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PubMed2005

Deconvolution and quantification of hydrocarbon-like and oxygenated organic aerosols based on aerosol mass spectrometry.

A new technique has been developed to deconvolve and quantify the mass concentrations of hydrocarbon-like and oxygenated organic aerosols (HOA and OOA) using highly time-resolved organic mass spectra obtained with an Aerodyne Aerosol Mass Spectrometer (AMS). This technique involves a series of multivariate linear regressions that use mass-to-charge ratios (ml/s) 57 (mostly C4H9+) and 44 (mostly CO2+)-the identified AMS mass spectral tracers for HOA and OOA, respectively-as the initial principal components. Two algorithms have been developed: algorithm 1 is based solely on m/z 44 and m/z 57, and algorithm 2 is an iterative procedure expanded from algorithm 1. This technique was applied to the AMS organic aerosol data acquired at the EPA Pittsburgh Supersite during September 2002. The reconstructed organic concentrations (= HOA + OOA) agree well with the measured values (r2 = 0.997, slope = 0.998), and the reconstructed organic data matrix (size = 3199 time steps x 300 m/z's) explains 99% of the variance in the measured time series. In addition, the extracted mass spectrum of HOA shows high similarity to those of diesel exhaust, lubricating oil, and freshly emitted traffic aerosols observed in urban areas, while the spectrum of OOA closely resembles those of aged organic aerosols sampled in rural areas and also shows similarity with the spectrum of fulvic acid- a humic-like substance that is ubiquitous in the environment and has previously been used as an analogue to represent polyacid components found in highly processed and oxidized atmospheric organic aerosols. There is evidence for the presence of a third component, although its contribution to the total organic signal appears to be small in this study. The most important result is that m/z 44 and m/z 57 are reliable AMS mass spectral "markers" that provide the "first guess" for algorithm 2 which allows the quantitative description of the organic aerosol concentration and mass spectra over a period of 16 days in a major urban area and allows the extraction of mass spectra of OOA and HOA that can be interpreted chemically. These findings indicate the potential of performing organic source apportionment on the basis of total particle mass, rather than on the basis of organic tracer compounds that contribute a small fraction of this mass.

Aerosols↗

PubMed2005

Influence of addition order and contact time on thorium(IV) retention by hematite in the presence of humic acids.

The influence of addition order and contact time in the system hematite (alpha-Fe2O3)-humic acid (HA)-thorium(IV) (Th(IV)) was studied in batch experiments. Th(IV) is considered here as a chemical analogue of other actinides (IV). The sorption isotherms were acquired varying pH in the range 2-10 and HA concentration in the range 1-100 mg/L. As already observed by numerous authors, Th(IV) retention was hindered when HA and hematite were equilibrated beforehand during 24 h. As it has been observed in a previous study, this effect was drastic when the ratio between humic and surface (iron oxide) sites exceeds a critical value. However, when HA was added after a 24-h equilibration of the hematite-Th(IV) system, Th(IV) was barely desorbed from the iron oxide surface. Furthermore, no drastic effect of the ratio between humic and surface sites could be evidenced, as the increase of HA concentration only results in a slight monotonic decrease in Th(IV) retention. Increasing contact time between components of the systems only indicated slight Th(IV) retention variation. This was interpreted as a consequence of slow kinetic controls of both the Th(IV)-HA complexation and HA-hematite sorption.

Adsorption↗

PubMed2005

Evaluation of a novel malathion immunoassay for groundwater and surface water analysis.

Malathion is an organophosphorus insecticide commonly used in crops and indoor applications. Negative effects of malathion on human health and ecosystems are of growing concern. In this work, novel malathion haptens are synthesized to develop an ELISA screening method. The immunoassay is based on a conjugate-coated format and shows a limit of detection of 0.11 ng/mL, an IC50 of 1.58 ng/mL, a dynamic range between 0.23 and 10.94 ng/ mL, and a cross-reactivity of <2% with structurally related compounds. The developed ELISA has been used to quantify malathion in groundwater and surface water samples. The good recoveries achieved and the agreement with those given by the GC-MS reference method indicate the potential of the assay for environmental monitoring of malathion in natural waters without purification or preconcentration steps. The effect of dissolved organic matter (humic acids) on the ELISA was evaluated, resulting in the conclusion that the immunoassay can be successfully performed in surface water samples with a humic acid content up to 10 mg/L, without sample pretreatment. Samples with a high humic acid content can be analyzed through ELISA after solid-phase extraction, eluting with acetone or acetonitrile.

Acetone↗

PubMed2005

Role of humic acid and ouinone model compounds in bromate reduction by zerovalent iron.

Experiments were conducted to examine the role of humic acid and quinone model compounds in bromate reduction by Fe(0). The reactivity of Fe(0) toward bromate declined by a factor of 1.3-2.0 in the presence of humic acid. Evidence was obtained that the quick complexation of humic acid with iron species and its adsorption passivated the iron surface and decreased the rate of bromate reduction by Fe(0). On the other hand, in the long run, the reduced functional groups present in humic acid were observed to regenerate Fe(II) and reduce bromate abiotically. Compared with the case of humic acid only, the simultaneous presence of Fe(II) and humic acid significantly increased the bromate removal rate. Fe(III)/Fe(II) acted as a catalyst in the oxidation of humic acid by bromate. Anthraquinone-2,6-disulfonate (AQDS) and lawsone did not cause any significant effect on the bromate reduction rate by Fe(0). However, the redox reactivity of lawsone in the presence of Fe(III) was evident, while AQDS did not show any under the tested conditions. The difference was attributable to the presence/ absence of reducing functional groups in the model compounds. The electron spin resonance further demonstrated that the redox functional groups in humic acid are most likely quinone-phenol moieties. Although the bromate reduction rate by regenerated Fe(II) is a few times slower than that by Fe(0), the reactive Fe(II) can be, alternatively, reductively formed to maintain iron surface activation and bromate reduction to prolong the lifetime of the zerovalent iron.

Adsorption↗

PubMed2004

Quantifying unfrozen water in frozen soil by high-field 2H NMR.

To understand wintertime controls of biogeochemical processes in high latitude soils it is essential to distinguish between direct temperature effects and the effects of changes in water availability mediated by freezing. Efforts to separate these controls are hampered by a lack of adequate methods to determine the proportion of unfrozen water. In this study we present a high-field 2H2O NMR method for quantifying unfrozen water content in frozen soil. The experimental material consisted of the humic layer of a boreal spruce forest soil mixed with varying proportions of quartz sand and humidified with deuterium-enriched water. The relative standard deviation of unfrozen water content (measured as NMR signal integral) was less than 2% for repeated measurements on a given sample and 3.5% among all samples, based on a total of 16 measurements. As compared to 1H NMR, this 2H NMR method was found to be superior for several reasons: it is less sensitive to field inhomogeneity and paramagnetic impurities, it gives a bigger line shape difference between the ice and liquid signal, it shows a sharper response to water fusion, and it excludes the possibility of hydrogen in the organic material interfering with the measurement.

Deuterium↗

PubMed2004

Chlorination byproduct formation in the presence of humic acid, model nitrogenous organic compounds, ammonia, and bromide.

The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and cyanogen halides (CNXs) after chlorination of synthetic solutions containing humic acid, nitrogenous organic (N-organic) compounds, ammonia, and bromide ions was studied. Humic acid (from Aldrich) was used to provide the source of the precursors. Glycine was chosen as the primary model N-organic compound and other four model N-organic compounds (including glutamic acid, glycylglycine, diethylamine, and methylamine) were also evaluated for comparison. The formation of THMs and HAAs was found to decrease with increasing glycine and ammonia concentrations but to increase with increasing bromide ion concentration. CNX formation was found to be highly sensitive to free chlorine to glycine ratios, and its formation trends were significantly affected bythe presence/absence of ammonia. The incorporation of bromine changed the byproducts speciation toward brominated species and enhanced the yields of total THMs, HAAs, and CNXs. Different model N-organic compounds exerted different effects on the formation of THMs, HAAs, and CNXs. Their effects on the formation of THMs and HAAs were likely dependent on their reactivity to chlorine in competing with the humic acid chlorination reactions. The difference in the CNCI yields was attributable to the variations in the compound structures.

Ammonia↗

PubMed2004

Investigation of interparticle forces in natural waters: effects of adsorbed humic acids on iron oxide and alumina surface properties.

The nature of interparticle forces acting on colloid particle surfaces with adsorbed surface films of the internationally used humic acid standard material, Suwannee River Humic Acid (SHA), has been investigated using an atomic force microscope (AFM). Two particle surfaces were used, alumina and a hydrous iron oxide film coated onto silica particles. Adsorbed SHA dominated the interactive forces for both surface types when present. At low ionic strength and pH > 4, the force curves were dominated by electrostatic repulsion of the electrical double layers, with the extent of repulsion decreasing as electrolyte (NaCl) concentration increased, scaling with the Debye length (kappa(-1)) of the electrolyte according to classical theory. At pH approximately 4, electrostatic forces were largely absent, indicating almost complete protonation of carboxylic acid (-COOH) functional groups on the adsorbed SHA. Under these conditions and also at high electrolyte concentration ([NaCl] > 0.1 M), the absence of electrostatic forces allowed observation of repulsion forces arising from steric interaction of adsorbed SHA as the oxide surfaces approached closely to each other (separation < 10 nm). This steric barrier shrank as electrolyte concentration increased, implying tighter coiling of the adsorbed SHA molecules. In addition, adhesive bridging between surfaces was observed only in the presence of SHA films, implying a strong energy barrier to spontaneous detachment of the surfaces from each other once joined. This adhesion was especially strong in the presence of Ca2+ which appears to bridge SHA layers on each surface. Overall, our results show that SHA is a good model for the NOM adsorbed on colloids.

Adsorption↗

PubMed2004

Solar photodecomposition of decabromodiphenyl ether: products and quantum yield.

Decabromodiphenyl ether (BDE209) is a widely used flame retardant, yet information regarding its environmental transformation rates and pathways are largely unknown. Because photochemical transformation is often suggested as a potentially important fate process for BDE209, the reaction rate and products of the solar degradation under favorable solvent conditions were determined in this study. Decabromodiphenyl ether (BDE209), dissolved in hexane, reacts in minutes via direct solar irradiation, at midlatitude (40 degrees 29' N, 86 degrees 59.5' W) in afternoon July and October sunlight. Observed first-order reaction rate constants, kobs, at the different exposure times were kobs = 1.86 x 10(-3) s(-1) (July) and kobs = 1.11 x 10(-3) s(-1) (October). The photodecomposition quantum yield was calculated from these data and from the solar irradiance data measured at 300, 305.5, 311.4, 317.6, 325.4, 332.4, and 368 nm reported at a USGS UVB monitoring station located nearby. The range of wavelengths where both the molar absorptivity of BDE209 and the solar irradiance flux are significant occurs between 300 and 350 nm. For this range, the wavelength average quantum yield for BDE209 photoreaction, phiave, was calculated to be 0.47. The difference between kobs values at the two exposure times is explained fully by the difference between the solar irradiation fluxes. Upon solar irradiation, BDE209 reductively dehalogenated to other polybrominated diphenyl ethers (PBDEs). During 34 h of irradiation, PBDEs ranging from nona- to tri-bromodiphenyl ethers were observed. In total, 43 PBDEs were detected, and the GC retention times and mass spectral fragment patterns of 21 products matched those of available congener standards, including congeners 2,2',4,4',5-pentabromodiphenyl ether and 2,2',4,4'-tetrabromodiphenyl ether.

Bromobenzenes↗

PubMed2004

Lead phosphate minerals: solubility and dissolution by model and natural ligands.

Due to their relatively low solubility, lead-phosphate minerals may control Pb solution levels at a low value in natural environments. We reportthe solubility of Pb from two lead-orthophosphate mineral suspensions (beta-Pb9(PO4)6 and PbHPO4) after aging for 3 years. Lead (Pb2+) activity in the aged suspensions was compared to the activity calculated using the Ksp values of various Pb-PO4 minerals reported in the literature. We also determine the time-dependent dissolution of the aged lead-phosphate minerals by organic and inorganic ligands containing S-functional groups (cysteine, methionine, and thiosulfate) and by a soil extracted humic acid. We find the activity of Pb2+ in the aged lead-phosphate suspensions to be 1-2 orders of magnitude higher than predicted by the Ksp values reported in the literature. Disagreement between measured and Ksp-calculated activities has been reported in other investigations of Pb-PO4 minerals; we compiled some of the data and present them together with our results. Furthermore, the time-dependent dissolution experiments indicate that, in most cases, lead phosphates are partly dissolved in the presence of soluble ligands, i.e., model sulfides and humic acid. The soil-extracted humic acid enhanced the dissolution of Pb from the high pH (7.2) lead-phosphate (beta-Pb9(PO4)6) mineral while suppressing Pb dissolution from the low pH (3.8) lead-phosphate (PbHPO4) mineral. While the low molecularweight sulfur-containing ligands enhanced Pb dissolution, their effect was less pronounced. We conclude that (i) nonequilibrium conditions prevail in the mineral suspensions even after 3 years of aging; and (ii) soluble ligands present in soils, sediments, and natural waters can potentially dissolve Pb from lead-phosphate minerals; such ligands, then, may enhance the biological availability and mobility of Pb in the environment.

Biological Availability↗

PubMed2004

Black carbon and kerogen in soils and sediments. 2. Their roles in equilibrium sorption of less-polar organic pollutants.

The first paper of this series reported that soil/sediment organic matter (SOM) can be fractionated into four fractions with a combined wet chemical procedure and that kerogen and black carbon (BC) are major SOM components in soil/sediment samples collected from the industrialized suburban areas of Guangzhou, China. The goal of this study was to determine the sorptive properties forthe four SOM fractions for organic contaminants. Sorption isotherms were measured with a batch technique using phenanthrene and naphthalene as the sorbates and four original and four Soxhlet-extracted soil/sediment samples, 15 isolated SOM fractions, and a char as the sorbents. The results showed that the sorption isotherms measured for all the sorbents were variously nonlinear. The isolated humic acid (HA) exhibited significantly nonlinear sorption, but its contribution to the overall isotherm nonlinearity and sorption capacity of the original soil was insignificant because of its low content in the tested soils and sediments. The particulate kerogen and black carbon (KB) fractions exhibited more nonlinear sorption with much higher organic carbon-normalized capacities for both sorbates. They dominate the observed overall sorption by the tested soils and sediments and are expected to be the most important soil components affecting bioavailability and ultimate fate of hydrophobic organic contaminants (HOCs). The fact that the isolated KB fractions exhibited much higher sorption capacities than when they were associated with soil/sediment matrixes suggested that a large fraction of the particulate kerogen and BC was not accessible to sorbing HOCs. Encapsulation within soil aggregates and surface coverage by inorganic and organic coatings may have caused large variations in the accessibility of fine kerogen and BC particles to HOCs and hence lowered the sorption capacity of the soil. This variability posts an ultimate challenge for precisely predicting HOC sorption by soils from the contents of different types of SOM.

Adsorption↗

PubMed2004

History-dependent sorption in humic acids and a lignite in the context of a polymer model for natural organic matter.

We examined sorption of two apolar compounds in three samples of macromolecular natural organic matter (NOM) in order to test whether history-dependent ("irreversible") behaviors, including sorption hysteresis and the conditioning effect, agree with a pore deformation/creation hypothesis applicable to the glassy organic solid state as proposed in the polymer literature. The compounds are 1,2,4-trichlorobenzene (TCB) and naphthalene (Naph). The NOM samples are a soil humic acid (H-HA), an Al3+-exchanged form of the same humic acid (Al-HA), and a low-rank coal (Beulah-Zap lignite, BZL). The HAs, at least, are believed free of environmental black carbon. The degree of nonlinearity in the isotherm and the ratio of hole-filling to solid-phase dissolution increased in the order of hardness (stiffness) of the solid: H-HA < Al-HA < BZL. Independent of solid, solutes show a 14-18 kJ/mol preference for hole "sites" as compared to dissolution "sites", which we attribute to the free energy needed in the dissolution domain to create a cavity to accommodate the solute. All solids exhibited hysteresis and the conditioning effect, which refers to enhanced re-sorption after pretreatment with a conditioning agent (in this case, chlorobenzene). Conditioning the sample results in increased sorption and increased contribution of hole-filling relative to dissolution. The effects of original hole population, matrix stiffness, and solute concentration on the hysteresis index and on the magnitude of the conditioning effect are consistent with a pore-deformation mechanism as the underlying cause of sorption irreversibility. This mechanism involves concurrent processes of irreversible hole expansion and the creation of new holes by the incoming sorbate (or conditioning agent). The results show that nonlinear and irreversible behavior may be expected for macromolecular forms of NOM that are in a glassy state and emphasize the case that NOM is not a passive sorbent but may be physically altered by the sorbate.

Adsorption↗

PubMed2004

Structure elucidation and characterization of polychlorinated biphenyl carboxylic acids as major constituents of chromophoric dissolved organic matter in seawater.

Chromophoric or colored dissolved organic matter (CDOM) is one of the principal light adsorbing components of seawater, particularly in the ultraviolet, where it attenuates over 90% of downwelling ultraviolet radiation. In highly productive coastal regions and throughout most of the global ocean, in situ biological production is the major source of CDOM. However, little is known about CDOM composition on the molecular level, and there are only a few reports that link CDOM composition to autochthonous biological sources. Here we report the isolation and characterization of CDOM components from one coastal and two open-ocean sites. Each sample contains a complex mixture of light absorbing (300-400 nm) components, including 2,4-dichlorobenzoic acid and a suite of novel, polychlorinated biphenyl carboxylic acids that closely resemble polychlorinated biphenyls (PCBs) of anthropogenic origin. However, the global inventory and isomer distribution of dissolved chlorinated aromatic acids suggest they are derived from in situ biological production rather than anthropogenic contaminants. These novel chlorinated aromatic acids account for a significant amount of CDOM adsorption in the ultraviolet.

Adsorption↗

PubMed2005

Effect of humic and fulvic acid concentrations and ionic strength on copper and lead binding.

We investigated the influence of humic and fulvic acid concentration (in the range of 1-1000 mg/L) on the binding of the two trace metals Cu(II) and Pb(II). The ability of the non-ideal competitive adsorption (NICA)-Donnan model to correctly predict Cu and Pb binding at low humic or fulvic acid concentration and lower ionic strength (0.01 M NaNO3), based on model parameters obtained from experiments conducted at high humic or fulvic acid concentrations (approximately 1000 mg/L) and higher ionic strength (0.1 M NaNO3), was tested. The binding of Cu and Pb to humic and fulvic acid in 0.01 M NaNO3 was determined over wide ranges in proton and metal ion activities using three different methods: ligand exchange-adsorptive differential pulse cathodic stripping voltammetry at low humic or fulvic acid concentrations (1-3 mg/L), differential pulse anodic stripping voltammetry at intermediate humic or fulvic acid concentrations (10-20 mg/L), and ion-selective electrodes at high humic or fulvic acid concentrations (approximately 1000 mg/L). The results demonstrate that binding isotherms for Cu and Pb can be measured at low humic or fulvic acid concentration using suitable voltammetric techniques. The binding isotherms for Cu and Pb to humic and fulvic acid obtained at constant pH values in the range of pH 4-8 are shown to be independent of humic and fulvic acid concentration. The NICA-Donnan model, calibrated for Cu and Pb binding using data measured at high humic and fulvic acid concentrations and an ionic strength of 0.1 M, accurately predicts Cu and Pb binding at low humic and fulvic acid concentrations and lower ionic strength (0.01 M). We conclude that NICA-Donnan parameters obtained by fitting experimental data measured with ion-selective electrodes at high humic or fulvic acid concentrations can be used for geochemical modeling of soils and aquatic environments with much lower concentrations of humic or fulvic acids.

Adsorption↗

PubMed2005

Impact of natural organic matter on floc size and structure effects in membrane filtration.

Hematite (10 mg of Fe/L) floc-humic acid assemblages have been formed at pH 4 either by first aggregating hematite particles with salt (100 mM KCl) and then adding humic acid (salt-particle-organic or SPO assemblages) or by suspending the hematite particles in humic acid solutions and then adding salt to induce aggregation (organic-particle-salt or OPS assemblages). The behavior of these assemblages upon deposition on microfiltration (MF) membranes has then been investigated. In the OPS case, the fractal dimension (dF) of the assemblages formed varied dramatically depending upon the extent of charge neutralization by added fulvic acid with dF values typical of diffusion-limited cluster aggregates at low (0.1-0.2 mg/L) humic acid concentrations and dF values typical of reaction-limited cluster aggregates either in the absence of humic acid or concentrations greater than 0.4-0.6 mg/L. In the SPO case, dF values on the order of 2.1 were initially observed and were found to decrease to around 1.8-1.9 for humic acid concentrations greater than 0.6-0.8 mg/L. OPS assemblages with low fractal dimensions were found to be highly compressible once deposited on MF membranes with significantly higher specific cake resistances than was the case for SPO assemblages at transmembrane pressures of 50 kPa and above. These results highlight the importance of both the choice of coagulant (e.g., preformed vs formed in situ) and the transmembrane pressure to which a membrane filtration process might be allowed to rise prior to removal of the fouling layer.

Benzopyrans↗

PubMed2005

Model assessment of biogeochemical controls on dissolved organic carbon partitioning in an acid organic soil.

A chemical model (constructed in the ORCHESTRA modeling framework) of an organic soil horizon was used to describe soil solution data (10 cm depth) and assess if seasonal variations in soil solution dissolved organic carbon (DOC) could be explained by purely abiotic (geochemical controls) mechanisms or whether factors related to biological activity are needed. The NICA-Donnan equation is used to describe the competitive binding of protons and cations and the charge on soil organic matter. Controls on organic matter solubility are surface charge and a parameter, gamma, that accounts for the distribution of humic molecules between hydrophobic and hydrophilic fractions. Calculations show that the variations in solute chemistry alone are not sufficient to account for the observed variations of DOC, but factors that alter gamma, such as biological activity, are. Assuming that DOC in organic soils is derived from soluble humic material and that gamma is modified seasonally due to biological activity (with monthly soil temperature used as a surrogate for biological activity) we are able to model the observed seasonality of soil solution DOC over a 10-year period. Furthermore, with modeled DOC coupled to other geochemical processes we also model soil solution pH and Al concentrations.

Carbon↗

PubMed2005

Photoinduced oxidation of antimony(III) in the presence of humic acid.

Interactions of antimony with natural organic matter (NOM) are important for the fate of Sb in aquatic systems. The kinetics of the photosensitized oxidation of Sb(III) to Sb(V) in the presence of Suwannee River Humic Acid (SRHA) was investigated using UV-A and visible light (medium-pressure mercury lamp). At a concentration of 5 mg L(-1) dissolved organic carbon (DOC) the light-induced reaction was 9000 times faster (rate coefficient k(exp) = 7.0 +/- 0.05 x 10(-4) s(-1)) than the dark reaction and followed pseudo-first-order kinetics. Rates increased linearly with the concentration of DOC. Between pH 4 and 8 rates increased by a factor of 5. Further results and kinetic considerations indicate that singlet oxygen, hydroxyl radicals, hydrogen peroxide, and hydroperoxyl radicals/superoxide are not important photooxidants in this system, while other NOM-derived reactive species, in particular excited triplet states and/or phenoxyl radicals, seem to be relevant. The dependence of rate coefficients on Sb(III)/DOC ratio was consistent with a two binding site model including (i) a strong binding site at low concentration inducing fast oxidation, (ii) a weak binding site at high concentration inducing slower oxidation, and (iii) the even slower oxidation of Sb(OH)3. Photoirradiation of natural water samples spiked with Sb(III) showed that the oxidation rates could be well predicted based on DOC.

Antimony↗

PubMed2005

Proton binding to humic acids from organic amendments and amended soils by the NICA-Donnan model.

The acid-base properties of humic acids (HAs) are known to significantly affect the acid-base buffering capacity of soils, thus having a marked influence on the speciation of cations in the soil solid and liquid phases. Detailed information on the proton binding behavior of humic-like acids (HALs) from organic amendments and humic acids (HAs) from amended soils is, therefore, of intrinsic interest for the evaluation of the agronomic efficacy and environmental impact of soil amendment. In this work, the acid-base properties of HLAs isolated from sewage sludge (SS) and municipal solid waste compost (MSWC), and HAs isolated from soils amended with either SS or MSWC and the corresponding nonamended control soils were investigated by potentiometric titrations at various ionic strengths (0.01, 0.05, 0.1, and 0.3 M) over the pH range from 3.5 to 10.5. The nonideal competitive adsorption (NICA)-Donnan model that describes proton binding by two classes of binding sites with low and high proton affinity, i.e., carboxylic- and phenolic-type groups, was fit to titration data, and a set of fitting parameters was obtained for each HLA and HA sample. The NICA-Donnan model successfully described the shapes of the titration curves, and highlighted substantial differences in site density and proton-binding affinity between the HLAs and HAs examined. With respect to the nonamended control soil HAs, SS-HLA and MSWC-HLA were characterized by smaller carboxylic-type and phenolic-type group contents, larger affinities for proton binding by the carboxylic-type groups, and smaller affinities for proton binding by the phenolic-type groups. Amendment with SS and MSWC determined a number of modifications in soil HAs, including decrease of acidic functional group contents, slight increase of proton affinity of carboxylic-type groups, and slight decrease of the affinities for proton binding by phenolic-type groups. These effects were more evident in the HA fraction from the SS-amended soil than in the HA fraction from the MSWC-amended soil. Thus, both organic amendments examined can be a considered as a valuable source of organic matter for soil. However, MSWC appears to be an amendment of greater quality producing a smaller impact than SS on proton-binding behavior of soil HA.

Binding Sites↗

PubMed2005

NMR spectroscopy study of freshwater humic material in light of supramolecular assembly.

The structural similarity-dissimilarity of several humic-type derivatives, separated from a strongly colored freshwater sample by different sorbing solid techniques, tangential-flow ultrafiltration (UF), and large-scale preparative high-performance size-exclusion chromatography (HPSEC), were in detail studied with one-dimensional liquid 1H and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, especially in light of the native humic-type dissolved organic matter (DOM-HM). The results support the applicability of functional cross-linked poly(vinylpyrrolidone) (PVP) or diethylaminoethyl-cellulose (DEAE) sorbents in concentrating representative integrated wholes of aquatic humic-type material along with a conventional nonionic XAD-8/DAX-8 (polymethyl methacrylates) technique. Apart from the fact that the acidification of the original humic water before a separation procedure seems not to be so destructive to the original structural composition of the DOM-HM as expected, the refinement of aquatic humic solutes, independent of the selected sorbing solid technique, will cause structural changes in the separated humic complexes in comparison with the situation predominating in the original starting material. Tangential-flow ultrafiltration (UF) proved an overpowering reliability to concentrate the aquatic DOM-HM. Most fundamental is the combined outcome of different HPSEC experiments and determined structural functionalities which indicate that almost all original DOM-HM solutes are aggregated mixtures consisting of structurally similar associations possessing various molecular size ranges, which can be separated from their integrated whole as nearly homogeneous and uniform species. This finding permits a reasonable starting point to go on working with more advanced multidimensional NMR techniques in resolving the uncertainty about supramolecular assembly of dissolved humic material. The tested conformity between the obtained molecular NMR descriptors and the corresponding previously collected FT-IR parameters was acceptable thus speaking for the fact that the less sensitive FT-IR spectroscopy can also provide valuable information on the structural and functional properties of heterogeneous humic-type mixtures.

Fresh Water↗