Formation of assimilable organic carbon (AOC) and specific natural organic matter (NOM) fractions during ozonation of phytoplankton

Ozonation of natural surface water increases the concentration of oxygen-containing low molecular weight compounds. Many of these compounds support microbiological growth and as such are termed assimilable organic carbon (AOC). Phytoplankton can contribute substantially to the organic carbon load when surface water is used as source for drinking water treatment. We have investigated dissolved organic carbon (DOC) formation from the ozonation of a pure culture of Scenedesmus vacuolatus under defined laboratory conditions, using a combination of DOC fractionation, analysis of selected organic acids, aldehydes and ketones, and an AOC bioassay. Ozonation of algae caused a substantial increase in the concentration of DOC and AOC, notably nearly instantaneously upon exposure to ozone. As a result of ozone exposure the algal cells shrunk, without disintegrating entirely, suggesting that DOC from the cell cytoplasm leaked through compromised cell membranes. We have further illustrated that the specific composition of newly formed AOC (as concentration of organic acids, aldehydes and ketones) in ozonated lake water differed in the presence and absence of additional algal biomass. It is therefore conceivable that strategies for the removal of phytoplankton before pre-ozonation should be considered during the design of drinking water treatment installations, particularly when surface water is used.     

Impact of UV/H(2)O(2) advanced oxidation treatment on molecular weight distribution of NOM and biostability of water

The presence of natural organic matter (NOM) poses several challenges to the commercial practice of UV/H₂O₂ process for micropollutant removal. During the commercial application of UV/H₂O₂ advanced oxidation treatment, NOM is broken down into smaller species potentially affecting biostability by increasing Assimilable Organic Carbon (AOC) and Biodegradable Organic Carbon (BDOC) of water. This work investigated the potential impact of UV/H₂O₂ treatment on the molecular weight distribution of NOM and biostability of different water sources. A recently developed flow cytometric method for enumeration of bacteria was utilized to assess biological stability of the treated water at various stages through measurement of AOC. BDOC was also assessed for comparison and to better study the biostability of water. Both AOC and BDOC increased by about 3-4 times over the course of treatment, indicating the reduction of biological stability. Initial TOC and the source of NOM were found to be influencing the biostability profile of the treated water. Using high performance size exclusion chromatography, a wide range of organic molecule weights were found responsible for AOC increase; however, low molecular weight organics seemed to contribute more. Positive and meaningful correlations were observed between BDOC and AOC of different waters that underwent different treatments.     

The effects of combined ozonation and filtration on disinfection by-product formation

The effects of combined ozonation and membrane filtration on the removal of the natural organic matter (NOM) and the formation of disinfection by-products (DBPs) were investigated. Ozonation/filtration resulted in a reduction of up to 50% in the dissolved organic carbon (DOC) concentration. Furthermore, humic substances were converted to non-humic substances, with changes in the humic and non-humic substance concentrations of up to −50% and +20%, respectively. Ozonation/filtration resulted in the formation of partially oxidized compounds from NOM that were less reactive with chlorine, decreasing the concentration of simulated distribution system total trihalomethanes (SDS TTHMs) and simulated distribution system halo acetic acids (SDS HAAs) by up to 80% and 65%, respectively. Reducing the molecular weight cut-off (MWCO) of the membranes resulted in reductions in the concentrations of SDS TTHMs and SDS HAAs. Using a membrane with a 5 kD MWCO, the minimum gaseous ozone concentration required to bring about effective NOM degradation and meet regulatory requirements for chlorinated DBPs was 2.5 g/m³.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

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.     

How to live at very low substrate concentration

Availability of carbon/energy sources and temperature are the two environmental factors that severely restrict heterotrophic growth in most ecosystems. DOC concentrations in ground, drinking and surface waters are typically in the range of 0.5-5 mg/L, but most of this is present in a polymeric, inaccessible form for microbes. Concentrations of microbiologically available carbon compounds (so-called assimilable organic carbon, AOC) are usually in the range of 10-100 μg/L, those of individual sugars or amino acids are not higher than a few μg/L. Until recently microbiologists assumed that such nutrient-poor (oligotrophic) environments are “deserts” for life, and that the majority of bacterial cells seen in the microscope are dead, dormant or at least severely starved. Nevertheless, despite the low concentrations of available carbon compounds, bacterial cell numbers recorded in these environments typically are in the range of 10⁵-10⁶ per mL. Over the last years, we have learnt that most of these microbes are perfectly alive, metabolizing and ready to grow when given the chance. Hence, microbes have adapted and developed strategies to cope with this situation.Laboratory studies with pure cultures suggest that bacterial cells have developed two strategies to live under such conditions. The first strategy is to perform a “multivorous” way of life by taking up and metabolizing dozens of different carbon substrates simultaneously (i.e., they are NOT specializing on a particular substrate, which they can take up with very high affinity). This “mixed substrate growth” equips the cell with a kinetic advantage and metabolic flexibility. Simultaneous utilization of a multitude of carbon substrates allows fast growth at minute concentrations of individual substrates. The second strategy is to minimize maintenance requirements (unfortunately we still know little about how this is achieved).Recently, flow cytometry has been employed to study microbial growth in very dilute, nutrient-poor environments. The technique allows fast and easy quantification of microbial growth of natural bacterial communities, including “uncultivable” members, under environmental conditions. When combined with strain-specific fluorescent immunoprobes, this technique allows investigation of the growth and competition of pathogens with the indigenous microbial flora. This method is particularly suited for studying questions concerning microbial growth and survival in drinking water systems.     

Characterising humic acid fouling of nanofiltration membranes using bisphenol A as a molecular indicator

Fouling of nanofiltration (NF) membranes by humic acids was investigated using bisphenol A (BPA) as an indicator chemical to differentiate between various mechanisms that may lead to a change in solute rejection. Three commercially available NF membranes were investigated and an accelerated fouling condition was achieved with a foulant mixture containing humic acids in an electrolyte matrix. The effects of membrane fouling on the rejection of BPA were interpreted with respect to the membrane pore sizes and the fouling characteristics. Results reported here indicate that calcium concentration in the feed solution could be a major factor governing the humic acid fouling process. Moreover, a critical concentration of calcium in the feed solution was observed, at which membrane fouling was most severe. Membrane fouling characteristics were observed by their influence on BPA rejection. Such influence could result in either an increase or decrease in rejection of BPA by the three different membranes depending on the rejection mechanisms involved. It is hypothesized that these mechanisms could occur simultaneously and that the effects of each might not be easily distinguished. However, it was observed that their relative contribution was largely dependent upon membrane pore size. Pore blocking, which resulted in a considerable improvement in rejection, was prominent for the more open pore size TFC-SR2 membrane. In contrast, the cake-enhanced concentration polarisation effect was more severe for the tighter NF-270 and NF-90 membranes. For hydrophobic solutes such as BPA, the formation of the fouling layer could also interfere with the solute-membrane interaction, and therefore, exert considerable influence on the separation process.     

Neurotoxic and hepatotoxic cyanotoxins removal by nanofiltration

This study investigates the influence of chemical feed characteristics on nanofiltration performance for cyanotoxins removal, namely the neurotoxic anatoxin-a (alkaloid of 166 g/mol, positively charged) and the hepatotoxic microcystins (cyclic peptides of approximately 1,000 g/mol, negatively charged). Results indicate that NF membranes are an effective barrier against anatoxin-a and microcystins in drinking water. Anatoxin-a and especially microcystins were almost completely removed, regardless of the variations in feed water quality (natural organic matter and competitive toxin), the water recovery rate and the pH values. Anatoxin-a removal was governed by electrostatic interactions and steric hindrance, whereas for microcystins the latter was the main mechanism. In turn, fluxes were significantly impacted by background organics and, especially, inorganics (pH, calcium).     

Influence of the sediment on lead speciation in the Tagus estuary

The aim of this work is to study the influence of the Tagus estuarine sediment on lead speciation in the overlying natural water. The water sample in the presence of the sediment was contaminated three times with Pb(II) in a laboratory experiment. In different periods of time, at 1-7 days after each contamination, small volumes of water were titrated with lead. The titration was followed by anodic stripping voltammetry in differential pulse mode. Before and after contamination systematic analysis of the voltammetric parameters (peak current, peak potential and peak width) were carried out to get a clear picture of Pb(II) complexation in the soluble fraction in contact with the sediment. Two main types of organic ligands, macromolecular ligands and small compounds, were detected before contamination. Both of them form labile complexes (degree of lability within the timescale of some milliseconds). The small compounds, with a diffusion coefficient similar to that of the free metal ion, present a homogeneous behaviour in terms of Pb complexation. On the other hand macromolecular ligands, with a diffusion coefficient of 1.2 x 10(-6) cm2s(-1), can be described by two different binding groups, which might be of phenolic and carboxylic type as presented by humic matter. The sediment eliminated lead contamination (10(-6) moldm(-3) was the maximum concentration added) from 12 dm3 of water (surface of 8 dm2) within 2 days. It was also found that the sediment released organic ligands responsible for both labile and inert Pb complexes "seen" by voltammetry. The release of organic ligands that decreases the bioavailability of Pb(II) was clearly detected 1 week after contamination. Therefore, the sediment acts as a buffer for lead through two mechanisms against lead contamination: removing lead ions from the solution and releasing organic ligands to the water column. In a short period of time the sediment responds as a self-cleaning system for Pb(II) contamination in the estuarine water, which may have a very important influence in environmental pollution.     

Effect of NOM, turbidity and floc size on the PAC adsorption of MIB during alum coagulation

The effect of natural organic material (NOM) and turbidity on the powdered activated carbon (PAC) adsorption of the odour compound 2-methylisoborneol (MIB) was evaluated during alum coagulation. The character of the flocs, in terms of their size and fractal dimensions (Df), was used to interpret the observed adsorption behaviour of MIB during the coagulation process. As the alum dose was increased, the adsorption of MIB decreased. This was determined to be due to the size of the flocs, with larger flocs incorporating PAC into their structure, reducing the efficiency of mixing, and the bulk diffusion kinetics for the MIB molecule. The presence of turbidity also reduced MIB adsorption due to the formation of larger flocs. The character of NOM was found to have a greater influence on the adsorption of MIB than the floc structure.     

The influence of natural organic matter and cations on the rejection of endocrine disrupting and pharmaceutically active compounds by nanofiltration

The impact of natural organic matter (NOM) and cations on the rejection of five endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs) (acetaminophen, carbamazepine, estrone, gemfibrozil, oxybenzone) by nanofiltration (NF) was examined. The water matrices included membrane bioreactor (MBR) effluent, Lake Ontario water and laboratory-prepared waters modelled to represent the characteristics of the Lake Ontario water. The impact of cations in natural waters on compound rejection was also examined by doubling the natural cation concentration (calcium, magnesium, sodium) in both the Lake Ontario water and the MBR effluent. The presence of Suwannee River NOM spiked into laboratory-grade water was found to cause an increase in compound NF rejection. In addition, the presence of cations alone in laboratory-grade water did not have a significant impact on rejection with the exception of the polar compound gemfibrozil. However, when cation concentration in natural waters was increased, a significant decrease in the rejection of EDCs and PhACs was observed. This suggests that the presence of cations may result in a reduction in the association of EDCs and PhACs with NOM.     

Application of powdered activated carbon for the adsorption of cylindrospermopsin and microcystin toxins from drinking water supplies

Cylindrospermopsin (CYN) and microcystin are two potent toxins that can be produced by cyanobacteria in drinking water supplies. This study investigated the application of powdered activated carbon (PAC) for the removal of these toxins under conditions that could be experienced in a water treatment plant. Two different PACs were evaluated for their ability to remove CYN and four microcystin variants from various drinking water supplies. The removal of natural organic material by the PACs was also determined by measuring the levels of dissolved organic carbon and UV absorbance (at 254 nm). The PACs effectively removed CYN and the microcystins from each of the waters studied, with one of the PACs shown to be more effective, possibly due to its smaller particle diameter. No difference in removal of the toxins was observed using PAC contact times of 30, 45 and 60 min. Furthermore, the effect of water quality on the removal of the toxins was minimal. The microcystin variants were adsorbed in the order: MCRR > MCYR > MCLR > MCLA. CYN was found to be adsorbed similarly to MCRR.     

可生物降解有机物在水厂净水工艺中的变化

以上海市两座不同水源的典型水厂为研究对象,分析了可生物降解有机物(BOM)和总有机物(以DOC表征)在水厂常规净水工艺中的变化规律.结果表明,水厂常规工艺对AOC、BDOC与DOC的去除能力均不高,且受水温影响明显,两水厂出水均为生物不稳定性饮用水;DOC主要在沉淀单元被去除,BDOC在沉淀、砂滤单元都有去除,AOC则主要在砂滤单元被去除;加氯可造成DOC(或BDOC)向AOC的转化,使出厂水AOC浓度增加,要确保出厂水的生物稳定性,必须同步削减水中BOM与总有机物的浓度.     

Mechanism of natural organic matter removal by polyaluminum chloride: effect of coagulant particle size and hydrolysis kinetics

The mechanism of natural organic matter (NOM) removal by AlCl(3) and polyaluminum chloride (PACl) was investigated through bench-scale tests. The fraction distributions of NOM and residual Al after coagulation in solution, colloid and sediment were analyzed as changes of coagulant dosage and pH. The influence of NOM, coagulant dose and pH on coagulation kinetics of AlCl(3) was investigated using photometric dispersion analyzer compared with PACl. Monomeric Al species (Al(a)) shows high ability to satisfy some unsaturated coordinate bonds of NOM to facilitate particle and NOM removal, while most of the flocs formed by Al(a) are small and difficult to settle. Medium polymerized Al species (Al(b)) can destabilize particle and NOM efficiently, while some flocs formed by Al(b) are not large and not easy to precipitate as compared to those formed by colloidal or solid Al species (Al(c)). Thus, Al(c) could adsorb and remove NOM efficiently. The removal of contaminant by species of Al(a), Al(b) and Al(c) follows mechanisms of complexation, neutralization and adsorption, respectively. Unlike preformed Al(b) in PACl, in-situ-formed Al(b) can remove NOM and particle more efficiently via the mechanism of further hydrolysis and transfer into Al(c) during coagulation. While the presence of NOM would reduce Al(b) formed in-situ due to the complexation of NOM and Al(a).     

Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate

Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 μg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment.     

Determination of hydrophobicity of NOM by RP-HPLC,and the effect of pH and ionic strength

A reverse phase high performance liquid chromatography method for the determination of the hydrophobicity of natural organic matter (NOM) was developed by modification of an existing method based on elution with acetic acid/acetonitrile. The modified method separates the NOM into two well-defined groups according to their retention on a C18 column. The recovery was 101±11% for samples containing between 4 and 40 mg/L dissolved organic carbon (DOC). The method was tested for effects of ionic strength up to 0.8 eq. /L. Testing the method on eleven well-described NOM samples at pH 4.7 and 7.0 revealed the strong pH dependency of the hydrophobicity. The effect of pH on the hydrophobicity could be predicted from the proton binding properties of the NOM. Application of the method to NOM samples fractionated by HPSEC demonstrated considerable variations in hydrophobicity among the fractions, particularly at low pH.     

Removal of VUV pre-treated natural organic matter by biologically activated carbon columns

A potential alternative water treatment process using VUV (185 nm+254 nm) irradiation followed by a biological treatment is described. The system uses sufficient VUV radiation (16J cm(-2)) to significantly enhance the production of biologically degradable moieties prior to treatment with biologically activated carbon (BAC). Two similar activated carbons were used, one virgin and one taken from a water treatment plant with an established biofilm. The VUV-BAC process decreased the overall dissolved organic carbon (DOC) concentration of a natural water sample by 54% and 44% for the virgin carbon and previously used BAC, respectively. Furthermore, VUV-BAC treatment decreased the trihalomethane (THM) formation potential (THMFP) by 60-70% and the haloacetic acid (HAA) formation potential (HAAFP) by 74%. The BAC systems effectively removed the hydrogen peroxide residual produced by VUV irradiation. Although nitrite formation can result from VUV treatment of natural organic matter (NOM), none was detected before or after BAC treatment.     

Removal of disinfection by-product precursors with ozone-UV advanced oxidation process

The efficacy of using ozone (O3), ultraviolet irradiation (UV) and the combined O3-UV advanced oxidation process (AOP) to remove 2 classes of disinfection by-product (DBP) precursors from raw surface water samples have been evaluated and compared. In particular, trihalomethane and haloacetic acids formation potentials were measured. Laboratory batch scale experiments were carried out as a function of ozone and UV dosage in order to study the removal kinetics. It is concluded that the combined O3-UV AOP is more effective than either the ozone or UV treatment alone. Ozone-UV AOP is capable of mineralizing up to 50% of the total organic carbon from the raw source water at an ozone dose of 0.62+/-0.019 mg O3/mL and a UV dose of 1.61 W s/cm2. In addition, O3-UV AOP can reduce trihalomethane formation potential by roughly 80% and haloacetic acids formation potential by roughly 70% at the same ozone and UV dosage.     

Influences of solution chemistry and polymeric natural organic matter on the removal of aquatic pharmaceutical residuals by nanofiltration

This study demonstrates the removal efficiency and the permeate flux behavior during cross-flow nanofiltration (NF) of aqueous solutions of five pharmaceutically active compounds (PhACs). Cephalexin, tetracycline, acetaminophen, indomethacin and amoxicillin were used as models of PhACs, and alginate was selected as model of natural organic matter (NOM). Two commercial composite NF membranes (SR2 and SR3) with different characteristics were used. The highest rejection was observed for tetracycline, i.e., 75-95% for membrane SR 2 and 95-100% for membrane SR 3, while the rejection was least for acetaminophen (32-36% for SR2 and 52-59% for SR3). As the pH of acetaminophen solution was increased (from 6 to 9) the rejection would increase. Changes of ionic content (from 10 to 20 mM) lead to increase (from 89 to 93% for SR 3) or decrease (from 100 to 91% for SR2) of cephalexin rejection depending on the membrane used. The permeate flux would decrease with decreasing the pH solution and increasing ionic strength. The addition of alginate in the feed stream decreased the permeate flux, with lower reduction for SR3, and increased the PhAC rejection except for acetaminophen and amoxicillin. Both size and Donnan exclusions seemed to occur, and the effect of Donnan exclusion was more pronounced for the NF membrane having larger effective pore size (SR2).     

Modeling monochloramine loss in the presence of natural organic matter

A comprehensive model describing monochloramine loss in the presence of natural organic matter (NOM) is presented. The model incorporates simultaneous monochloramine autodecomposition and reaction pathways resulting in NOM oxidation. These competing pathways were resolved numerically using an iterative process evaluating hypothesized reactions describing NOM oxidation by monochloramine under various experimental conditions. The reaction of monochloramine with NOM was described as biphasic using four NOM specific reaction parameters. NOM pathway 1 involves a direct reaction of monochloramine with NOM (k_doc1=1.05×10⁴-3.45×10⁴ M⁻¹ h⁻¹). NOM pathway 2 is slower in terms of monochloramine loss and attributable to free chorine (HOCl) derived from monochloramine hydrolysis (k_doc2=5.72×10⁵-6.98×10⁵ M⁻¹ h⁻¹), which accounted for the majority of monochloramine loss. Also, the free chlorine reactive site fraction in the NOM structure was found to correlate to specific ultraviolet absorbance at 280 nm (SUVA₂₈₀). Modeling monochloramine loss allowed for insight into disinfectant reaction pathways involving NOM oxidation. This knowledge is of value in assessing monochloramine stability in distribution systems and reaction pathways leading to disinfection by-product (DBP) formation.