Chemical heterogeneity of organic soil colloids investigated by scanning transmission X-ray microscopy and C-1s NEXAFS microspectroscopy

Colloid release and deposition in soils and sorption of inorganic and organic pollutants to soil colloids are strongly influenced by the composition and chemical heterogeneity of colloidal soil particles. To investigate the chemical heterogeneity of organic soil colloids at the particle scale, we used synchrotron scanning transmission X-ray microscopy (STXM) and C-1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy on 49 individual particles isolated from the surface horizons of three forest soils. Stacks of 130 images of each particle were collected at different X-ray energies between 280 and 310 eV. From these image arrays, NEXAFS spectra were obtained for each pixel and analyzed by principle component analysis and cluster analysis (PCA-CA) to characterize the intraparticle heterogeneity of the organic components. The results demonstrate that the organic matter associated with water-dispersible soil colloids is chemically heterogeneous at the single-particle scale. PCA-CA identified at least two distinct regions within single particles. However, the spectral variations between these regions were much smaller than the variations of averaged NEXAFS spectra representing different particles from the same soil horizon, implying that interparticle heterogeneity is much larger than intraparticle heterogeneity. Especially the contents of aromatic and carboxyl carbon exhibited a large variability. Overall, the NEXAFS spectra of water-dispersible soil colloids were similar to the NEXAFS spectrum of the humic acid fraction, but differed clearly from the fulvic acid and dissolved organic matter fractions extracted from the same soil horizon using conventional techniques.     

Factors influencing the formation and relative distribution of haloacetic acids and trihalomethanes in drinking water

Various water quality and treatment characteristics were evaluated under controlled chlorination conditions to determine their influences on the formation and distribution of nine haloacetic acids and four trihalomethanes in drinking water. Raw waters were sampled from five water utilities and were coagulated with alum and fractionated with XAD-8 resin. The resulting four fractions--raw and coagulated water and the hydrophobic and hydrophilic extracts--were then chlorinated at pH 6 and 8 and held at 20 degrees C for various contact times. The results show that increasing pH from 6 to 8 increased trihalomethane formation but decreased trihaloacetic acid formation, with little effect on dihaloacetic acid formation. More trihalomethanes were formed than haloacetic acids at pH 8, while the reverse was true at pH 6. Hydrophobic fractions always gave higher haloacetic acid and trihalomethane formation potentials than their corresponding hydrophilic fractions, but hydrophilic carbon also played an important role in disinfection byproduct formation for waters with low humic content. The bromine-containing species comprised a higher molar proportion of the trihalomethanes than of the haloacetic acids. The hydrophilic fractions were more reactive with bromine than their corresponding hydrophobic fractions. Coagulation generally removed more haloacetic acid precursors than trihalomethane precursors. Waters with higher specific ultraviolet absorbance values were more amenable to removal of organic material by coagulation than waters with low specific ultraviolet absorbance values. Experimental evidence suggests that haloacetic acid precursors have a higher aromatic content than trihalomethane precursors.     

Influence of electrostatics on the oxidation rates of organic compounds in heterogeneous Fenton systems

Electrostatic effects influence the oxidation rates of charged dissolved organic compounds in systems where the hydroxyl radical (*OH) is produced by the iron oxide-catalyzed decomposition of hydrogen peroxide (H2O2). Experiments were performed using goethite and the *OH probes 14C-labeled formic acid, 2-chlorophenol (2-CP), and nitrobenzene. At pH 4 and an ionic strength of 0.01 M, formic acid (pKa = 3.745) detected a steady-state concentration of *OH ([*OH]ss, calculated as a solution average) approximately 50 times higher than the two neutral probes did in the same systems, indicating significant enrichment of formate at the surface of the positively charged iron oxide where the *OH is being produced. Increasing the pH and ionic strength decreased formic acid oxidation rates by factors consistent with predicted decreases in electrostatic effects. In the presence of high 2-CP concentrations, the [*OH]ss measured by formic acid decreased with time, and goethite coagulation increased, due to loss of positive charge on the oxide surface as the oxidation products of 2-CP complexed surface Fe species. The [*OH]ss detected by 2-CP did not change significantly, indicating that neither goethite coagulation nor surface complexation of 2-CP oxidation products interfered with the rate of *OH generation; however, such an effect could have occurred in experiments using dissolved Fe instead of goethite. Model predictions of organic compound oxidation rates in mineral-catalyzed Fenton-like systems were improved by taking electrostatic effects into account.     

Biodegradability of fractions of dissolved organic carbon leached from decomposing leaf litter

Dissolved organic matter leached from decomposing organic matter is important in the leaching of nutrients from the root zone of ecosystems, eluviation of metals, and transport of hydrophobic pollutants. The objective of this study was to compare microbial mineralization rates in intact soil cores of various fractions of water-soluble dissolved organic matter. Uniformly 14C-labeled Populus fremontii leaf litter that had decomposed for 1 year was extracted in water and this extract was fractionated into phenolic, humic acid, fulvic acid, hydrophilic acid, and hydrophilic neutral fractions. Fulvic acid comprised 42.1% of C in dissolved organic carbon (DOC) extracted from the litter. These fractions were added to intact cores of soil or sand, and respired 14CO2 was collected. The percentage of labeled substrate C mineralized in soil at the end of 1 year was, in order from least to greatest, hydrophilic acid (30.5), fulvic acid (33.8), humic acid (39.0), whole, unfractionated DOC (43.5), unseparated hydrophilic acid and neutral (44.7), phenolic (63.3), glucose (66.4), and hydrophilic neutral (70.2). In acid-washed nutrient-amended sand that was inoculated with soil microbes, mineralization rates of fulvic acid and glucose were lower. The fractionation appeared to separate the DOC into components with widely different rates of mineralization. Results also supported the ideas that the dissolved humic substance and hydrophilic acid fractions are inherently difficult for microbes to mineralize, and this property can contribute to movement of refractory C in soil and into aquatic ecosystems.     

Reactions of hydroxyl radical with humic substances: bleaching, mineralization, and production of bioavailable carbon substrates

In this study, we examine the role of the hydroxyl (OH*) radical as a mechanism for the photodecomposition of chromophoric dissolved organic matter (CDOM) in sunlit surface waters. Using gamma-radiolysis of water, OH* was generated in solutions of standard humic substances in quantities comparable to those produced on time scales of days in sunlit surface waters. The second-order rate coefficients of OH* reaction with Suwannee River fulvic (SRFA; 2.7 x 10(4) s(-1) (mg of C/L)(-1)) and humic acids (SRHA; 1.9 x 10(4) s(-1) (mg of C/L)(-1)) are comparable to those observed for DOM in natural water samples and DOM isolates from other sources but decrease slightly with increasing OH* doses. OH* reactions with humic substances produced dissolved inorganic carbon (DIC) with a high efficiency of approximately 0.3 mol of CO2/mol of OH*. This efficiency stayed approximately constant from early phases of oxidation until complete mineralization of the DOM. Production rates of low molecular weight (LMW) acids including acetic, formic, malonic, and oxalic acids by reaction of SRFA and SRHA with OH* were measured using HPLC. Ratios of production rates of these acids to rates of DIC production for SRHA and for SRFA were similar to those observed upon photolysis of natural water samples. Bioassays indicated that OH* reactions with humic substances do not result in measurable formation of bioavailable carbon substrates other than the LMW acids. Bleaching of humic chromophores by OH* was relatively slow. Our results indicate that OH* reactions with humic substances are not likely to contribute significantly to observed rates of DOM photomineralization and LMW acid production in sunlit waters. They are also not likely to be a significant mechanism of photobleaching except in waters with very high OH* photoformation rates.     

Comparison of Cd(II), Cu(II), and Pb(II) biouptake by green algae in the presence of humic acid

The present study examines the role of humic acid, as a representative of dissolved organic matter, in Cd(II), Cu(II), and Pb(II) speciation and biouptake by green microalgae. Cellular and intracellular metal fractions were compared in the presence of citric and humic acids. The results demonstrated that Cd and Cu uptake in the presence of 10 mg L(-1) humic acid was consistent with that predicted from measured free metal concentrations, while Pb biouptake was higher. By comparing Cd, Cu, and Pb cellular concentrations in the absence and presence of humic acid, it was found that the influence of the increased negative algal surface charge, resulting from humic acid adsorption, on cellular metal was negligible. Moreover, the experimental results for all three metals were in good agreement with the ternary complex hypothesis. Given that metal has much higher affinity with algal sites than humic acid adsorbed to algae, the contribution of the ternary complex to metal bioavailability was negligible in the case of Cd (II) and Cu (II). In contrast, the ternary complex contributed to over 90% of total cellular metal for Pb(II), due to the comparable affinity of Pb to algal sites in comparison with humic acid adsorbed to algae. Therefore, the extension of the biotic ligand model by including the formation of the ternary complex between the metal, humic acid, and algal surface would help to avoid underestimation of Pb biouptake in the presence of humic substances by green algae Chlorella kesslerii.     

Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil

The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.     

Chromium(VI) reduction kinetics by zero-valent iron in moderately hard water with humic acid: iron dissolution and humic acid adsorption

In zerovalent iron treatment systems, the presence of multiple solution components may impose combined effects that differ from corresponding individual effects. The copresence of humic acid and hardness (Ca2+/Mg2+) was found to influence Cr(VI) reduction by Feo and iron dissolution in a way different from their respective presence in batch kinetics experiments with synthetic groundwater at initial pH 6 and 9.5. Cr(VI) reduction rate constants (k(obs)) were slightly inhibited by humic acid adsorption on iron filings (decreases of 7-9% and 10-12% in the presence of humic acid alone and together with hardness, respectively). The total amount of dissolved Fe steadily increased to 25 mg L(-1) in the presence of humic acid alone because the formation of soluble Fe-humate complexes appeared to suppress iron precipitation. Substantial amounts of soluble and colloidal Fe-humate complexes in groundwater may arouse aesthetic and safety concerns in groundwater use. In contrast, the coexistence of humic acid and Ca2+/Mg2+ significantly promoted aggregation of humic acid and metal hydrolyzed species, as indicated by XPS and TEM analyses, which remained nondissolved (>0.45 microm) in solution. These metal-humate aggregates may impose long-term impacts on PRBs in subsurface settings.     

Influence of humic substance adsorptive fractionation on pyrene partitioning to dissolved and mineral-associated humic substances

Changes in pyrene binding by dissolved and mineral-associated humic substances (HS) due to HS adsorptive fractionation processes were examined in model environmental systems using purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). For PAHA, carbon-normalized pyrene binding coefficients for nonadsorbed, residual fractions (Koc(res)) were different from the original dissolved PAHA Koc value (Koc(orig)) prior to contact with the mineral suspensions. A strong positive correlation between pyrene log Koc(res) and log weight-average molecular weight (MWw) for residual PAHA fractions was observed, which was relatively independent of the specific mineral adsorbent used and hypothesized fractionation processes. A strong positive correlation between log Koc(ads) and log MWw was also found for PAHA fractions adsorbed to kaolinite at low mass fraction organic carbon levels, although the relationship was statistically different from the one found with residual PAHA fractions. The same trends and correlations found for PAHA were not observed with SRFA, suggesting that the impacts of HS adsorptive fractionation on changes in hydrophobic organic contaminants binding are also influenced by the source and other biogeochemical characteristics of HS.     

Arsenite and arsenate binding to dissolved humic acids: influence of pH, type of humic acid, and aluminum

The fate of arsenic in the aquatic environment is influenced by dissolved natural organic matter (DOM). Using an equilibrium dialysis method, conditional distribution coefficients (Dom) for As(III) and As(V) binding onto two commercial humic acids were determined at environmentally relevant As/dissolved organic carbon (DOC) ratios and as a function of pH. At all pH values, As(V) was more strongly bound than As(III). Maximum binding was observed around pH 7, which is consistent with H+ competition for binding sites at low pH values and OH- competition for the arsenic center at high pH. For both oxidation states, Dom values increased with decreasing As/DOC ratios. Dom values were fitted as a function of the As/DOC ratio for As(III) and As(V). Compared to the aquatic humic acid, the terrestrial humic acid had a higher affinity for arsenic binding with 1.5-3 times higher Dom values under the same conditions. Al3+ in excess to arsenic successfully competed for strong binding sites at low As/DOC ratios. Under environmentally relevant conditions, about 10% of total As(V) may be bound to DOM, whereas >10% of As(III) is bound to DOM at very low As/DOC ratios only. Binding of arsenic to DOM should be considered in natural systems.     

Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite

This work examines the contribution of solution phase reactions, especially those involving a chain reaction mechanism, to the decomposition of hydrogen peroxide (H2O2) and organic compounds in the presence of dissolved iron and ferrihydrite. In solutions at pH 4, where Fe was introduced as dissolved Fe(III), both H2O2 and 14C-labeled formic acid decomposed at measurable rates that agreed reasonably well with those predicted by a kinetic model of the chain reaction mechanism, using published rate constants extrapolated to pH 4. The ratio of the formic acid and H2O2 decomposition rates, as well as the dramatic effect of tert-butyl alcohol on these rates, confirmed that a solution chain reaction mechanism involving *OH controlled the decomposition kinetics of both compounds. In the presence of ferrihydrite as the iron source, the ratio of the rate of formic acid decomposition to that of H2O2 decomposition was significantly lower than that observed in the presence of only dissolved Fe. Moreover, neither rate diminished drastically upon addition of tert-butyl alcohol, indicating that the solution phase chain reaction is not a dominant decomposition pathway of H2O2 and formic acid. Relative decomposition rates of formic acid and a second *OH probe, benzoic acid, were consistent with oxidation of these compounds by *OH. These observations can be reproduced by a kinetic model including (a) decomposition of H2O2 at the iron oxide surface, producing *OH with lower yield than the reaction sequence with dissolved Fe, and (b) low concentrations of dissolved Fe in the presence of ferrihydrite, preventing propagation of the solution phase chain reaction.     

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.     

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: evidence for the presence of nitrogenous binding site

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.     

Immobilizing humic acid in a sol-gel matrix: a new tool to study humic-contaminants sorption interactions

Humic substances originated from aquatic, soil, or sediment environments are mixtures of humic compounds with various characteristics. Sorption interactions with isolated, well defined humic fractions can be studied either in an aqueous phase ("dissolved humic substances"), or in a solid-phase, by coating mineral particles with the humic materials, or simply by working with humic acid particles (powder) at low pH to minimize dissolution. Each attitude, by definition, can be studied by different experimental techniques and has a different meaning for understanding natural environmental processes. In this study, a new tool for studying sorption interactions is presented. Sol-gel was used as an inert matrix to immobilize (entrap) various humic acids (HAs), and then used to study the interactions of several polycyclic aromatic hydrocarbons (PAHs) with the entrapped HA. Linear and nonlinear sorption coefficients were highly correlated with contaminant hydrophobicity. Sorption of pyrene to immobilized HA was in the order of soil HA > Aldrich HA approximately = peat HA. It was concluded that the entrapped HAs retained their original properties in the gel matrix and were accessible to the external contaminant through the pore network. Additionally, binding coefficients of pyreneto dissolved humic substances and to dissolved organic matter (DOM) were determined from the reduction in pyrene sorption to immobilized HA in the presence of dissolved humic material or DOM in solution. Binding coefficients of pyrene were in the order of the following: dissolved Aldrich HA > dissolved peat fulvic acid (FA) > DOM derived from mature compost > DOM derived from fresh compost.     

Trace metal levels in uncontaminated groundwater of a coastal watershed: importance of colloidal forms

Groundwater and surface water were collected using trace metal clean techniques from the upper glacial aquifer of West Neck Bay (Shelter Island) in eastern Long Island, NY, during the late spring and summer of 1999. The collection sites on Shelter Island are located in an area that is primarily residential and believed to have uncontaminated groundwater. Ultrafiltration was used to size-fractionate the dissolved (<0.45 microm) fraction into colloidal (1 kDa - 0.45 microm) and low molecular weight (<1 kDa) size pools. These fractions were analyzed for trace metals (Al, Ag, Cd, Cu, Mn, Pb, and Zn), organic carbon, and inorganic nutrients (NH4, NO3, PO4). The levels of metals and organic carbon in the groundwater were as low as those found in the open ocean, far removed from anthropogenic inputs. These findings corroborate the need to apply trace metal clean techniques in the determination of metal levels in uncontaminated groundwater. A significant fraction of dissolved metals (22-96%) and organic carbon (approximately 40%) in the groundwater and in surface waters of the Bay was found to be associated with colloids. The significance of the metal association with the colloidal fraction decreased in the order of Al > Cu > Ag > Zn = Cd = Mn and appeared to be dependent on the affinities of these metals for humic substances. In contrast, NO3 and NH4 were found to be almost entirely (approximately 98-99%) in the low molecular weight size fraction. Metal/aluminum and metal/carbon ratios measured in the colloids were similar to those reported for humic substances and significantly different from those of soils. This suggests that colloidal particles might originate from humic materials as opposed to purely inorganic minerals. These results indicate the need to consider the colloidal fraction in the fate and mobility of metals in groundwater and that, despite the low levels of organic matter (<50 microM of DOC) measured in groundwater, some groundwater colloids appear to be organic in nature.     

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn-S-NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn-S-NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.     

Formation of N-nitrosodimethylamine (NDMA) from humic substances in natural water

N-nitrosodimethylamine (NDMA)formation in chloraminated Iowa River water (IRW) is primarily attributed to reactions with natural organic matter (NOM) generally classified as humic substances. Experiments were conducted to determine the contribution of various NOM humic fractions to the NDMA formation potential (NDMA FP) in this drinking water source. NOM was concentrated by reverse osmosis (RO) and humic fractions were obtained by a series of resin elution procedures. Mass balances showed that nearly 90% of the NDMA formation potential could be recovered in the NOM concentrate and in water reconstituted using additions of the various humic fractions. Generally, the hydrophilic fractions tended to form more NDMA than hydrophobic fractions, and basic fractions tend to form more NDMA than acid fractions when normalized to a carbon basis. Overall, the hydrophobic acid fraction was the dominant source of NDMA when both formation efficiency and water composition were considered. The amount of NDMA formed in a sample was found to correlate linearly with an oxidation-induced decrease in specific UV absorbance (SUVA) value at 272 nm. This is consistent with a mechanism in which precursors are formed as the direct consequence of the oxidation of NOM. The NDMA FP estimated using the slope of this relationship and the initial SUVA value compared closely to the value obtained by measuring the NDMA formed in solutions dosed with excess concentrations of monochloramine that presumably exhaust all potential precursor sources. However, the NOMA FP could not be correlated to the SUVA value of the individual humic fractions indicating that the relationship of the NDMA FP to SUVA value is probably a water-specific parameter dependent on the exact composition of humic fractions. It is hypothesized that either specific NDMA precursors are distributed among the various humic fractions or that the humic material itself represents a "generic" nonspecific precursor source that requires some degree of oxidation to eventually produce NDMA. The nonmonotonic behavior of NOM fluorescence spectra during chloramination and lack of correlation between NOM fluorescence characteristics and NDMA formation limited the usage of fluorescence spectra into probing NDMA formation.     

Solid-solution partitioning of organic matter in soils as influenced by an increase in pH or Ca concentration

Organic matter is an important component of soil with regard to the binding of contaminants. Hence, the partitioning of organic matter influences the partitioning of soil contaminants. The partitioning of organic matter is, among other factors, influenced by the ionic composition and ionic strength of the soil solution. This study focuses on the behavior of organic matter after a change in the ionic composition of the soil solution, particularly in Ca concentration and pH. Different amounts of Ca(NO3)2 and NaOH were added to soil suspensions. The dissolved organic carbon (DOC) concentration increased with increasing pH (addition of NaOH), whereas an increase in Ca (addition of Ca(NO3)2) had the opposite effect. A stronger increase in DOC was observed if a single dose of NaOH was added, compared to a gradual addition of the same amount of NaOH. Cation binding by organic matter in the supernatant was calculated using the NICA-Donnan model. The log DOC concentration appeared to be correlated to the Donnan potential, calculated under the assumption that all DOC equals humic acid. This correlation was found for all eight neutral to acidic soils used in this study, although the slopes and elevations of the regression lines varied. The slope varied by a factor of 2 and the elevation appeared to be strongly influenced by the DOC concentration in the untreated soils, which is related to the total organic matter in the soil. Finally, we predicted the Donnan potential on the basis of an extraction of untreated soil with 0.03 M NaNO3, and the total additions of Ca(NO3)2 and NaOH. Comparison of these predictions with speciation calculations in solution showed a good correlation, indicating that a combination of one batch experiment and the presented calculation procedure can provide good estimations of DOC concentrations after addition of chemicals.     

Rates of hydroxyl radical generation and organic compound oxidation in mineral-catalyzed Fenton-like systems

The iron oxide-catalyzed production of hydroxyl radical (*OH) from hydrogen peroxide (H2O2) has been used to oxidize organic contaminants in soils and groundwater. The goals of this study are to determine which factors control the generation rate of *OH (VOH) and to show that if VOH and the rate constants of the reactions of *OH with the system's constituents are known, the oxidation rate of a dissolved organic compound can be predicted. Using 14C-labeled formic acid as a probe, we measured VOH in pH 4 slurries of H2O2 and either synthesized ferrihydrite, goethite, or hematite or a natural iron oxide-coated quartzitic aquifer sand. In all of our experiments, VOH was proportional to the product of the concentrations of surface area of the iron oxide and H2O2, although different solids produced *OH at different rates. We used these results to develop a model of the decomposition rate of formic acid as a function of the initial formic acid and hydrogen peroxide concentrations and of the type and quantity of iron oxide. Our model successfully predicted the VOH and organic compound oxidation rates observed in our aquifer sand experiment and in a number of other studies but overpredicted VOH and oxidation rates in other cases, possibly indicating that unknown reactants are either interfering with *OH production or consuming *OH in these systems.     

Molecular fractionation of dissolved organic matter with metal salts

Coagulation of dissolved organic matter (DOM) by hydrolyzing metals is an important environmental process with particular relevance, e.g., for the cycling of organic matter in metal-rich aquatic systems or the flocculation of organic matter in wastewater treatment plants. Often, a nonremovable fraction of DOM remains in solution even at low DOM/metal ratios. Because coagulation by metals results from interactions with functional groups, we hypothesize that noncoagulating fractions have a distinct molecular composition. To test the hypothesis, we analyzed peat-derived dissolved organic matter remaining in solution after mixing with salts of Ca, Al, and Fe using 15 T Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Addition of metals resulted in a net removal of DOM. Also a reduction of molecular diversity was observed, as the number of peaks from the ESI-FT-ICR-MS spectra decreased. At DOM/metal ratios of ～9 Ca did not show any preference for distinct molecular fractions, while Fe and Al removed preferentially the most oxidized compounds (O/C ratio >0.4) of the peat leachate. Lowering DOM/metal ratios to ～1 resulted in further removal of less oxidized as well as more aromatic compounds ("black carbon"). Molecular composition in the residual solution after coagulation was more saturated, less polar, and less oxidized compared to the original peat leachate and exhibited a surprising similarity with DOM of marine origin. By identifying more than 9200 molecular formulas we can show that structural properties (saturation and aromaticity) and oxygen content of individual DOM molecules play an important role in coagulation with metals. We conclude that polyvalent cations not only alter the net mobility but also the very molecular composition of DOM in aquatic environments.