Photochemical fate of atorvastatin (lipitor) in simulated natural waters

Cholesterol-lowering statin drugs are among the most frequently prescribed for reducing human blood cholesterol and they have been detected as contaminants in natural waters. In this study the photochemical behavior of atorvastatin (lipitor) was investigated at two different concentrations of 35.8 μM (20 mg L⁻¹) and 35.8 nM (20 μg L⁻¹) using a solar simulator and a UV reactor. Photochemical fate in natural waters can be described in most cases by the sum of the loss due to hydrolysis, direct photolysis, and, reaction with hydroxyl radical (OH), singlet oxygen (¹O₂) (or O₂ (¹D)), and excited state dissolved organic matter (DOM). The absolute bimolecular reaction rate constant with OH was measured, using pulsed radiolysis, (1.19 ± 0.04) × 10¹⁰ M⁻¹ s⁻¹. The reaction rate constant of ¹O₂ was determined to be (3.1 ± 0.2) × 10⁸ M⁻¹ s⁻¹. Under the experimental conditions used, at high atorvastatin concentration (35.8 μM) the contribution of singlet oxygen (¹O₂) to the photodegradation of atorvastatin in natural waters was higher than that of hydroxyl radical, and accounted for up to 23% of the loss in aqueous solutions. Whereas, at a concentration of 35.8 nM, ¹O₂ (and OH) both played a minor role in the removal of this compound. Lastly, it also appears that atorvastatin reacts with ³DOM* contributing to its loss in simulated natural waters.     

Photochemistry of excited-state species in natural waters: A role for particulate organic matter

Laser flash photolysis (LFP) was used to characterize a triplet excited state species isolated from Black River and San Joaquin wetlands particulate organic matter (POM). The solubilized organic matter, isolated from POM by pH-independent diffusion in distilled water, was named PdOM. UV–visible absorption spectroscopy, excitation–emission matrix spectroscopy (EEMs), and ¹H NMR were used to characterize the PdOM. While LFP of dissolved organic matter (DOM) is known to generate the solvated electron, LFP of the PdOM transient in argon-, air-, and nitrous oxide-saturated solutions indicated that this was a triplet excited state species (³PdOM*). The lifetime and the reactivity of ³PdOM* with sorbic acid, a triplet state quencher, were compared with that of the triplet excited state of benzophenone, a DOM proxy. A second excited state species (designated DOM*), with a longer lifetime, was reported in a number of previous studies but not characterized. The lifetime of DOM*, measured for seventeen organic matter isolates, lignin, tannic acid, and three wetlands plant extracts, was shown to differentiate allochthonous from autochthonous DOM. ³POM* and DOM* were also observed in lake water and a constructed wetlands' water. Aqueous extracts of fresh and aged plant material from the same wetland were shown to be one source of these excited state species. This study provides evidence of a role for POM in the photochemistry of natural and constructed wetland waters.     

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM-diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D_F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D_F compared to B, C_F, C_M and D_M increasing diuron-DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D_F and D_M. After equilibrium dialysis measurement of diuron-DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.     

Thermal fluorescence quenching properties of dissolved organic matter

The fluorescence excitation-emission matrices of dissolved organic matter (DOM) are investigated between 10 and 45 degrees C for river and waste waters and organic matter standards. With increased temperature, fluorescence intensity is quenched. It is demonstrated that for a range of river and wastewater samples, that tryptophan-like fluorescence exhibits a greater range of quenching (between 20+/-4% and 35+/-5%) than fulvic-like fluorescence (19+/-4 to 26+/-3%) over this temperature range. Humic substance standards exhibit similar fulvic-like (23+/-4%) fluorescence thermal quenching properties to river water samples (23+/-3%); however none of the samples exhibit quenching of tryptophan-like fluorescence to the same extent as the tryptophan standards (approximately 50%). Thermal fluorescence quenching is related to the exposure of the fluorophores to the heat source; our findings suggest that the tryptophan-like groups within DOM is more exposed in untreated wastewaters than in treated wastewaters riverine DOM. Thermal fluorescence properties have the potential to be used to source DOM, to provide additional chemical structural information, to temperature correct laser-induced remotely sensed DOM fluorescence, and to characterise DOM through the wastewater treatment process.     

Development and application of functional assays for freshwater dissolved organic matter

A series of 11 standardised, reproducible, assays have been developed of physico-chemical functions of dissolved organic matter (DOM) in freshwaters. The assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo(a)pyrene binding, hydrophilicity and adsorption to alumina. To obtain DOM for the assays, a 45 L sample of filtered freshwater was rotary-evaporated to reduce the volume to ca. 500 cm3. The concentrate was then passed through a strong cation exchanger, in the Na+ form, to remove alkaline-earth cations, and then through 0.7 and 0.2 microm filters. Eight samples, two each from a lake and three streamwaters, were processed. The yields of dissolved organic carbon (DOC) ranged from 70% to 107% (average 91%). The samples of DOM, stored in the dark at 4 degrees C, retained their functional assay characteristics for up to 7 months. When assaying the concentrates, parallel assays were performed with Suwannee River fulvic acid (SRFA), as a quality control standard. For most of the assays, the results for eight freshwater DOM samples are similar to those obtained with SRFA, the chief exception being the greater hydrophilicity of the DOM samples. For eight of the assays, variability among the DOM samples is significantly (p < 0.01) greater than can be explained by analytical error, i.e. by comparison with results for the SRFA quality standard; the three exceptional assays are photochemical fading, copper binding and benzo(a)pyrene binding. The two lakewater samples studied gave the most extreme assay results, probably because of the influence of phytoplankton-derived DOM. Significant correlations of hydrophilicity and adsorption with optical absorbance may mean that some DOM functional properties can be predicted from comparatively simple measurements.     

Photo-dissolution of flocculent, detrital material in aquatic environments: contributions to the dissolved organic matter pool

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC⁻¹) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.     

Spectrofluorometric properties of dissolved organic matter from Central and Southern Ontario streams and the influence of iron and irradiation

Fluorescence measurements were used to compare characteristics of dissolved organic matter (DOM) from distinctly different origins: boreal, agricultural and urban streams as well as a storm runoff pond and the outlet of a tertiary wastewater treatment plant. The primary goal was to determine if differences among stream types could be detected using DOM fluorescence in lieu of isolated fulvic acids (FA). Differences in peak excitation and peak emission wavelengths, fluorescence integrated over the 3-D matrix volume integrated fluorescence (VIF), and in a fluorescence index (FI) were examined. In general, peak fluorescence excitation and emission wavelengths as well as FI best distinguished DOM from the various origins. Results suggested that DOM from the boreal streams was of a higher molecular weight and more complex than that of agricultural and urban streams. The effects of irradiation as well as Fe on fluorescence of natural stream waters were also investigated, both of which decreased the ability of optical properties to distinguish DOM source.     

Photochemical transformation of terbutaline (pharmaceutical) in simulated natural waters: Degradation kinetics and mechanisms

In this study, varied nature organic matter isolates were employed to investigate the indirect photo transformation of terbutaline, which is a major feed additive medicine to increase the proportion of lean meat in the livestock. In the indirect photolysis of terbutaline under solar simulated irradiation, ¹O₂ plays an important role among the •OH and ³DOM^∗. The reaction rate constant of ¹O₂ was determined as (7.1 ± 0.3) × 10⁶ M⁻¹ s⁻¹ at pH 7.0, while the reaction rate constant of •OH was (6.87 ± 0.43) × 10⁹ M⁻¹ s⁻¹. The contribution of singlet oxygen to the indirect photolysis of terbutaline (19–44%) was higher than that of the hydroxyl radical (1–7%). The pseudo first order rate constants for the photodegradation of terbutaline increase with increasing pH, which indicates that pH mainly affects the reaction rate of the singlet oxygen with the phenolic part of the terbutaline. The Quinone was identified as the main photosensitized product through LC–MS/MS analysis. It is also proposed that the degradation pathway of terbutaline involves reaction between the phenolic part of terbutaline and singlet oxygen. This finding strongly suggests that singlet oxygen was important factor for the photodegradation of terbutaline in natural waters.     

Modeling heavy metal uptake by sludge particulates in the presence of dissolved organic matter

The uptake of the seven heavy metal ions Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) by sludge particulates in single-metal systems was investigated. Results showed that under acidic and neutral pH conditions, the uptake of all heavy metals by sludge particulates increases with the increase of pH. However, in the alkaline pH region, the uptake of Cu(II), Ni(II), and Co(II) decreases with the increase of pH, primarily due to the high dissolved organic matter (DOM) concentration in high pH conditions. Based on chemical reactions among heavy metal, sludge solids, and DOM, a mathematical model describing metal uptake as functions of DOM and pH was developed. The stability constants of metal–sludge and metal–DOM complexes can be determined using this model in conjunction with experimental metal uptake data. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on March 1997, the stability constants of Cu(II)–sludge complex (log K_S) and Cu(II)–DOM complex (log K_L) are 5.3±0.2 and 4.7±0.3, respectively; for Ni(II), they are 4.0±0.2 and 3.9±0.2, respectively. Results also showed that under neutral and low pH conditions (pH<8), the DOM effects on metal uptake for all heavy metals are insignificant. Therefore, the DOM term in the model can be ignored. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on December 1996, the estimated log K_S values of metal–sludge complexes for Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) are, respectively, 3.6±0.2, 3.0±0.1, 5.5±0.1, 4.8±0.1, 3.1±0.1, 5.1±0.1, and 4.4±0.3.     

Influence of dissolved organic matter on estrone removal by NF membranes and the role of their structures

The influence of different dissolved organic matter (DOM) on the removal of steroid hormone estrone during nanofiltration (NF) processes was investigated. Commercial dextran and humic acid (HA) as well as hydrophobic acid fraction (HpoA) derived from treated effluent were selected as DOM. To better understand the mechanism by which they affect estrone transport across NF membrane, the structural characteristics of DOM were also examined. The experimental results showed that DOM studied displayed obviously diverse impacts on estrone removal by NF membranes. These impacts were found to correlate with the structural characteristics of DOM. The presence of dextran without aromatic ring had little effects on the fate and transport of estrone during NF processes. The addition of HA without phenolic groups but great aromaticity improved estrone adsorption on membrane significantly while the “enhancement effect” on estrone rejection was limited. Moreover, estrone rejection by NF membranes was obviously increased by the presence of HpoA which possesses both phenolic groups and aromaticity. Some of the findings reported may be critically important for understanding the removal mechanism of estrone by NF membrane in real water matrix where various DOM co-present.     

Effect of dissolved organic compounds on the photodegradation of the herbicide MCPA in aqueous solution

This work shows that the addition of phenol and 2-propanol as model organic compounds significantly decreases the direct photolysis quantum yield of 4-chloro-2-methylphenoxyacetic acid (MCPA) upon UVB irradiation in aqueous solution. Laser flash photolysis data suggest that 2-propanol is able to decrease the formation of the MCPA excited states under irradiation. A decrease from 0.54 to 0.34 of the photolysis quantum yield of the anionic form of MCPA (which prevails over the undissociated one in surface waters) could have a considerable impact on the MCPA lifetime in ecosystems where the direct photolysis is the main phototransformation pathway. In surface water bodies where the direct photolysis has comparable kinetics as the reaction with OH, a decrease of the quantum yield would enhance the relative importance of the OH pathway, which yields considerably less toxic intermediates than the direct photolysis.     

Atrazine removal from water by polycation-clay composites: Effect of dissolved organic matter and comparison to activated carbon

Atrazine removal from water by two polycations pre-adsorbed on montmorillonite was studied. Batch experiments demonstrated that the most suitable composite poly (4-vinylpyridine-co-styrene)-montmorillonite (PVP-co-S90%-mont.) removed 90-99% of atrazine (0.5-28 ppm) within 20-40 min at 0.367% w/w. Calculations employing Langmuir's equation could simulate and predict the kinetics and final extents of atrazine adsorption. Column filter experiments (columns 20 × 1.6 cm) which included 2 g of the PVP-co-S90%-mont. composite mixed with excess sand removed 93-96% of atrazine (800 ppb) for the first 800 pore volumes, whereas the same amount of granular activated carbon (GAC) removed 83-75%. In the presence of dissolved organic matter (DOM; 3.7 ppm) the efficiency of the GAC filter to remove atrazine decreased significantly (68-52% removal), whereas the corresponding efficiency of the PVP-co-S90%-mont. filter was only slightly influenced by DOM. At lower atrazine concentration (7 ppb) the PVP-co-S90%-mont. filter reduced even after 3000 pore volumes the emerging atrazine concentration below 3 ppb (USEPA standard). In the case of the GAC filter the emerging atrazine concentration was between 2.4 and 5.3 μg/L even for the first 100 pore volumes. Thus, the PVP-co-S90%-mont. composite is a new efficient material for the removal of atrazine from water.     

UV-induced photochemical heterogeneity of dissolved and attached organic matter associated with cyanobacterial blooms in a eutrophic freshwater lake

Cyanobacterial blooms represent a significant ecological and human health problem worldwide. In aquatic environments, cyanobacterial blooms are actually surrounded by dissolved organic matter (DOM) and attached organic matter (AOM) that bind with algal cells. In this study, DOM and AOM fractionated from blooming cyanobacteria in a eutrophic freshwater lake (Lake Taihu, China) were irradiated with a polychromatic UV lamp, and the photochemical heterogeneity was investigated using fluorescence excitation–emission matrix (EEM)-parallel factor (PARAFAC) analysis and synchronous fluorescence (SF)-two dimensional correlation spectroscopy (2DCOS). It was shown that a 6-day UV irradiation caused more pronounced mineralization for DOM than AOM (59.7% vs. 41.9%). The EEM-PARAFAC analysis identified one tyrosine-, one humic-, and two tryptophan-like components in both DOM and AOM, and high component photodegradation rates were observed for DOM versus AOM (k > 0.554 vs. <0.519). Moreover, SF-2DCOS found that the photodegradation of organic matters followed the sequence of tyrosine-like > humic-like > tryptophan-like substances. Humic-like substances promoted the indirect photochemical reactions, and were responsible for the higher photochemical rate for DOM. The lower photodegradation of AOM benefited the integrality of cells in cyanobacterial blooms against the negative impact of UV irradiation. Therefore, the photochemical behavior of organic matter was related to the adaptation of enhanced-duration cyanobacterial blooms in aquatic environments.     

Behavior and characteristics of dissolved organic matter during column studies of soil aquifer treatment

Soil column experiments were performed to investigate the behavior and characteristics of dissolved organic matter (DOM) during soil aquifer treatment (SAT), and to differentiate among the mechanisms responsible for the changes in the structural and functional properties of DOM during SAT. To determine the biological transformation of DOM, biodegradability tests using a biodegradation-column system were conducted. DOM was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). Dissolved organic carbon (DOC) was removed by 70% during SAT, and the sorption and anaerobic biodegradation in SAT led to a DOC reduction of 27.4%. The significant changes in fluorescence properties of DOM were observed during SAT. However, the sorption and anaerobic biodegradation in SAT seemed to have no significant effect on the chemical structure of fluorescing constituents in DOM. The DOM fractions exhibited different changes in Fourier-transform infrared (FT-IR) spectra characteristics during SAT. Biodegradation resulted in the enrichment of aromatic structures and the decreased content of the oxygen-containing functional groups, such as CO and C-O, in DOM. On the other hand, the production of C-O and amide-2 functional groups occurred as a result of the sorption combined with anaerobic biodegradation in SAT.     

Transformation and characterisation of dissolved organic matter during the thermophilic aerobic biodegradation of faeces

We conducted a comparison of the characteristics of dissolved organic matter (DOM) taken from the bio-toilet and other sources. A characterisation of DOM was carried out to assess the stability of the compost generated during the thermophilic and aerobic biodegradation of faeces. In addition, levels of soluble microbial products generated in the bio-toilet composting reactor were compared with those taken from other sources. The results showed that (i) the main component of DOM from the bio-toilet are solutes with molecular weight (MW)>30,000 Da (40%), whereas micromolecules (MW< 1000 Da) constituted more than 60% of the DOM from other solid samples, while liquid samples reached even more than 90%; (ii) the DOM stabilisation level in the composting reactor of the bio-toilet system was greater than that shown by DOM from other sources; (iii) stabilisation of DOM in the bio-toilet system was characterised by an increasing amount of macromolecules (MW>30,000 Da) after a decreasing trend was observed in the early stages of the biodegradation process; and (iv) net production of lipopolysaccharide (LPS) in wastewater treatment plants is greater than in the bio-toilet.     

Combined ion exchange treatment for removal of dissolved organic matter and hardness

Dissolved organic matter (DOM) and hardness cations are two common constituents of natural waters that substantially impact water treatment processes. Anion exchange treatment, and in particular magnetic ion exchange (MIEX), has been shown to effectively remove DOM from natural waters. An important advantage of the MIEX process is that it is used as a slurry in a completely mixed flow reactor at the beginning of the treatment train. Hardness ions can be removed with cation exchange resins, although typically using a fixed bed reactor at the end of a treatment train. In this research, the feasibility of combining anion and cation exchange treatment in a single completely mixed reactor for treatment of raw water was investigated. The sequence of anion and cation exchange treatment, the number of regeneration cycles, and the chemistry of the regeneration solution were systematically explored. Simultaneous removal of DOM (70% as dissolved organic carbon) and hardness (>55% as total hardness) was achieved by combined ion exchange treatment. Combined ion exchange is expected to be useful as a pre-treatment for membrane systems because both DOM and divalent cations are major foulants of membranes.     

Sorption of phenols onto sandy aquifer material: the effect of dissolved organic matter (DOM)

The influence of dissolved organic matter (DOM) on the sorption of four phenols, 2,4,6-trichlorophenol (2,4,6-TCP), pentachlorophenol (PCP), 2,4-dinitrophenol (2,4-DNP) and 2-methyl-4,6-dinitrophenol (2-M-4,6-DNP), onto sandy aquifer material at different pH values was investigated using flow through column experiments. The pH-dependent sorption of the chlorinated phenols 2,4,6-TCP and PCP was not significantly affected by DOM (measured as dissolved organic carbon, DOC), whereas in the case of nitrophenols a significant lower retardation was found, depending on the DOC concentration and pH value of the aqueous solution. Sorption decreases with increasing DOC concentration, which indicates a binding of these compounds by DOM. The degree of sorption reduction depends on the pH value and increases with increasing fraction of neutral species. The different behaviour of nitrophenols in comparison to the chlorophenols is assumed to be a result of specific charge-transfer interactions. A combined sorption and complex formation model was used to describe the effect of pH and DOC concentration on the sorption of nitrophenols onto aquifer material and to estimate binding coefficients of neutral nitrophenols on DOM.     

Freeze/thaw and pH effects on freshwater dissolved organic matter fluorescence and absorbance properties from a number of UK locations

The UV-visible and fluorescence excitation-emission matrix spectrophotometric properties of dissolved organic matter (DOM) were compared for the effects of both pH and freeze/thaw on a wide range of freshwater DOM samples from the United Kingdom. It was observed that the spectrophotometric properties of our freshwater samples were sensitive to pH and that the recorded change varies with fluorescence and absorbance intensity, DOC concentration and the wavelength observed. Large and variable responses to pH were particularly severe at extremes of pH, but within the natural levels typically observed in freshwaters the response to pH was limited. For the same sample set large and variable responses were observed when subjected to freeze/thaw. From our data, knowledge of the original properties cannot be used to determine the amount of change that will occur with freezing and subsequent thawing. It is therefore recommended that in future research, to maintain the natural signal of the DOM, analysis is conducted at natural pH and without freezing to facilitate ease of comparison between studies. Our results also have implications for studies that utilise spectrophotometric techniques to investigate long-term trends in dissolved organic carbon in rivers. Spectrophotometric parameters from upland derived samples show varied responses of samples to pH and there is clear potential to complicate trends in the interpretation of long-term water colour data if pH is changing over time in a system or if samples are treated with different storage protocols with respect to acidification and freezing.     

Characterization of dissolved organic matter in drinking water sources impacted by multiple tributaries

The characterization of dissolved organic matter (DOM) in drinking water sources is important as this material contributes to the formation of disinfection by-products (DBPs) and affects how water treatment unit operations are optimized. Drinking water utilities often draw water from sources impacted by multiple tributaries, with possible shifts in DOM concentrations and reactivity over time, depending on specific environmental conditions. In this study, results are presented on the characterization of DOM under varying ambient conditions from the four main tributaries of Lake Mead, a large reservoir in the southwest United States. The tributaries include the Las Vegas Wash (LVW), Muddy River (MR), Virgin River (VR) and the upper Colorado River (UCR). One additional sample was collected at the outflow of the reservoir (lower Colorado River (LCR)). The DOM was characterized by both bulk parameters (specific ultraviolet absorbance (SUVA)) and specific physicochemical properties, i.e. size, polarity and fluorescence. The analyses were performed emphasizing limited changes in its natural configuration by eliminating analytical preparation steps, excluding sample filtration (0.45 microm filter). Results indicate that each tributary had a different molecular weight distribution, as well as fluorescence properties, which helped in the identification of the relative source of DOM (allochthonous versus autochthonous). The largest apparent molecular weight distribution was observed for DOM samples collected at the MR site, which is fed mostly by groundwater seepage. The smallest apparent molecular weight was observed for DOM collected at the LCR site, suggesting that retention in the reservoir resulted in a decrease in molecular weight as a probable result of photo oxidation and microbial processes. Fluorescence analysis aided the differentiation of DOM by clearly identifying waters that were affected by microbial activity (LVW, UCR, and LCR), either by wastewater influence or by autochthonous processes, versus limited microbial influence (MR and VR). Polarity analysis revealed clear differences in the hydrophobic/hydrophilic nature between waters, including temporal differences within individual waters at a particular site. The DOM from the LVW and VR sites had higher hydrophobic character, as measured by retention onto non-polar sorbents. Additionally, the DOM collected at the LCR had the least hydrophobic character. This type of analysis would be beneficial to utilities who want to better understand and manage their source waters, especially in the evaluation of temporal variation within a watershed.     

Adsorption of Cu(II) to schwertmannite and goethite in presence of dissolved organic matter

Sorption processes involving secondary iron minerals may significantly contribute to immobilisation of metals in soils and surface waters. In the present work the effect of dissolved organic matter (DOM) from a concentrated bog-water on the adsorption of Cu(II) onto schwertmannite (Fe₈O₈(OH)₆SO₄) and goethite (α-FeOOH) has been studied. The acid/base behaviour of DOM up to pH 6 was explained by assuming a diprotic acid with a density of carboxylate groups of 6.90 μeq (mg C)⁻¹. The resulting acidity constants, recalculated to zero ionic strength were and .The uptake of DOM to schwertmannite and goethite was highest at low pH although adsorption was significant also under mildly alkaline conditions. Adsorption to the two minerals was similar although at high pH more DOM was adsorbed to schwertmannite than to goethite.DOM enhanced the adsorption of Cu(II) at moderately low pH in the goethite system but there was no effect of DOM in the case of schwertmannite. The presence of Cu(II) resulted in a decreased adsorption of DOM to goethite at weakly acidic pH and increased adsorption at high pH. In the case of schwertmannite, Cu(II) did not affect DOM uptake.