Comparison of advanced oxidation processes for the removal of natural organic matter

This study examined the impact of UV, ozone (O₃), advanced oxidation processes (AOPs) including O₃/UV, H₂O₂/UV H₂O₂/O₃ in the change of molecular weight distribution (MWD) and disinfection by-product formation potential (DBPFP). Bench-scale experiments were conducted with surface river water and changes in the UV absorbance at 254 nm (UV₂₅₄), total organic carbon (TOC), trihalomethane and haloacetic acid formation potential (THMFP, HAAFP) and MWD of the raw and oxidized water were analyzed to evaluate treatment performance. Combination of O₃ and UV with H₂O₂ was found to result in more TOC and UV₂₅₄ reduction than the individual processes. The O₃/UV process was found to be the most effective AOP for NOM reduction, with TOC and UV₂₅₄ reduced by 31 and 88%, respectively. Application of O₃/UV and H₂O₂/UV treatments to the source waters organics with 190-1500 Da molecular weight resulted in the near complete alteration of the molecular weight of NOM from >900 Da to <300 Da H₂O₂/UV was found to be the most effective treatment for the reduction of THM and HAA formation under uniform formation conditions. These results could hold particular significance for drinking water utilities with low alkalinity source waters that are investigating AOPs, as there are limited published studies that have evaluated the treatment efficacy of five different oxidation processes in parallel.     

Characterization of natural organic matter fractions separated by ultrafiltration using flow field-flow fractionation

Natural organic matter (NOM) from two sites in South Australia were separated by Amicon YM and YC ultrafiltration (UF) membranes into five nominal fractions (<0.5, 0.5-3, 3-10, 10-30 and >30 kDa). These nominal fractions were then characterized for size and molecular weight (MW) distributions using flow field-flow fractionation. The results show that separation by UF did not produce fractions with the expected MW and size. Electrophoretic mobility measurements of the NOM fractions adsorbed to colloidal goethite showed no significant difference between the fractions. However solid-state (13)C NMR of the NOM fractions showed that the separation was influenced by molecular structure as well as molecular size. The results suggest that great caution needs to be exercised when interpreting molecular size and speciation results for humic substances obtained by membrane UF.     

Dispersion of C60 in natural water and removal by conventional drinking water treatment processes

The first objective of this study is to examine the fate of C₆₀ under two disposal scenarios through which pristine C₆₀ is introduced to water containing natural organic matter (NOM). A method based on liquid-liquid extraction and HPLC to quantify nC₆₀ in water containing NOM was also developed. When pristine C₆₀ was added to water either in the form of dry C₆₀ or in organic solvent, it formed water stable aggregates with characteristics similar to nC₆₀ prepared by other methods reported in the literature. The second objective of this study is to examine the fate of the nC₆₀ in water treatment processes, which are the first line of defense against ingestion from potable water - a potential route for direct human consumption. Results obtained from jar tests suggested that these colloidal aggregates of C₆₀ were efficiently removed by a series of alum coagulation, flocculation, sedimentation and filtration processes, while the efficiency of removal dependent on various parameters such as pH, alkalinity, NOM contents and coagulant dosage. Colloidal aggregates of functionalized C₆₀ could be well removed by the conventional water treatment processes but with lesser efficiency compared to those made of pristine C₆₀.     

Granular iron oxide adsorbents to control natural organic matter and membrane fouling in ultrafiltration water treatment

Fine iron oxide particles (IOPs) are effective in removing natural organic matter (NOM) that causes membrane fouling in water treatment, but the separation of used IOPs is problematic. This study focused on the fabrication and use of granular iron oxide adsorbents, in combination with ultrafiltration (UF) membranes while investigating the NOM removal efficiency and fouling control. Sulfonated styrene-divinylbenzene copolymer beads were coated with two types of iron oxides (ferrihydrite and magnetite) and their performances were compared to that of fine IOPs. A significant amount of iron oxide coating (52–63 mg of Fe per g bead) was achieved by means of electrostatic binding and hydrolysis of iron ions. Iron oxide coated polymer (IOCP) beads were able to remove some amounts (～20%) of dissolved organic carbon (DOC) comparable to that achieved by IOPs within a short period of time (<15 min). Regenerated IOCPs exhibited the same sorption capacity as the fresh ones. The integrated IOCP/UF system operation with a 15-min empty bed contact time and 10-h cyclic regeneration maintained the 20% DOC removal with no sign of significant membrane fouling. In contrast, a sharp transmembrane pressure buildup occurred in the UF system when no iron oxide pretreatment was applied, regardless of the types of membranes tested. Iron oxide adsorbed the NOM fraction with molecular weights of >1000 kDa which is believed to be responsible for severe UF fouling.     

Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters

Since the mid-1990s, numerous studies on the treatment of drinking water by photocatalysis have been reported. Once optimised, the photocatalytic process can completely degrade numerous natural and artificial organic compounds. In this study, a hybrid photocatalysis/membrane process was used as a polishing treatment of surface water containing a small concentration of natural organic matters (i.e. total organic carbon (TOC) concentration of around 3mg/L) which may be difficult to remove using conventional filtration or coagulation. An optimum pH of 4.5 and a TiO(2) concentration of 0.1g/L were found to lead to the highest removal efficiencies. The relative effect of the individual processes featuring in the hybrid system (UV radiation, TiO(2) adsorption and membrane filtration) was also assessed for different pH values. The membrane separation process was accounted to remove around 18% of the initial TOC concentration, while TiO(2) adsorption alone was generally responsible for less than 5% of TOC removal during the 120 min of the experiments. However, when the natural water was only radiated by UV light, up to 70% of TOC was removed. A synergetic effect was observed when the three processes (TiO(2), UV and membrane) were used together. Comparison of removal efficiencies obtained during real and model (International Humic Substance Society) waters treatment by photocatalysis is also presented, revealing the importance of the nature of the feed in this type of treatment.     

An overall isotherm for activated carbon adsorption of dissolved natural organic matter in water

Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.     

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1–25 mA/cm² and CLR in a range of 12–300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm²) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe₃O₄) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography.     

Similarities in effluent organic matter characteristics from Connecticut wastewater treatment plants

Effluent organic matter (EfOM) from five Connecticut (USA) municipal wastewater treatment plants was isolated with DAX8 (hydrophobic fraction) and XAD4 (transphilic fraction) resins. Isolate recoveries ranged from 18 to 42% of the total organic carbon for DAX8 resin and from 6 to 12% for XAD4 resin. Isolated EfOM was characterized by traditional organic geochemistry techniques. Weight-averaged molecular weights of extracted EfOM by size exclusion chromatography were 450-670 Da with higher weights observed for the hydrophobic fractions than the transphilic fractions. Fluorescence characterization showed both humic- and fulvic-like fluorescence, as well as tryptophan- and tyrosine-like fluorescence, the latter not commonly observed for terrestrial organic matter. Fluorescence indices were between 1.5 and 1.9 with lower values observed for hydrophobic EfOM fractions than for transphilic fractions. Specific ultraviolet absorbance was measured between 0.8 and 3.0 L mg⁻¹ m⁻¹ with higher values for the hydrophobic EfOM fractions. Together these results indicated that isolated EfOM is similar in characteristics to microbially derived organic matter from natural aquatic systems. Little variation in EfOM characteristics was observed between the five wastewater treatment plants, suggesting that the characteristics of EfOM are similar, regardless of treatment plant design.     

A simple simulation of the degradation of natural organic matter in homogeneous and heterogeneous advanced oxidation processes

The degradation of natural organic matter (NOM) in homogeneous and heterogeneous advanced oxidation processes (AOP) was simulated using a simple underlying physical model. By treating the NOM molecules as linear chains and allowing them to be cleaved at any point selected at random, it is possible to reproduce well the results for homogeneous AOP experiments.To simulate a heterogeneous process, a bias was introduced (in the form of different weights for different chain lengths) according to literature data on the adsorption of NOM onto TiO₂ nanoparticle agglomerates. After introduction of the (adsorption) bias, the simulation closely followed the degradation sequence observed in heterogeneous photocatalysis with TiO₂ suspensions.Thus, the experimental results for homogeneous AOP may well be explained by a random breakdown of the NOM molecules; that is, we find no evidence for a selective degradation of the large molecular size material. However, a selectivity is present in the heterogeneous system due to the differential adsorption of NOM onto the reactive surface.     

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

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.     

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.     

The role of extracellular polymeric substances on the sorption of natural organic matter

In this study, the influence of extracellular polymeric substances (EPS) composition and quantity was explored for biosorption of natural organic matter (NOM), using variants of Pseudomonas aeruginosa and Pseudomonas putida. Model EPS (sodium alginate beads) were tested and sorption capacity for NOM was also elucidated. In the absence of divalent ions, minimal NOM biosorption was observed and differences among strains were negligible. Under presence of divalent ions, biosorption of NOM was proportional to the amount of EPS secreted by P. aeruginosa variants. For sorption tests with model EPS, divalent ions also promoted biosorption of tested NOM, and total biosorption was also proportional to alginate quantity. Carboxyl group content in both alginate EPS and NOM appeared to be linked to increased biosorption via bridging with divalent ions. The alginate overproducing strain possessed more potential NOM biosorption sites, while the wild-type and alginate deficient strains possessed fewer potential binding sites. In comparison, P. putida, secreting protein-based EPS, behaved differently for NOM biosorption, due to its hydrophobicity and the structural characteristics of proteins. Hydrophobic interactions appeared to enhance the biosorption of more hydrophobic Suwannee River humic acid by P. putida, whose biosorption of more hydrophilic NOM variants was similar to the alginate deficient strain. Mechanistically, the presence of a diffuse electrical double layer will present potential energy barriers limiting biosorption; however, divalent ion concentrations in the aquatic environment will promote biosorption processes, permitting functional group interactions between EPS and NOM. Bridging between hydrophilic carboxyl groups on alginate EPS and NOM appeared to be the dominant form of biosorption, while hydrophobic interactions enhanced biosorption for protein-based EPS.     

Effect of selected metal ions on the photocatalytic degradation of bog lake water natural organic matter

Herein we report the photocatalytic degradation of natural organic matter from a bog lake (Lake Hohloh, Black Forest, Germany) in the presence of 0, 5, and 10 μmol L⁻¹ of added Cu²⁺, Mn²⁺, Zn²⁺ and Fe³⁺. The reactions were followed by size exclusion chromatography with organic carbon detection (SEC-DOC) and by measurements of low molecular weight organic acids. Addition of Cu²⁺ had the largest effect of all four studied metals, leading to a retardation in the molecular size changes in NOM: degradation of the larger molecular weight fraction was inhibited leading to reduced production of smaller molecular weight metabolites. Similarly, addition of Cu²⁺ reduced the production of formic and oxalic acids, and reduced the bioavailability of the partially degraded NOM.     

Removal of natural organic matter and THM formation potential by ultra- and nanofiltration of surface water

Natural organic matter (NOM) and trihalomethane formation potential (THMFP) removal were evaluated by ultrafiltration (UF) and nanofiltration (NF). Ten different raw water sources in Alicante province (SE Spain) were analysed. Five types of membranes of different materials were tested with a dead-end-type stirred UF cell. Additional measurements, such as dissolved organic carbon, ultraviolet absorbance (254nm), THMFP, ion concentration, pH, conductivity, etc. were made on raw water, permeates and concentrates. The SUVA value was used to determine the hydrophobicity of the water analysed. The elimination of NOM and THMFP is correlated with the molecular weight (MW) of NOM determined by size exclusion chromatography (SEC). The flux decline trends were correlated with cation concentration. NOM removal by UF is low, which correlates with the average MW determined by SEC with an average value of 922g/mol (between 833 and 1031g/mol). However, the NOM removal obtained with the NF90 and NF270 NF membranes for all water sources is almost complete (90%). THMFP removal is related to hydrophobicity and permeability of membrane. The NFT50 membrane removes almost 100% of the THMFP of more hydrophobic waters.     

Comparison of airflow and particulate matter transport in multi-room buildings for different natural ventilation patterns

This study numerically investigates airflow characteristics and particulate matter (PM) transport in multi-room buildings for different natural ventilation patterns with the same air change rate. Four typical natural ventilation patterns (full-open, pass-through, right short-circuit and left short-circuit), representing the ratios of the outlet-to-inlet opening size ranging from 1.67 to 0.17, are considered to study multi-room airflow characteristics. A measured indoor PM₁₀ profile in Taipei Metropolis is input into the above four ventilation patterns as the initial condition of the PM size distribution. The time variation of indoor PM₁₀/PM_2.5/PM₁ concentrations in each room for various ventilation patterns is next investigated. The effect of ventilation pattern on particle removal mechanism is emphasized. The results show that although the air change rate of the building is the same, airflow characteristics and PM transport behaviors are quite different for various ventilation patterns. The removal efficiencies of PM₁₀ for the four ventilation patterns are all found to be much better than those of PM_2.5 and PM₁. Particle escape is the major mechanism to remove PM for rooms with double-sided ventilation, whereas particle deposition is important for single-sided ventilation rooms.     

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.     

The effect of different drinking water treatment processes on the rate of chloroform formation in the reactions of natural organic matter with hypochlorite

This study is concerned with the changes in the rate of chloroform formation during the reactions of groundwater natural organic matter (NOM) and sodium hypochlorite caused by different drinking water treatments schemes: coagulation with FeCl₃, Al₂(SO₄)₃ and polyaluminum chloride (PACl), filtration of the raw water through granular activated carbon (GAC) and filtration through the columns filled with strong base macroporous ion-exchange resins (Purolite A501P and A500P) with and without pretreatment by coagulation process. It was found that the change of the concentration of chloroform, within 2 h and c(Cl₂)=100 mg l⁻¹, can be described by a kinetic equation of the form [CHCl₃]=a+bt^c. On the basis of this equation rates of the reaction were calculated. All processes applied decreased the rate of chloroform formation (process of coagulation moderately decreased the rate of reactions, while GAC adsorption caused dramatically drop of the rate). Also, it was found that the resins have had a higher affinity towards slow-reacting chloroform precursors.

The value of the chloroform formation potential was conventionally determined after a 7-day reaction at pH 7. In addition, the same parameter was estimated with a satisfactory deviation for raw water and for treated water on the basis of the kinetic constant (k) or by determining the chloroform concentration after 2 h (ChFP₂) under rigourous chlorination conditions at pH 8.4.     

Membrane bioreactor process for removing biodegradable organic matter from water

This research investigated a membrane bioreactor (MBR) process for removing biodegradable organic matter (BOM) and trihalomethane (THM) precursors from pre-ozonated water. Bench-scale and mini-pilot-scale MBR experiments were conducted using powdered activated carbon (PAC) and acclimated biomass. Dissolved organic carbon (DOC) was removed through a combination of adsorption and biodegradation mechanisms, and the initial DOC removals depended on carbon dose, while steady-state removals were in the 20-60 percent range under various operating conditions. Both assimilable organic carbon (AOC) and total aldehydes were mostly removed to near detection limits and were not affected by PAC dosage. The AOC(NOX) removals were significantly higher than AOC(P17) or total AOC removals probably because the MBR microbial consortium was closer in characteristics to Aquaspirillum NOX than to Pseudomonas fluorescens (P17). The DOC was used instead of biodegradable organic carbon (BDOC) as a parameter for evaluating disinfection byproduct formation and bacterial regrowth potentials because BDOC assays did not yield consistent and conclusive results due to analytical difficulties. The removals of THM precursors were high when PAC was added; however, steady-state removals were a function of operating conditions and PAC dosage. Addition of PAC enhanced DOC removals and membrane permeate fluxes. Furthermore, pre-ozonation reduced membrane fouling and enhanced membrane permeate flux.     

Surface-retained organic matter of Microcystis aeruginosa inhibiting coagulation with polyaluminum chloride in drinking water treatment

Algogenic organic matter produced by the excess growth of cyanobacteria in semi-closed water areas causes coagulation inhibition in drinking water production. In this study, hydrophilic substances of Microcystis aeruginosa, which were mainly composed of lipopolysaccharide (LPS) and RNA, were prepared, and the involvement of these cyanobacterial hydrophilic substances in coagulation inhibition was investigated. As a result, it was found that the negatively charged hydrophilic substances with a molecular weight higher than 10 kDa have a significant role in coagulation inhibition. Further fractionation of cyanobacterial hydrophilic substances revealed that surface-retained organic matter (SOM), including LPS, could exhibit a potent inhibitory effect on the coagulation using polyaluminum chloride (PACl), presumably because of the direct interaction of hydrophilic SOM with cations originated from PACl, which could impede the hydrolysis of the coagulant.