Measurement of humic and fulvic acid concentrations and dissolution properties by a rapid batch procedure

Although humic substances (HS) strongly facilitate the transport of metals and hydrophobic organic contaminants in environmental systems, their measurement is hampered by the time-consuming nature of currently available methods for their isolation and purification. We present and apply a new rapid batch method to measure humic (HA) and fulvic (FA) acid concentrations and dissolution properties in both solid and aqueous samples. The method is compared with the conventional procedures and is shown to substantially facilitate HS concentration measurements, particularly for applications such as geochemical modeling where HS purification is not required. The new method can be performed within 1.5-4 h per sample and multiple samples can be processed simultaneously, while the conventional procedures typically require approximately 40 h for a single sample. In addition, specific dissolution properties of HS are identified and are consistent with recent views on the molecular structure of HS that emphasize molecular interactions of smaller entities over distinct macromolecular components. Because the principles of the new method are essentially the same as those of generally accepted conventional procedures, the identified HA and FA properties are of general importance for the interpretation of the environmental occurrence and behavior of HS.     

Evidence for surface precipitation of phosphate on goethite

Recent studies have suggested that the interaction between phosphate and goethite includes ternary adsorption/ surface precipitation as well as surface complexformation. The ternary adsorption/surface precipitation process envisioned involves the dissolution of the goethite crystal and subsequent adsorption of iron on the surface-bound phosphate. Further evidence to support the suggested process is needed. The process was investigated using two approaches. First, the sorption of iron spiked into a slurry of phosphated goethite and the effect of the iron sorption on phosphate uptake kinetics were investigated to determine whether iron would be adsorbed on the phosphated surface and whether it would enhance phosphate adsorption. Lead was also spiked into solution for comparison. Second, changes in the xi-potential of phosphated goethite were monitored with time. Adsorption of iron on the surface of phosphated goethite should increase the xi-potential of the goethite. Iron spiked into a phosphated goethite slurry was adsorbed on the solid with a concurrent adsorption of phosphate. The iron adsorption did not change the slow phosphate adsorption kinetics. Lead spiked into the solution was also sorbed but to a lesser extent than iron and with a lower apparent P:Pb mole ratio. Lead addition also changed the phosphate adsorption kinetics. With time, the xi-potential of phosphated goethite became more positive, returning almost to the potential of unphosphated goethite at low surface coverages. The slow increase in xi-potential over time indicates that long-term reactions are occurring on the goethite surface, most likely involving the dissolution of goethite to release iron and the subsequent reaction between the iron and surface-bound phosphate. These results provide strong support for the surface precipitation model, and are inconsistent with models envisioning the reaction between phosphate and the goethite surface as involving only monolayer surface complex formation.     

Sterols and anionic surfactants in urban aerosol: emissions from wastewater treatment plants in relation to background concentrations

Aerosol particles that are emitted from aeration tanks of wastewater treatment plants (WWTPs) can be enriched with environmentally relevant wastewater constituents. In this study, aerosol particles were sampled simultaneously at the pre-aeration tank of a municipal WWTP and at two urban locations approximately 1 km away from the WWTP to evaluate the significance of these aerosol emissions. Moreover, aerosol particles were sampled at a small wastewater irrigation facility and at a rural site. In aerosol particles and wastewater, six sterols (cholesterol, coprostanol, campesterol, beta-sitosterol, stigmasterol, stigmastanol) and anionic surfactants (expressed in terms of methylene blue active substances, MBAS) were quantified. The results showed significantly higher concentrations of sterols and MBAS at the WWTP than atthe urban locations. At the WWTP, average concentrations of cholesterol (848 +/- 321 pg m(-3)), coprostanol (1132 +/- 565 pg m(-3)), and MBAS (132 +/- 43 ng m(-3)) in aerosol were approximately twice as high. This can be attributed to emissions from the treatment tank. Coprostanol, a unique tracer for wastewater, was detected only occasionally at the urban locations. The results of this study show that the aeration of wastewater is a continuously operating local source for organic compounds in aerosol. The wastewater irrigation facility was a minor source of aerosol-bound sterols (coprostanol, 287 +/- 218 pg m(-3)) and anionic surfactants (64 +/- 32 ng m(-3)). Except for coprostanol, all compounds were also present in samples of rural aerosol.     

Adsorption of glyphosate on goethite: molecular characterization of surface complexes

As a component of herbicides, the fate of glyphosate (PMG) in the environment is of significant interest. The nature of PMG adsorption on mineral surfaces plays a significant role in the degradation of PMG. The adsorption of PMG on goethite (alpha-FeOOH) has been studied as a function of pH and PMG concentration. Adsorption was investigated with batch experiments, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The N 1s line in XPS spectra showed deprotonation of the amine group of PMG (NH2+) with increasing pH. IR analyses showed no evidence for the interaction of PMG's carboxylate group with the goethite surface, while the phosphonate group formed inner-sphere complexes. There is evidence for intramolecular hydrogen bonding between NH2+ and both the carboxylate and the phosphonate groups at low pH. Intramolecular hydrogen bonding is lost when the amine group is deprotonated, and the trend in intramolecular hydrogen bonding between NH2+ and phosphonate shows that PMG adsorbs via predominantly monodentate complexation. A minor quantity of bidentate complexes is thought to form both at near-neutral pH and when the surface concentration of PMG is low. While the phosphonate group of PMG binds directly, the carboxylate group remains relatively "free" from complexation with goethite, leaving it subject to degradation and/or complexation with metal ions present in the environment.     

Photoinduced oxidation of arsenite to arsenate in the presence of goethite

The photochemistry of an aqueous suspension of goethite in the presence of arsenite (As(III)) was investigated with X-ray absorption near edge structure (XANES) spectroscopy and solution-phase analysis. Irradiation of the arsenite/goethite under conditions where dissolved oxygen was present in solution led to the presence of arsenate (As(V)) product adsorbed on goethite and in solution. Under anoxic conditions (absence of dissolved oxygen), As(III) oxidation occurred, but the As(V) product was largely restricted to the goethite surface. In this circumstance, however, there was a significant amount of ferrous iron release, in stark contrast to the As(III) oxidation reaction in the presence of dissolved oxygen. Results suggested that in the oxic environment ferrous iron, which formed via the photoinduced oxidation of As(III) in the presence of goethite, was heterogeneously oxidized to ferric iron by dissolved oxygen. It is likely that aqueous reactive oxygen species formed during this process led to the further oxidation of As(III) in solution. Results from the current study for As(III)/goethite also were compared to results from a prior study of the photochemistry of As(III) in the presence of another iron oxyhydroxide, ferrihydrite. The comparison showed that at pH 5 and 2 h of light exposure the instantaneous rate of aqueous-phase As(V) formation in the presence of goethite (12.4 × 10(-5) M s(-1) m(-2)) was significantly faster than in the presence of ferrihydrite (6.73 × 10(-6) M s(-1) m(-2)). It was proposed that this increased rate of ferrous iron oxidation in the presence of goethite and dissolved oxygen was the primary reason for the higher As(III) oxidation rate when compared to the As(III)/ferrihydrite system. The surface area-normalized pseudo-first-order rate constant, for example, associated with the heterogeneous oxidation of Fe(II) by dissolved oxygen in the presence of goethite (1.9 × 10(-6) L s(-1) m(-2)) was experimentally determined to be considerably higher than if ferrihydrite was present (2.0 × 10(-7) L s(-1) m(-2)) at a solution pH of 5.     

Bidentate complexation modeling of heavy metal adsorption and competition on goethite

Accurate sorption modeling is critical for environmental risk assessment and development of sound remedial technologies. Adsorption to iron oxide phases is one of the important sorption processes regulating the bioavailability and toxicity of metal ions in natural systems. In this study, we used spectroscopically derived bidentate surface species to constrain surface complexation modeling in addressing Ni(ll) and Zn(ll) adsorption and competition on goethite surfaces. The 2-pK(a) triple layer model successfully predicted adsorption in single adsorbate systems. The curvature in adsorption isotherms was accurately depicted using two types of sites: high affinity and low affinity, and mononuclear bidentate surface complexes. A constrained set of parameters was found for each metal (log K(L) = -6.63 and log K(H) = -2.45 for Ni, log K(L) = -3.92 and log K(H) = 2.14 for Zn) that successfully described adsorption over a large range of experimental conditions, covering 6 to 7 orders of magnitude in concentration, ionic strength from 10(-3) to 10(-2), and environmentally relevant pH range between 4 and 6.5. Adsorption competition was predicted using the bidentate surface species with parameters calibrated using single adsorbate data.     

Degradation of drinking water disinfection byproducts by synthetic goethite and magnetite

Corrosion of iron pipes leads to the release of ferrous iron, Fe(II), and the formation of iron oxides, such as goethite and magnetite, on the pipe surface. Fe(II), a potent reductant when associated with iron oxide surfaces, can mediate the reduction of halogenated organic compounds. Batch experiments were performed to investigate the kinetics and pathways of the degradation of selected chlorinated disinfection byproducts (OBPs) by Fe(II) in the presence of synthetic goethite and magnetite. Trichloronitromethane was degraded via reduction, while trichloroacetonitrile, 1,1,1-trichloropropanone, and trichloroacetaldyde hydrate were transformed via both hydrolysis and reduction. Chloroform and trichloroacetic acid were unreactive. Observed pseudo-first-order reductive dehalogenation rates were influenced by DBP chemical structure and identity of the reductant. Fe(II) bound to iron minerals had greater reactivity than either aqueous Fe(II) or structural Fe(II) present in magnetite. For DBPs of structure Cl3C-R, reductive dehalogenation rate constants normalized by the surface density of Fe(II) on both goethite and magnetite correlated with the electronegativity of the -R group and with one electron reduction potential. In addition to chemical transformation, sorption onto the iron oxide minerals was also an important loss process for 1,1,1-trichloropropanone.     

Time scales for sorption-desorption and surface precipitation of uranyl on goethite

The sorption of uranium on mineral surfaces can significantly influence the fate and transport of uranium contamination in soils and groundwater. The rates of uranium adsorption and desorption on a synthetic goethite have been evaluated in batch experiments conducted at constant pH of 6 and ionic strength of 0.1 M. Adsorption and desorption reactions following the perturbation of initial states were complete within minutes to hours. Surface-solution exchange rates as measured by an isotope exchange method occur on an even shorter time scale. Although the uranium desorption rate was unaffected by the aging of uranium-goethite suspensions, the aging process appears to remove a portion of adsorbed uranium from a readily exchangeable pool. The distinction between sorption control and precipitation control of the dissolved uranium concentration was also investigated. In heterogeneous nucleation experiments, the dissolved uranium concentration was ultimately controlled by the solubility of a precipitated uranyl oxide hydrate. The X-ray diffraction pattern of the precipitate is characteristic of the mineral schoepite. Precipitation is kinetically hindered at low degrees of supersaturation. In one experiment, metastable sorption controlled dissolved uranium concentrations in excess of the solubility limit for more than 30 d.     

Molecular-scale structure of uranium(VI) immobilized with goethite and phosphate

The molecular-scale immobilization mechanisms of uranium uptake in the presence of phosphate and goethite were examined by extended X-ray absorption fine structure (EXAFS) spectroscopy. Wet chemistry data from U(VI)-equilibrated goethite suspensions at pH 4-7 in the presence of ~100 μM total phosphate indicated changes in U(VI) uptake mechanisms from adsorption to precipitation with increasing total uranium concentrations and with increasing pH. EXAFS analysis revealed that the precipitated U(VI) had a structure consistent with the meta-autunite group of solids. The adsorbed U(VI), in the absence of phosphate at pH 4-7, formed bidentate edge-sharing, ≡ Fe(OH)(2)UO(2), and bidentate corner-sharing, (≡ FeOH)(2)UO(2), surface complexes with respective U-Fe coordination distances of ~3.45 and ~4.3 ?. In the presence of phosphate and goethite, the relative amounts of precipitated and adsorbed U(VI) were quantified using linear combinations of the EXAFS spectra of precipitated U(VI) and phosphate-free adsorbed U(VI). A U(VI)-phosphate-Fe(III) oxide ternary surface complex is suggested as the dominant species at pH 4 and total U(VI) of 10 μM or less on the basis of the linear combination fitting, a P shell indicated by EXAFS, and the simultaneous enhancement of U(VI) and phosphate uptake on goethite. A structural model for the ternary surface complex was proposed that included a single phosphate shell at ~3.6 ? (U-P) and a single iron shell at ~4.3 ? (U-Fe). While the data can be explained by a U-bridging ternary surface complex, (≡ FeO)(2)UO(2)PO(4), it is not possible to statistically distinguish this scenario from one with P-bridging complexes also present.     

Ultrasonic characterization of lactose dissolution

The ultrasonic properties (at 2.25 MHz) of lactose solutions and suspension of lactose crystals (d ∼ 50 μm) were measured as a function of concentration (0–40 wt.%). Ultrasonic velocity increased linearly with concentration regardless of the state of dissolution of the lactose crystals while ultrasonic attenuation was low and concentration-independent when the lactose was dissolved and increased approximately linearly with the concentration of suspended crystals. Therefore the amount of lactose present and the state of dissolution can be determined simultaneously with single ultrasonic sensor. A sensor based on this principle was applied to a stirred tank and used to measure the time taken to mix powdered lactose into a solution and the time for the added lactose to dissolve.     

Kinetic and microscopic studies of reductive transformations of organic contaminants on goethite

Reactions mediated by iron mineral surfaces play an important role in the fate of organic contaminants in both natural and engineered systems. As such reactions proceed, the size, morphology, and even the phase of iron oxide minerals can change, leading to altered reactivity. The reductive degradation of 4-chloronitrobenzene and trichloronitromethane by Fe(II) associated with goethite (alpha-FeOOH) was examined by performing sequential-spike batch experiments. The particle size and size distribution of the pre- and postreaction particles were quantified using transmission electron microscopy (TEM). Results demonstrate that the degradation reactions result in goethite growth in the c-direction. Furthermore, pseudo-first-order reaction rate constants for the degradation of 4-chloronitrobenzene and trichloronitromethane and for the loss of aqueous Fe(II) decrease dramatically with each subsequent injection of organic compound and Fe(II). This result indicates that the newly formed material, which TEM and X-ray diffraction results confirm is goethite, is progressively less reactive than the original goethite. These results represent an important step toward elucidating the link between mineral surface changes and the evolving kinetics of contaminant degradation at the mineral-water interface.     

Recent food applications of microbial surfactants

Owing to their natural origin and environmental compatibility, interest in microbial surfactants or biosurfactants has gained attention during last few years. These characteristics fulfill the demand of regulatory agencies and society to use more sustained and green chemicals. Microbial-derived surfactants can replace synthetic surfactants in a great variety of industrial applications as detergents, foaming, emulsifiers, solubilizers, and wetting agents. Change in the trend of consumers toward natural from synthetic additives and the increasing health and environmental concerns have created demand for new “green” additives in foods. Apart from their inherent surface-active properties, biosurfactants have shown antimicrobial and anti-biofilm activities against food pathogens; therefore, biosurfactants can be versatile additives or ingredients of food processing. These interesting applications will be discussed in this review.     

Sorption of two naphthoic acids to goethite surface under flow through conditions

While the transport of low molecular weight organic acids was widely investigated, little is known about the mobility of the carboxylated aromatic compounds containing double rings in natural porous media. This study combines macroscopic (batch and column), microscopic (vibration spectroscopy), and surface complexation modeling to evaluate the mobility of two PAH degradation products: naphthoic acid (1-naphthoic acid (NA) and 1-hydroxy-2-naphthoic acid (HNA)), in porous media consisting of goethite-coated sand. The loss of ligands from aqueous solution was attributed to (1) a hydrogen-bonded surface complex present over the entire 3-10 pH range as well as protonated (2) surface and (3) bulk precipitates below pH 5. Mobility in column experiments was strongly affected by ligand functionality. Adsorption breakthrough predictions that make use of surface complexation parameters accurately predicted NA mobility. Those for HNA however predicted much less adsorption reactions than in the batch sorption experiments. Additional breakthrough experiments and test calculations confirmed that these differences were not related to sorption kinetics. HNA adsorption breakthrough data could only be predicted by lowering intrinsic complexation constant of the formation of hydrogen-bonded species, thereby suggesting modifications of the diffuse layer properties under flow conditions. These findings have strong implications in the assessment and prediction of contaminant transport and environmental remediation.     

Low concentrations of chitosan coating reduce water spot incidence and delay peel pigmentation of Clementine mandarin fruit

The effect on fruit ripening and on water spot incidence in Clemenules mandarin fruit of preharvest (86 days before harvesting) or postharvest application of a low concentration (12.5–125 mg l^?1) of chitosan was investigated. Chitosan delayed the natural and ethylene‐induced peel pigmentation without affecting the internal maturation, and reduced the softness and the water absorption capacity of the fruit at maturity irrespective of the concentration applied. In association with these antisenescence effects, chitosan reduced the water spot incidence, and this effect increased with increasing concentration. Best results were achieved with 125 mg l^?1 chitosan, which reduced water spot incidence by 65%. It is unlikely that chitosan produces a coating film on the fruit surface, which would modify its gas exchange with the atmosphere and its internal gas composition. At these concentrations chitosan is probably absorbed by the peel cells and acts inside them, having a dual effect, antisenescent and antifungal. Copyright © 2005 Society of Chemical Industry     

Sorption of perfluorinated surfactants on sediments

The sorption of anionic perfluorochemical (PFC) surfactants of varying chain lengths to sediments was investigated using natural sediments of varying iron oxide and organic carbon content. Three classes of PFC surfactants were evaluated for sorptive potential: perfluorocarboxylates, perfluorosulfonates, and perfluorooctyl sulfonamide acetic acids. PFC surfactant sorption was influenced by both sediment-specific and solution-specific parameters. Sediment organic carbon, rather than sediment iron oxide content, was the dominant sediment-parameter affecting sorption, indicating the importance of hydrophobic interactions. However, sorption also increased with increasing solution [Ca2+] and decreasing pH, suggesting that electrostatic interactions play a role. Perfluorocarbon chain length was the dominant structural feature influencing sorption, with each CF2 moiety contributing 0.50-0.60 log units to the measured distribution coefficients. The sulfonate moiety contributed an additional 0.23 log units to the measured distribution coefficient, when compared to carboxylate analogs. In addition, the perfluorooctyl sulfonamide acetic acids demonstrated substantially stronger sorption than perfluorooctane sulfonate (PFOS). These data should prove useful for modeling the environmental fate of this class of contaminants.