are often associated such that it is unclear how the presence of the former component influences the sorptive properties of the latter one. In this study, sorption and desorption of the herbicides 4,6-dinitro-o-cresol (C 7 H 6 N 2 O 5 ) and dichlobenil (C 7 H 3 Cl 2 N) by Ca 2+ -, K + -smectites, and humic acid-smectite complexes, was investigated using batch-equilibrations and x-ray diffraction (XRD). Greater sorption of 4,6-dinitro-o-cresol compared with dichlobenil was observed for both smectites and humic acid-smectite complexes. For both pesticides, K + smectites were more effective sorbents than Ca 2+ smectites, with the lower charge-density day (SWy-2) displaying a greater sorption capacity than the higher charge-density day (SAz-1). The presence of humic add did not impact pesticide sorption by K + clays, but could enhance or suppress pesticide sorption by Ca 2+ -clays. A composite model for estimating pesticide sorption, which assumes mineral and organic matter function individually as sorbent phases, predicted sorption within a factor of 0.8 to 1.5 times the measured values. Humic add did not contribute to pesticide desorption hysteresis in K + -humic add-day complexes, but was a source of hysteresis in the corresponding Ca 2+ complexes. The basal spacings of K-SWy-2 and humic add-modified K-SWy-2 increased gradually from approximately 10.4 to 12.2 A with increasing 4,6-dinitro-o-cresol loadings. Also, XRD patterns of humic acid-modified and unmodified K-SWy-2 smectite days were found identical. These results demonstrate the Intercalation of 4,6-dinitro-o-cresol and suggest that humic adds are restricted to the external surfaces of day tactoids. Together, these results indicate that clay mineral fractions in soils, including those with organic coatings, may play an important role in the retention of certain pesticides.

Molecular weight fractionation of humic substances by adsorption onto minerals

Abstract: 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.

Hygroscopic properties of two model humic-like substances and their mixtures with inorganics of atmospheric importance.

Abstract: Water-soluble macromolecular polyacids can play a potentially important role in the hygroscopic properties of atmospheric aerosols. These acids have molecular structures similar to natural fulvic acids (FA) (or humic acids) and are referred to as humic-like substances (HULIS). In this study, the hygroscopicity of HULIS and the mixture of HULIS and sodium chloride (NaCl) and that of HULIS and ammonium sulfate (AS) aerosols at a mass ratio of 1:1 are studied using two natural FA: the Nordic Aquatic Fulvic Acid (NAFA) and the Suwannee River Fulvic Acid (SRFA) as model compounds in an electrodynamic balance. NAFA and SRFA both absorbed and desorbed water reversibly without crystallization and retained water at a relative humidity (RH) < 10%. NAFA and SRFA have a mass growth ratio of 1.25 and 1.45 from RH = 10% to RH = 90%, respectively. However, these results are different from those of another natural FA (the Nordic River Fulvic Acid Reference) in the literature. The differences are possibly due to the differences in the chemical composition of the natural FA, which depends on their sources and the isolation methods. These results suggest that a standardization of the isolation methods of HULIS is needed for better understanding of their atmospheric properties and environmental impacts. In general, the deliquescence and crystallization RH of FA-inorganic mixtures are comparable with those of their respective pure inorganic species. Since FA are less hygroscopic than NaCl and AS, all mixtures absorb less water compared to their respective pure inorganic species of equal particle mass. The FA-AS mixtures have a larger water uptake than the sum of those of the FA and AS individually following a simple additivity rule as noninteracting species at RH = 90%. This enhancement effect increases as the RH decreases. There is no such enhancement effect for the FA-NaCl mixtures until RH is below 90%. These results reveal that the effect of the interactions between FA and inorganic species on the water uptake of the mixtures, in general, is a function of RH.