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PubMed2003

Strong hg(II) complexation in municipal wastewater effluent and surface waters.

The speciation of mercury(II) in the aquatic environment is greatly affected by the presence of ligands capable of forming extremely strong complexes with Hg(II). In this study, a novel competitive ligand exchange (CLE) technique was used to characterize Hg(II)-complexing ligands in samples collected from three municipal wastewater treatment plants, a eutrophic lake, a creek located downstream of an abandoned mercury mine, and a model water containing dissolved Suwannee River humic acid. These samples contained 3.3-15.9 mg/L dissolved organic carbon and were amended with 1.0-1.7 nM Hg(II) for CLE analysis. Results indicated that all samples contained labile Hg(II)-complexing ligands with conditional stability constants similar to those of reduced sulfur-containing ligands. Two wastewater effluent samples also contained approximately 0.5 nM of ligands that formed extremely strong Hg(II) complexes that did not dissociate in the presence of competing ligands. The conditional stability constant of these extremely strong or nonlabile complexes (i.e., (c)K(HgL)) were estimated to be greater than 10(30), for the reaction Hg(2+) + L' = HgL. The third wastewater sample and the eutrophic lake sample contained lower concentrations, 0.07-0.09 nM, of nonlabile Hg(II)-complexing ligands. The results suggested that these extremely strong Hg(ll)-complexing ligands should account for most of the dissolved Hg(II) species in municipal wastewater effluent and may dominate Hg(II) speciation in effluent-receiving waters.

Ditiocarb↗

PubMed2004

Key role of the low molecular size fraction of soil humic acids for fluorescence and photoinductive activity.

The IHSS soil humic acid (HA) standard and two HAs from soils of very different origin (Chernozem and Ranker) were fractionated by tandem size-exclusion chromatography-polyacrylamide gel electrophoresis. From each HA, three fractions with different molecular sizes (MSs) and electrophoretic mobilities were obtained and investigated for their fluorescence properties and abilityto photoinduce the transformation of 2,4,6-trimethylphenol and herbicide fenuron. Regardless of the source of the HA, the two high MS fractions were found to be very weakly fluorescent. They photoinduced the degradations of fenuron and 2,4,6-trimethylphenol less efficiently than the bulk HA (10-50-fold and 1.4-5.3-fold, respectively). In contrast, the low MS fraction was proved to be fluorescent and to photoinduce the transformation of probes as least as efficiently than the bulk HA. These results show that (i) most of fluorophores and a great part of photoinductive chromophores are located in the low MS fractions of soil HAs and (ii) this distribution of photochemically active constituents may be characteristic across broad soil types.

Chromatography, Gel↗

PubMed2004

Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), coupled with cross-polarization magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy and Kendrick mass defect analysis, was used to study the molecular composition of an aromatic carbon-rich humic acid extracted from a dark black soil from Iwata, Japan. Black carbon, produced by the incomplete combustion of fossil fuels and organic matter, has been suggested as a major component of humic acids having intense peaks in the aromatic and carboxyl regions of the 13C NMR spectrum. Taking advantage of the high resolving power of FT-ICR MS to make precise formula assignments, three different types of highly carboxylated polycyclic aromatic compounds were identified in the sample: linearly fused aromatic structures, aromatic structures linked by carbon-carbon single bonds, and highly condensed aromatic structures. These carboxylated aromatic structures have a low mass defect in their mass spectra due to their abundance of oxygen and deficiency of hydrogen. This mass defect is observed in the vast majority of peaks present in the entire mass spectrum, differentiating them from structures that are hydrogen-rich (e.g., fatty acids, proteins, carbohydrates). Thus, we conclude that the bulk of the sample analyzed is comprised of these heavily carboxylated, hydrogen-deficient, condensed aromatic structures, features believed to be characteristic of black carbon-like material.

Carbon↗

PubMed2003

"Humic coverage index" as a determining factor governing strain-specific hydrocarbon availability to contaminant-degrading bacteria in soils.

We report development of a novel parameter for quantifying the amount of humic and fulvic acids per unit surface area in a particular soil. This quantity, the "humic coverage index" (HCI), provides a measurement of the relative spatial extents and/or thicknesses of the humic/fulvic overlayers in different soils, and, therefore, can be used in modeling various soils' behavior in sequestration processes in which humic materials are involved. HCI is herein applied to modeling biodegradation of aromatic and aliphatic hydrocarbons (phenanthrene, pyrene, and hexadecane) by several bacterial strains. Results indicate that, for the cases studies here, contaminant biodegradation is highest at a particular HCI and decreases if the coverage density of humic material is lower or higher than this optimum value. The HCI value at which maximal degradation was observed varied across different strains (indicating strain-specific differences in ability to degrade contaminants sorbed to humic materials) and, to a lesser extent, across different contaminants. The HCI concept is also demonstrated to be useful in explaining soil-, strain-, and contaminant-specific variations in the ability of fulvic acid supplementation to enhance contaminant biodegradation. Finally, we show that, in general, strains which are comparatively better at degrading contaminants in high-HCI soils also show enhanced contaminant mineralization in vitro in the presence of humic acids, such as when hydrocarbons are adsorbed onto these materials.

Alkanes↗

PubMed2004

Investigations of the reactions of monochloramine and dichloramine with selected phenols: examination of humic acid models and water contaminants.

Our paper reports on the reactivities and orientations of two common phenols, phenol (2) and m-cresol (3), and some of their chlorinated intermediates with aqueous monochloramine, NH2Cl, and dichloramine, NHCl2. We also examined the further reactivity of 2,4,6-trichlorophenol (4) with the chloramines. The phenols are an important area of investigation because they are substituents in the humic acids and are common contaminants in water. m-Cresol (3) was found to be more reactive than phenol (2)with both chlorinating agents. Both NH2Cl and NHCl2were sufficiently reactive to chlorinate all positions ortho and para to the hydroxyl groups. Mono- and dichloramine showed the same orientation with 2 but different orientations in their reactions with the substituent phenols. Indophenol (as its salt) was formed to a minor extent at high pH but not at pH 9. Both NH2Cl and NHCl2 rapidly replaced the parachlorine in 2,4,6-trichlorophenol (4) to give a mixture of 2,6-dichloro-1,4-benzoquinone-4-(N-chloro) imine (5) and 2,6-dichloro-1,4-benzoquinone (18). Similar reactions occurwith 2,4,6-trichloro-m-cresol (17) and 2,4,6-trichloro-3-methoxyphenol (29). The products for 17 were confirmed by mass spectrometry (El and Cl), 1H NMR, 13C NMR, and IR; the products for 29 were confirmed by mass spectrometry (El and Cl) and IR. An ion radical mechanism is suggested to account for the chlorine replacement by the chloramines. [No side chain oxidation of the methyl group in 17 in H20 or ether occurred, with or without ultraviolet radiation.] Both 5 and 18 underwent further chlorination with NH2Cl or NHCl2. Imine 5 did not function as a chlorinated agent.

Chloramines↗

PubMed2003

Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter.

Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the > 10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (phi(i,n)). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (phi(T,n) = sigma phi(i,n)) was observed for hydrophobic neutral DOM fractions, followed by lower phi(T,n) values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

Biomass↗

PubMed2004

In-situ speciation of Ni and Zn in freshwaters: comparison between DGT measurements and speciation models.

The technique of DGT (diffusive gradients in thin films) was used for the first time to measure in situ the distribution of Zn and Ni between inorganic species and complexes with fulvic and humic acids in natural waters. With DGT, metals are bound to a resin embedded in a layer of hydrogel after diffusive transport through an adjacent layer of hydrogel. The metal concentrations in the waters can be quantified using simple diffusion equations. By using devices with hydrogels of different pore size, large and small complex species were discriminated. Inorganic species diffuse freely through all gels, but larger organic complexes with fulvic and humic acids diffuse less freely through more restricted gels (gels with smaller pore size). Systematic differences between DGT devices containing gels of different pore size were obtained. Their calibration for the diffusion of fulvic and humic complexes allowed calculation of the concentrations of labile inorganic (Zn, 34.6 +/- 2.5 nM; Ni, 23.5 +/- 0.9 nM) and labile organic (Zn, 43.1 +/- 2.9 nM; Ni, 11.2 +/- 0.7 nM) complexes. The concentration of Zn measured by anodic stripping voltammetry in samples returned to the laboratory lay between the DGT-measured inorganic concentration and the total dissolved concentration, consistent with partial measurement of organic complexes of Zn. The speciation model WHAM successfully predicted the species distribution of Ni, Zn, and Cu, provided that competitive binding by Fe(III) was considered. Using the speciation models WHAM and ECOSAT, free ion activities of Zn and Ni were calculated from (1) the total inorganic species measured by DGT and (2) the total dissolved species and dissolved organic carbon. The calculations confirmed the good model predictions of metal-humic binding but highlighted problems with default databases used for the speciation of inorganic components.

Benzopyrans↗

PubMed2004

Cadmium bioavailability and accumulation in the presence of humic acid to the zebra mussel, Dreissena polymorpha.

Metal speciation in aquatic systems is mainly determined by the type and concentration of ligands present in solution. A very important group of complexing agents is dissolved organic matter (DOM), e.g., humic and fulvic acids. According to the free-ion activity model, only the free metal ion is available to biota. Nevertheless, DOM has been reported to decrease or increase metal uptake, leading to uncertainty concerning the bioavailability of metal-DOM complexes. In this work the effect of Aldrich humic acid on cadmium accumulation by the zebra mussel, Dreissena polymorpha, was studied under laboratory conditions. Mussels, collected in a drinking water reservoir, were exposed to varying environmentally relevant concentrations of cadmium in the presence and absence of humic acid. Cadmium concentrations in the mussel tissues were analyzed, and measurements with a cadmium-ion-selective electrode were made to determine the free cadmium ion activity in the exposure waters. The uptake of humic acid by the zebra mussels was measured by the decrease of the total organic carbon (TOC) concentration in the water over time. The free cadmium ion activity in the water decreased from 51.6% to 19.9% of the total cadmium concentration in the presence of humic acid. This decrease by a factor of 2.6 resulted in a decrease in the cadmium uptake rate in the soft tissue of zebra mussels from 12.9 to 7.9 nmol/g dry wt/day, which corresponds to a decrease by a factor of 1.6. This implies that cadmium uptake rates were higher than predicted by the free-ion activity model and indicates that cadmium-humic acid complexes are partly available to zebra mussels.

Animals↗

PubMed2004

Investigating the molecular interactions of oxytetracycline in clay and organic matter: insights on factors affecting its mobility in soil.

The interactions of oxytetracycline with model clay adsorbents were investigated as a function of suspension pH. The clay adsorbents used were native montmorillonite (SWy-2), Na-montmorillonite (Na-SWy-2), and hexadecyl trimethylammonium-montmorillonite (HDTMA-montmorillonite). The adsorption of oxytetracycline to the clay could be described by Freundlich-type adsorption isotherms. It was observed that the adsorption of oxytetracycline in the native and sodium forms of montmorillonite decreases with increasing pH in the order pH 1.5 > 5.0 > 8.7 > 11.0. This trend is consistent with cationic exchange interactions that are dominant at lower pH values when oxytetracycline has a net positive charge. On the other hand, hydrophobic interactions when oxytetracycline is zwitterionic (at pH 5.0) are predominant over other mechanisms, as evident from the FT-IR spectrum of the HDTMA-montmorillonite and humic acid-montmorillonite adsorbed with oxytetracycline. The presence of a large amount of dissolved organic matter (DOM) was also found to decrease the sorption of oxytetracycline to clay, suggesting that DOM may increase its mobility in the natural environment. Several mechanisms of interaction of oxytetracycline in clay are proposed based on the adsorption isotherms and the results from X-ray diffraction (XRD) and Fourier transform-infrared (FT-IR) analyses.

Adsorption↗

PubMed2004

Predominance and mineral stability diagrams revisited.

Predominance and mineral stability diagrams are most useful if they are based on a full chemical speciation. The diagrams can then include a wide range of reactions of importance in environmental chemistry including adsorption and ion exchange reactions. They can also take into account the possible interactions between a large number of components and are able to model changes at a fixed total concentration of each component rather than under the commonly used but less realistic assumption of a fixed activity. A "hunt-and-track" algorithm is described that enables predominance and mineral stability diagrams to be constructed using any general-purpose speciation program. Examples are given using PHREEQC and Orchestra.

Algorithms↗

PubMed2004

Competition for sorption and degradation of chlorinated ethenes in batch zero-valent iron systems.

The sorption and degradation of the chlorinated ethenes tetrachloroethene (PCE, 5 mg L(-1)) and trichloroethene (TCE, 10 mg L(-1)) were investigated in zero-valent iron systems (ZVI, 100 g L(-1)) in the presence of compounds common to contaminated groundwater with varying physicochemical properties. The potential competitors were chlorinated ethenes, monocyclic aromatic hydrocarbons, and humic acids. The effect of a complex matrix was tested with landfill contaminated groundwater. Nonlinear Freundlich isotherms adequately described chloroethene sorption to ZVI. In the presence of the more hydrophobic PCE (5 mg L(-1)), TCE sorption and degradation decreased by 33% and 30%, respectively, while TCE (10 mg L(-1)) decreased PCE degradation by 30%. In the presence of nonreactive hydrophobic hydrocarbons (i.e., benzene, toluene, and m-xylene at 100 mg L(-1)), TCE and PCE sorption decreased by 73% and 55%, respectively. The presence of the hydrocarbons had no effect on TCE degradation and increased PCE reduction rates by 50%, suggesting that the displacement of the chloroethenes from the sorption sites by the aromatic hydrocarbons enhanced the degradation rates. Humic acids did not interfere significantly with chloroethene sorption or with TCE degradation but lowered PCE degradation kinetics by 36% when present at high concentrations (100 mg L(-1)). The landfill groundwater with an organic carbon content of 109 mg L(-1) C had no effect on chloroethene sorption but inhibited TCE and PCE degradation by 60% and 70%, respectively.

Adsorption↗

PubMed2004

Thermodynamics of peat-, plant-, and soil-derived humic acid sorption on kaolinite.

Humic acids (HAs) form coatings on clays and minerals that can play an important role in nutrient and contaminant migration in soil and water. Humic acid-clay mineral interactions are known to be affected by pH and ionic strength, but little attention has been paid to the effects of temperature. In this paper we report the stoichiometry and thermodynamics of interactions of aqueous HAs (isolated from two peats, two soils and a marine alga with a method that removes lipids) with kaolinite clay, Al2Si2O5(OH)4, at seven temperatures from 5.0 to 35.0 degrees C in 0.05 M NaCl at pH 3.5. All the sorption isotherms exhibit consecutive steps ascribed to HA monolayer and bilayer formation, respectively. Site capacity comparisons suggest different HA molecular conformations on kaolinite. Linearly correlated enthalpy and entropy changes for HA sorption point to the importance of hydration and dehydration in the sorption mechanism.

Adsorption↗

PubMed2004

Contribution of natural organic matter to copper leaching from municipal solid waste incinerator bottom ash.

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is a concern in many countries and may inhibit the beneficial reuse of this secondary material. The enhanced leaching of copper from three MSWI bottom ash samples by dissolved organic carbon (DOC) was investigated with specific attention for the nature of the organic ligands. A competitive ligand exchange-solvent extraction (CLE-SE) method was used to measure Cu binding to DOC. Two types of binding sites for Cu were identified and geochemical modeling showed that the organically bound fraction varied from 82% to 100% between pH 6.6 and 10.6. Model calculations showed that complexation by previously identified aliphatic and aromatic acids was unable to explain the enhanced Cu leaching from the MSWI residues. High-performance size-exclusion chromatography (HPSEC) and the standard extraction procedure to isolate and purify natural organic matter revealed that about 0.5% of DOC consists of humic acids and 14.3-25.6% consists of fulvic acids. Calculated Cu binding isotherms based on these natural organic compounds, and the nonideal competitive adsorption-Donnan (NICA-Donnan) model, provide an adequate description of the organic Cu complexation in the bottom ash leachates. The results show that fulvic acid-type components exist in MSWI bottom ash leachates and are likely responsible for the generally observed enhanced Cu leaching from these residues. These findings enable the use of geochemical speciation programs, which include models and intrinsic parameters for metal binding to natural organic matter, to predict Cu leaching from this widely produced waste material under variable environmental conditions (e.g., pH, ionic strength, and concentrations of competing metals). The identified role of fulvic acids in the leaching of Cu and possibly other heavy metals can also be used in the development of techniques to improve the environmental quality of MSWI bottom ash.

Air Pollutants↗

PubMed2004

Hydration of natural organic matter: effect on sorption of organic compounds by humin and humic acid fractions vs original peat material.

Natural organic matter (NOM) hydration is found to change activity-based sorption of test organic compounds by as much as 2-3 orders of magnitude, depending on the compound and the specific NOM sorbent. This is demonstrated for sorption on humin, humic acid, and the NOM source material. Hydration assistance in organic compound sorption correlates with the ability of the sorbate to interact strongly with hydrated sorbents, demonstrating the important role of noncovalent polar links in organizing the sorbent structure. Differences in hydration effect between the sorbents are caused mainly by differences in compound-sorbent interactions in the dry state. For a given compound, hydration of the sorbent tends to equalize the sorption capability of the three sorbents. No correlation was found between the strength of sorbate-sorbent interactions or the type of sorbate functional groups and the extent of sorption nonlinearity. Sorption nonlinearity compared over the same sorbed concentration range is greater on the original NOM than on either of the two extracted fractions. In elucidating sorption mechanisms on hydrated NOM, it is important to explicitly consider the participation of water molecules in organic compound interactions in the NOM phase.

Adsorption↗

PubMed2004

Organic fouling and chemical cleaning of nanofiltration membranes: measurements and mechanisms.

Fouling and subsequent chemical cleaning of nanofiltration (NF) membranes used in water quality control applications are often inevitable. To unravel the mechanisms of organic fouling and chemical cleaning, it is critical to understand the foulant-membrane, foulant-foulant, and foulant-cleaning agent interactions at the molecular level. In this study, the adhesion forces between the foulant and the membrane surface and between the bulk foulant and the fouling layer were determined by atomic force microscopy (AFM). A carboxylate modified AFM colloid probe was used as a surrogate for humic acid, the major organic foulant in natural waters. The interfacial force data were combined with the NF membrane water flux measurements to elucidate the mechanisms of organic fouling and chemical cleaning. A remarkable correlation was obtained between the measured adhesion forces and the fouling and cleaning behavior of the membrane under various solution chemistries. The AFM measurements further confirmed that divalent calcium ions greatly enhance natural organic matter fouling by complexation and subsequent formation of intermolecular bridges among organic foulant molecules. Efficient chemical cleaning was achieved only when the calcium ion bridging was eliminated as a result of the interaction between the chemical cleaning agent and the fouling layer. The cleaning efficiency was highly dependent on solution pH and the concentration of the chemical cleaning agent.

Adsorption↗

PubMed2005

Solid phase dosing and sampling technique to determine partition coefficients of hydrophobic chemicals in complex matrixes.

Determination of polymer-water and dissolved organic carbon (DOC)-water distribution coefficients of very hydrophobic chemicals (log K0w > 6) is not straightforward. Poor water solubility of the test compounds complicates the spiking and analysis of actual freely dissolved concentrations. By dosing a system via a PDMS-fiber and monitoring the depletion in the polymer, spiking and analysis of concentrations in the aqueous phase are avoided, and sorption to the polymer and other hydrophobic phases can be determined easily and accurate. In this publication we report the determination of poly(dimethyl-siloxane) (PDMS)-water, and Aldrich humic acid-water distribution coefficients for six PAHs with log K0w values varying from 4.56 to 6.85. The distribution coefficients to a PDMS fiber llog Kf) and the DOC (log KDOC) range from 3.86 to 5.39 and 4.78 to 7.43, respectively. Even for the most hydrophobic compounds, the distribution coefficients show small standard errors (< or = 0.05 log units). Therefore, this method might be applied to determine sorption coefficients of numerous, even more hydrophobic compounds, to humic acids as well as other dissolved hydrophobic matrixes.

Adsorption↗

PubMed2005

Fractionation of UV and VUV pretreated natural organic matter from drinking water.

Recent studies have examined the potential of ultraviolet (UV, 254 nm) and vacuum ultraviolet (VUV, 185 nm + 254 nm) irradiation as either a pretreatment for a biological process or as a sole treatment for the removal of natural organic matter as dissolved organic carbon from drinking water. To understand the potential of UV and VUV irradiation followed by subsequent biological treatment, treated water was fractionated into four components: very hydrophobic acid (VHA), slightly hydrophobic acid (SHA), hydrophilic charged (CHA), and hydrophilic neutral (NEU). The VHA fraction was found to be very susceptible to both UV and VUV irradiation, and the fragmentation products of the high molecular weight VHA and SHA molecules contributed to the CHA and NEU fractions to form a pool of biodegradable, non-UV-absorbing, low molecular weight moieties. The NEU fraction was the most difficult to remove, as most of the components in this fraction were refractory to both the biological and photo-oxidative processes. Therefore, enhanced removal of the NEU fraction is required to increase the effectiveness and potential of the treatment process.

Carbon↗

PubMed2005

Characterzation of colloidal and humic-bound Ni and U in the "dissolved" fraction of contaminated sediment extracts.

The dissolved phase of environmental aqueous samples is generally defined by filtration at 0.2 microm or even 0.45 microm. However, it is also acknowledged that colloids <0.2 microm suspended in the aqueous phase can be important for determining contaminant availability and mobility. We have used flow field-flow fractionation (FI FFF) and size exclusion chromatography (SEC) coupled to UV-absorbance (UVA) and inductively coupled plasma mass spectrometry (ICP-MS) to study the dissolved organic matter (DOM) and colloidal binding of U and Ni in water extracts of sediments collected from a contaminated area of the Savannah River Site, a U.S. Department of Energy former nuclear materials production and processing facility, near Aiken, SC. High-performance SEC-UVA-ICP-MS was well-suited to the separation of DOM overthe molecular weight (MW) range of approximately 200-7000 Da. The ICP-MS element specific data indicated that a significant fraction of U was associated with DOM. Uranium exhibited a bimodal distribution and the other fraction was greater than the exclusion limit for the column and coeluted with Al. Flow FFF was used to size this fraction as colloidal with an approximate effective spherical diameter of 0.09-0.12 microm. Element specific ICP-MS data confirmed that U and Al were associated with the colloidal phase. High-field FI FFF was also applicable to sizing DOM but resolution was poorer than SEC. The results of this study suggest that "dissolved" U at this site is predominantly either complexed by DOM or bound to a colloidal fraction while Ni is predominately present as labile complexes or the free cation and, therefore, potentially bioavailable.

Biological Availability↗