Mechanistic and kinetic evaluation of organic disinfection by-product and assimilable organic carbon (AOC) formation during the ozonation of drinking water

Ozonation of drinking water results in the formation of low molecular weight (LMW) organic by-products. These compounds are easily utilisable by microorganisms and can result in biological instability of the water. In this study, we have combined a novel bioassay for assessment of assimilable organic carbon (AOC) with the detection of selected organic acids, aldehydes and ketones to study organic by-product formation during ozonation. We have investigated the kinetic evolution of LMW compounds as a function of ozone exposure. A substantial fraction of the organic compounds formed immediately upon exposure to ozone and organic acids comprised 60-80% of the newly formed AOC. Based on experiments performed with and without hydroxyl radical scavengers, we concluded that direct ozone reactions were mainly responsible for the formation of small organic compounds. It was also demonstrated that the laboratory-scale experiments are adequate models to describe the formation of LMW organic compounds during ozonation in full-scale treatment of surface water. Thus, the kinetic and mechanistic information gained during the laboratory-scale experiments can be utilised for upscaling to full-scale water treatment plants.     

Dissolved organic matter: Precautions for the study of hydrophilic substances using XAD resins

This study concerns the possible changes in the repartition and the molecular characteristics of hydrophilic substances (HyS) isolated by XAD resins from the same source of organic matter as a function of the distribution coefficient k′ and the DOM concentration. We tested that on two different sources of organic matter (a surface water and a landfill leachate). Breakthrough curves column experiments highlighted a modification of the repartition between hydrophilic and humic substances according to the k′ value applied. But, we find that the composition of HyS is significantly modified between k′ = 50 and 100. Our observations tend to suggest a higher contribution of humic-like matter (high-molecular weight aromatic compounds) with an increase of the k′ value. This results in a shift of fluorescence bands to longer wavelengths and changing patterns of the SEC profiles and molecular fingerprints performed by flash pyrolysis. Our results show that DOM concentration also influences the composition of HyS while little effect is observed on their quantification at k′ = 50 or 100.     

Characterization of the colloidal organic matter from the Amazonian basin by asymmetrical flow field-flow fractionation and size exclusion chromatography

Colloidal organic matter (COM) collected in small and large watercourse tributaries of the Negro River (Brazil) were fractionated and characterized by an asymmetrical flow field-flow fractionation (AFlFFF) coupled to UV and seven angle laser light scattering (LS) detectors, and by size exclusion chromatography (SEC) coupled with a UV detection. Number and weight average molar masses, weight average gyration radiuses R_Gw and polydispersity indexes were obtained for each sample in two separate runs under conditions optimized for lower and larger size fractions. The results demonstrate the existence of a decrease of size of the colloidal matter when passing from first order streams to higher order rivers. No significant changes were found in size distributions of samples collected during the low and high flow stages at the same site. The influence of selected pre-treatments such as filtration and reverse osmosis pre-concentration on the size and molar mass distributions was also studied.     

Algal-derived organic matter as precursors of disinfection by-products and mutagens upon chlorination

Algal-derived organic materials (including algal cells, hydrophilic and hydrophobic proteins) from Chlamydomonas sp. (a common green alga in local reservoirs), were chlorinated in the laboratory (20 °C, pH 7, Cl₂/DOC ratio of 20 mg Cl₂ mg⁻¹). Levels of disinfection by-products and mutagenicity (via Salmonella T100 mutation assay, -S9) over 2 h of chlorination time were determined. The hydrophilic proteins were more effective precursors of chloroform (35.9 μmol L⁻¹ at 120 min), 35 times greater than that from the hydrophobic proteins; whereas the hydrophobic proteins were more potent precursors of direct-acting mutagens (maximum level of 50.1 rev μL⁻¹ at 30 s) than the hydrophilic proteins (maximum level of 3.38 rev μL⁻¹ at 60 min). The mutagenicity of the chlorinated solutions generally reached a peak level shortly after chlorination and then declined afterwards, a pattern different from that of chloroform generation. The results indicate that algal hydrophilic proteins, containing low aromaticity and difficult to be removed via coagulation/flocculation, are important chloroform precursors. It is also suggested that hydrophobic organic intermediates with low molecular weight formed during chlorination may serve as the direct-acting mutagens.     

Disinfection by-product formation of natural organic matter surrogates and treatment by coagulation, MIEX and nanofiltration

Potentially the most effective means of controlling disinfection by-products (DBPs) is to remove precursors before disinfection. To understand relationships between physical properties, treatability and DBP formation, nine natural organic matter (NOM) surrogates were studied. Their DBP formation and removal by coagulation, MIEX^® anion exchange resin and two nanofiltration membranes was measured. Whereas treatability of NOM surrogates was explained in terms of their physicochemical properties, the same was not true of DBP formation. Hence it was not possible to selectively remove compounds which generate high amounts of DBPs. Instead, precursor removal strategies based upon empirical DBP formation potential testing are more apt. Under conditions simulating full-scale performance, MIEX^® did not offer improved performance over coagulation. A hydrophobic nanofiltration membrane proved successful for removing neutral, hydrophilic surrogates, and hence is also suitable for DBP precursors of this character.     

Air quality biomonitoring: assessment of air pollution genotoxicity in the Province of Novara (North Italy) by using Trifolium repens L. and molecular markers

Mixed air pollutants are considered a major cause of DNA damage in living species. In this study Trifolium repens L. cv Regal was used as a bioindicator to assess the genotoxicity of air stressors in the Italian province of Novara. Two on-site biomonitoring experiments were performed during the spring and autumn of 2004. Test plants were exposed at 19 monitoring sites distributed homogeneously throughout the province, and each experiment lasted for a period of 6 weeks. Genotoxicity was evaluated with Amplified Fragment Length Polymorphism (AFLP) molecular markers. The results show the predominantly rural central-west region of the Novara Province to have the worst air quality with regard to genotoxicity. Analyses of geomorphology, land use and climatic factors suggest that the compromised air quality in the region could be attributed to wind strength and direction, transporting pollution from vehicular traffic on the A4 highway and from the urban/industrialized centres of Novara and Vercelli. Plant growth, changes in plant photochemical efficiency and the presence of ozone related leaf injuries were also measured to better interpret the results of genotoxicity. Statistical analyses show that although climatic factors such as light intensity and temperature influence plant growth, they do not contribute to atmospheric stressor-induced DNA damage. Further analyses indicated that, as expected, a mixture of genotoxic and non-genotoxic pollutants coexist in the Novara Province troposphere, and that the elevated ozone concentrations experienced during the study may have contributed to the DNA damage in the tested plants by enhancing genotoxicity via interaction with other air stressors.     

Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L⁻¹ resulted in a two-fold decrease in the collision efficiency.     

Multi-wavelength spectroscopic and chromatography study on the photocatalytic oxidation of natural organic matter

The effect of TiO₂ photocatalytic oxidation on the natural organic matter (NOM) properties of two Australian surface waters were quantified using UV-vis spectroscopy, high performance size exclusion chromatography (HPSEC) with a multi-wavelength UV detector, liquid chromatography with organic carbon detector (LC-OCD), and trihalomethane formation potential (THMFP) analyses. Both the UV absorbance at wavelengths greater than 250 nm and dissolved organic carbon (DOC) content decreased significantly with treatment, although complete mineralization of NOM could not be achieved. Multi-wavelength UV detection of HPSEC analysis was shown to be useful to display further changes to NOM composition and molecular weight profiles because the organic molecules was transformed into compounds that absorb weakly at the typical detection wavelength of 250-260 nm. The multi-wavelength HPSEC results also revealed that photocatalytic oxidation yields by-products with a low aromaticity and low molecular weight. The LC-OCD chromatograms indicated that low molecular acids and neutral compounds remained after photocatalytic oxidation. Those groups of compounds did not seem to contribute significantly to the formation of trihalomethanes.     

Chemical coupling of photocatalysis with flocculation and adsorption in the removal of organic matter

An experimental investigation was made to study the effects of chemical coupling of flocculation and adsorption with photocatalysis in treating persistent organic pollutants in wastewater. The photocatalysis alone showed initial reverse reaction when titanium oxide (TiO(2)) was used in catalysis. The effect of the pretreatment of adsorption with powdered activated carbon (PAC) on photocatalysis was studied. The results showed that PAC adsorption followed by photocatalysis was not effective in alleviating reverse reaction. On the other hand, when PAC and TiO(2) were added simultaneously, the reverse reaction was eliminated. Further, the organic removal was also improved by simultaneous PAC and TiO(2) additions. When flocculation with ferric chloride (FeCl(3)) was used as pretreatment, the organic removal efficiency was superior. The initial reverse reaction was also eliminated/minimized. However, inadequate doses of FeCl(3) (less than 30 mgl(-1)) resulted in initial reverse reaction and inferior DOC removal.     

Characterization of intracellular & extracellular algae organic matters (AOM) of Microcystic aeruginosa and formation of AOM-associated disinfection byproducts and odor & taste compounds

Algae organic matters (AOM), including intracellular organic matters (IOM) and extracellular organic matters (EOM), are causing numerous water quality issues, among which formation of disinfection byproducts (DBPs) and odor & taste (O&T) compounds are of particular concern. In this study, physiochemical properties of IOM and EOM of Microcystic aeruginosa under an exponential growth phase (2.01 × 10¹¹/L) were comprehensively characterized. Moreover, the yields of DBPs during AOM disinfection and O&T-causing compounds were quantified. Hydrophilic organic matters accounted for 86% and 63% of DOC in IOM and EOM, respectively. Molecular weight (MW) fractions of IOM in <1 kDa, 40-800 kDa, and >800 kDa were 27%, 42%, and 31% of DOC, respectively, while EOM primarily contained 1-100 kDa molecules. Besides, a low SUVA (0.84 L/mg m) and the specific fluorescence spectra suggested that AOM (especially IOM) was principally comprised of protein-like substances, instead of humic-like matters. The formation potentials of chloroform, chloroacetic acid, and nitrosodimethylamine were 21.46, 68.29 and 0.0096 μg/mg C for IOM, and 32.44, 54.58 and 0.0189 μg/mg C for EOM, respectively. Furthermore, the dominant O&T compound produced from EOM and IOM were 2-MIB (68.75 ng/mg C) and β-cyclocitral (367.59 ng/mg C), respectively. Of note, dimethyltrisulfide became the prevailing O & T compound following anaerobic cultivation.     

Partitioning of hydrophobic organic chemicals (HOC) into anionic and cationic surfactant-modified sorbents

Surfactant-modified sorbents have been proposed for the removal of organic compounds from aqueous solution. In the present study, one cationic (HDTMA) and three anionic (DOWFAX-8390, STEOL-CS330, and Aerosol-OT) surfactants were tested for their sorptive behavior onto different sorbents (alumina, zeolite, and Canadian River Alluvium). These surfactant-modified materials were then used to sorb a range of hydrophobic organic chemicals (HOCs) of varying properties (benzene, toluene, ethylbenzene, 1,2-dichlorobenzene, naphthalene, and phenanthrene), and their sorption capacity and affinity (organic-carbon-normalized sorption coefficient, K(oc)) were quantified. The HDTMA-zeolite system proved to be the most stable surfactant-modified sorbent studied because of the limited surfactant desorption. Both anionic and cationic surfactants resulted in modified sorbents with higher sorption capacity and affinity than the unmodified Canadian River Alluvium containing only natural organic matter. The affinities of the surfactant-modified sorbents (K(oc)) for most HOCs are lower than octanol/water partition coefficient (K(ow)) normalized to the organic carbon content (f(oc)) and the density of octanol (K(oc) octanol); naphthalene and phenanthrene are the exceptions to this rule.     

Role of biodegradation in the removal of pharmaceutically active compounds with different bulk organic matter characteristics through managed aquifer recharge: batch and column studies

Natural water treatment systems such as bank filtration have been recognized as providing effective barriers in the multi-barrier approach for attenuation of organic micropollutants for safe drinking water supply. In this study, the role of biodegradation in the removal of selected pharmaceutically active compounds (PhACs) during soil passage was investigated. Batch studies were conducted to investigate the removal of 13 selected PhACs from different water sources with respect to different sources of biodegradable organic matter. Neutral PhACs (phenacetine, paracetamol, and caffeine) and acidic PhACs (ibuprofen, fenoprofen, bezafibrate, and naproxen) were removed with efficiencies greater than 88% from different organic matter water matrices during batch studies (hydraulic retention time (HRT): 60 days). Column experiments were then performed to differentiate between biodegradation and sorption with regard to the removal of selected PhACs. In column studies, removal efficiencies of acidic PhACs (e.g., analgesics) decreased under conditions of limited biodegradable carbon. The removal efficiencies of acidic PhACs were found to be less than 21% under abiotic conditions. These observations were attributed to sorption under abiotic conditions established by a biocide (20 mM sodium azide), which suppresses microbial activity/biodegradation. However, under biotic conditions, the removal efficiencies of these acidic PhACs were found to be greater than 59%. This is mainly attributed to biodegradation. Moreover, the average removal efficiencies of hydrophilic (polar) neutral PhACs (paracetamol, pentoxifylline, and caffeine) with low octanol/water partition coefficients (log K_ow less than 1) were low (11%) under abiotic conditions. However, under biotic conditions, removal efficiencies of the neutral PhACs were greater than 98%. In contrast, carbamazepine persisted and was not easily removed under either biotic or abiotic conditions. This study indicates that biodegradation represents an important mechanism for the removal of PhACs during soil passage.     

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.     

Coagulation of peptides and proteins produced by Microcystis aeruginosa: Interaction mechanisms and the effect of Fe-peptide/protein complexes formation

This paper focuses on elucidation of the mechanisms involved in the coagulation of peptides and proteins contained in cellular organic matter (COM) of cyanobacterium Microcystis aeruginosa by ferric coagulant. Furthermore, coagulation inhibition due to the formation of Fe-peptide/protein surface complexes was evaluated. The results of coagulation testing imply that removability of peptides and proteins is highly dependent on pH value which determines charge characteristics of coagulation system compounds and therefore the mechanisms of interactions between them. The highest peptide/protein removal was obtained in the pH range of 4-6 owing to charge neutralization of peptide/protein negative surface by positively charged hydrolysis products of ferric coagulant. At low COM/Fe ratio (COM/Fe <0.33), adsorption of peptides/proteins onto ferric oxide-hydroxide particles, described as electrostatic patch model, enables the coagulation at pH 6-8. On the contrary, steric stabilization reduces coagulation at pH 6-8 if the ratio COM/Fe is high (COM/Fe >0.33). Coagulation of peptides and proteins is disturbed at pH 6-7 as a consequence of Fe-peptide/protein complexes formation. The maximum ability of peptides/proteins to form soluble complexes with Fe was found just at pH 6, when peptides/proteins bind 1.38 mmol Fe per 1 g of peptide/protein DOC. Complex forming peptides and proteins of relative molecular weights of 1, 2.8, 6, 8, 8.5, 10 and 52 kDa were isolated by affinity chromatography.