Hydrophobic Natural Organic Matter Research Articles

Insights into Co3O4 nano-rod/peroxymonosulfate catalytic oxidation system for chemical cleaning ultrafiltration membrane: Performance, mechanisms, and effects on the membrane stability

In this study, Co3O4 nano-rod (Co3O4-NR) with (110) crystal plane predominant exposure is prepared by a hydrothermal method, and peroxymonosulfate (PMS) was activated via them for ultrafiltration membrane (PVDF and PES membrane) cleaning. Co3O4-NR with (110) planes exposed obtained abundant oxygen vacancies (OV) and low oxidation state Co (Co2+) and therefore showed excellent ability for PMS activation. The Co3O4-NR/PMS system did not require long-term immersion in a high-concentration chemical reagent solution compared with conventional ultrafiltration membrane chemical cleaning. The cleaning process, which was conducted for only 15 min in Co3O4-NR (1.6 g/L)/PMS (2 mM) solution, was sufficient to restore almost all the permeate flux and could remove essentially all the irreversible foulants. The excellent membrane cleaning performance of the Co3O4-NR/PMS system was attributed to the generation of 1O2 and O2•−, which degraded the large-molecule, hydrophobic natural organic matter (NOM) into small-molecule, hydrophilic organic matter. Cyclic experiments showed that Co3O4-NR had excellent reusability, which offered significant cost savings. The consecutive chemical cleaning experiments indicated that the Co3O4-NR/PMS maintained the membrane stability better than the traditional chlorine cleaning method. The system effectively averts membrane damage and polymer structure changes caused by long-term exposure to oxidants. In conclusion, the Co3O4-NR/PMS system has significant advantages in membrane cleaning and broad application prospects.

Enhanced coagulation coupled with cyclic IX adsorption-ARP regeneration for removal of PFOA in drinking water treatment.

Laboratory investigations were conducted to demonstrate a potentially transformative, cost-efficient per- and polyfluoroalkyl substances (PFAS) treatment approach, consisting of enhanced coagulation and repeated ion exchange (IX)-advanced reduction process (ARP) for concurrent PFAS removal and IX resin regeneration. Enhanced alum coagulation at the optimal conditions (pH6.0, 60 mg/L alum) could preferentially remove high molecular-weight, hydrophobic natural organic matter (NOM) from 5.0- to ~1.2-mg/L DOC in simulated natural water. This facilitated subsequent IX adsorption of perfluorooctanoic acid (PFOA, a model PFAS in this study) (20 μg/L) using IRA67 resin by minimizing the competition of NOM for functional sites on the resin. The PFOA/NOM-laden resin was then treated by ARP, generating hydrated electrons (eaq - ) that effectively degraded PFOA. The combined IX-ARP regeneration process was applied over six cycles to treat PFOA in pre-coagulated simulated natural water, nearly doubling the PFOA removal compared with the control group without ARP regeneration. This study underscores the potential of enhanced coagulation coupled with cyclic IX-ARP regeneration as a promising, cost-effective solution for addressing PFOA pollution in water. PRACTITIONER POINTS: Enhanced alum coagulation can substantially mitigate NOM to favor the following IX removal of PFOA in water. Cyclic IX adsorption-ARP regeneration offers an effective, potentially economical solution to the PFOA pollution in water. ARP can effectively degrade PFOA during the ARP regeneration of PFOA/NOM-laden resin.

Linking water quality, fouling layer composition, and performance of reverse osmosis membranes

Fouling of polyamide membranes during reverse osmosis (RO) is a major challenge for adopting membrane technologies to treat highly contaminated waters, especially those containing organic foulants (e.g., natural organic matter (NOM), polysaccharides) and dominant cations (e.g., sodium, magnesium, calcium). This work combines bench-scale membrane fouling experiments with detailed characterization of feedwater chemistry and fouling layer composition/morphology to reveal fundamental mechanisms of (in)organic fouling during RO. Divalent cations are shown to promote fouling by hydrophobic NOM containing aromatic and carboxyl groups, while NOM fouling in the presence of a monovalent cation, sodium, occurs by smaller fulvic acids containing larger fractions of carboxyl groups and other oxygen-rich moieties. Calcium-carboxyl bridging occurs in solution and near the membrane surface to induce NOM aggregation on nanometer length scales. In complex waters containing foulant mixtures, co-fouling by calcium-carboxyl bridging and CaCO3 precipitation influence membrane performance at longer timeframes. However, the flux decline observed for the co-fouling mechanism was less significant than the sum of its parts, suggesting both synergistic and antagonistic fouling mechanisms should be considered in membrane design/operation. These results encourage the design of pretreatment processes to reduce concentrations of multivalent ions and hydrophobic NOM in RO feedwaters, and of membrane materials to limit attachment/deposition of aggregates to/on polyamide surfaces.

Cation-π Interactions Contribute to Hydrophobic Humic Acid Removal for the Control of Hydraulically Irreversible Membrane Fouling.

Hydraulically irreversible membrane fouling is a major problem encountered during membrane-based water purification. Membrane foulants present large hydrophobic fractions, with humic acid (HA) being a prevalent example of hydrophobic natural organic matter. Furthermore, HA contains numerous aromatic rings (π electrons), and its hydrophobic interactions are a major cause of irreversible membrane fouling. To address this issue, in this study, we used the cation-π interaction, which is a strong noncovalent, competitive interaction present in water. Because the strength of cation-π interactions depends on the combination of cations and π molecules, utilizing the appropriate cations will effectively remove irreversible fouling caused by hydrophobic HA. We performed macroscale experiments to determine the cleaning potential of the test cations, nanomechanically analyzed the changes in HA cohesion caused by the test cations using a surface force apparatus and an atomic force microscope, and used molecular dynamics simulations to elucidate the HA removal mechanism of test studied cations. We found that the addition of 1-ethyl-3-methylimidazolium, an imidazolium cation with an aromatic moiety, effectively removed the HA layer by weakening its cohesion, and the size, hydrophobicity, and polarity of the HA layer synergistically affected the HA removal mechanism based on the cation-π interactions.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) adsorbed on microplastics in drinking water: Implications for female exposure, reproductive health risk and its mitigation strategies through in silico methods

In this paper, molecular dynamics (MD) simulations were used to analyze the effects of different additive combinations in microplastics (MPs) on the female reproductive toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFAS). It was found that 59.38% of plastic additive combinations had synergistic toxicity effects. And the plastic additive combination scheme with 31.10% decrease of joint toxic action was selected. By simulating the PFAS adsorption by MPs in drinking water through MD, it was found that hydrophobic PFAS was more easily adsorbed by MPs, and the van der Waals interaction energy may have an influential role in MPs adsorbing PFAS. The degree of interference with PFAS adsorption by MPs is greater when the MP is supplemented with a more hydrophobic additive. During AC adsorbing PFAS and MPs, it was found that some of the PFAS was adsorbed by MPs, and improving the adsorption of MPs by AC could also improve the removal rate of PFAS from drinking water. The effect of hydrophobic natural organic matter (NOM) on AC adsorbing PFAS and MPs was more significant, and the higher the molecular weight, the greater the effect on the adsorption performance of the AC. Within a certain range, ACs show an increasing tendency to adsorb PFAS and MPs with decreasing pore size and increasing amine functionalization. Machine learning method was used to get the influence rule of molecular parameters on improving PFAS function and reducing female reproductive toxicity. This study aims to mitigate the toxic hazards to female reproductive from current exposure to PFAS through drinking water, and to provide theoretical guidance for designing PFAS alternatives with low female reproductive toxicity.

Flexible Electroflotocoagulation Reactor: New Design and Testing in Treatment of Real Surface Water

A novel continuous and flexible electroflotocoagulation (EFC) reactor was built using concentric cylindrical Al and Fe electrodes, which can be operated either as anodes or cathodes linked to a DC connection. The reactor was operationally assessed related to various cell configurations that assured the required stages of coagulant dosage, mixing, reaction, and settling or flotation. The effects of several design variables and operational parameters (such as the electrode position that determines the reactor configuration, current density (i), flow rate (F), and the electrode area-treated volume ratio (Sel/V)) on the specific energy consumption versus the aluminum dose and charge loading rate were investigated. The most energy-efficient cell configuration using an aluminum anode and iron cathode was tested for the treatment of surface water (Bega river, Timisoara city, Romania) rich in hydrophobic natural organic matter (8.3 mg C∙L−1 and specific UV absorbance parameter of 3.9 L∙m−1∙mg−1) and with a high turbidity of 92 NTU, under flood conditions. The best results that assured 97% turbidity removal, 87% for absorbance recorded at 254 nm, and 60% for DOC removal, through enhanced electroflotocoagulation, were achieved for an operational current density of 10 A∙m−2 with specific energy and electrode consumption of 0.1 kW h∙m−3 and 0.017 kg Al∙m−3, respectively.

Coagulation-ultrafiltration integrated process for membrane fouling control: Influence of Al species and SUVA values of water

Natural organic matter (NOM) pollution is a great challenge for the ultrafiltration (UF) process owing to the inevitable membrane fouling. In this study, three Al species coagulants (Ala/Alb/Alc) and their composites in combination with Poly dimethyl ammonium chloride (PolyDMDAAC) were used as a pretreatment strategy for the UF process. Then, test waters with different NOM fractions (i.e., humic acid, fulvic acid, protein, and polysaccharide) were prepared to analyze the effects of NOM characteristics on membrane fouling behaviors. The results indicated that compared with Alb and Alc, Ala showed higher removal efficiencies for hydrophobic NOM, aromatic organic matters, and suspended particles, but a limited effect on removing dissolved organic carbon (DOC). Ala or Ala-PolyDMDAAC effectively mitigated membrane fouling by removing the hydrophobic NOM in the coagulation process and forming the porous cake layer in the UF process. The test waters with higher specific ultraviolet absorbance (SUVA) resulted in more severe total and reversible membrane fouling but lighter irreversible fouling. After pretreatment by Ala or Ala-PolyDMDAAC, water samples with the medium SUVA value exhibited remarkable alleviation of membrane fouling due to the formation of large, compact, and robust flocs, as well as the construction of loose and poriferous cake layer on the membrane surface. Although hydrophilic NOM was challenging to be removed by coagulation, the interception and re-adsorption of porous cake layers contributed to the alleviation of irreversible fouling.

Augmentation of the coagulation activity of alum using a porous bio-flocculant for the remediation of trihalomethanes-generating hydrophobic natural organic matter

Augmentation of the coagulation activity of alum using a porous bio-flocculant for the remediation of trihalomethanes-generating hydrophobic natural organic matter

On the surface hydrophilization of a blended polysulfone membrane: atomic force microscopy measurement and molecular dynamics simulation

This study elucidates a mechanism to improve fouling resistance for a polysulfone (PSf) membrane by blending polyvinylpyrrolidone (PVP). PSf is generally hydrophobic in nature and tends to be fouled by natural organic matter (NOM) due to a hydrophobic bonding during membrane filtration. Thus, to reduce hydrophobic bonding, a hydrophilic treatment is conducted using non-solvent induced phase separation, in which PVP is added to the PSf membrane. To investigate the chemical properties of the membrane surface, a surface elemental analysis using x-ray photoelectron spectroscopy and contact angle measurement of water droplets is conducted. It is found that, with an increase in PVP additive, macroscopic hydrophilicity increases. Next, to measure the surface adsorption of hydrophobic bonding, atomic force microscopy (AFM) is used. In this study, the AFM probe tip is chemically modified with hydrophobic matter that mimics hydrophobic NOM. With this AFM tip, contact force measurements are conducted in order to measure the absorption characteristics between the membrane surface and the NOM. Furthermore, a cross-flow filtration test is carried out to measure adsorption amounts of tannic acid (as a model hydrophobic substance) into the PSf membrane. Finally, these experimental results were phenomenologically investigated using a molecular dynamics simulation to clarify the hydrophilicity mechanism and improvement of anti-fouling performance of the membrane.

Adsorption kinetics and aggregation for three classes of carbonaceous adsorbents in the presence of natural organic matter

In this study, adsorption kinetics of phenanthrene (PNT) and trichloroethylene (TCE) by a graphene nanosheet (GNS), a graphene oxide nanosheet (GO), a single-walled carbon nanotube (SWCNT), a multi-walled carbon nanotube (MWCNT), and two coal based activated carbons (ACs) (F400 and HD3000) were examined in distilled and deionized water (DDW) and under natural organic matter (NOM) preloading conditions. The results showed the times needed for the adsorption of PNT and TCE to reach apparent equilibrium (i.e., ≤3% change per day) followed the order of GO ≥ MWCNT > GNS > SWCNT ∼ HD3000∼F400 and SWCNT > GNS ∼ HD3000 > F400 ∼ MWCNT > GO, respectively. The pseudo second order model successfully represented kinetics data for three classes of carbonaceous adsorbents. The Weber-Morris intraparticle diffusion model indicated three steps adsorption process for PNT and two step adsorption for TCE. In addition, the times needed to reach apparent equilibrium for the adsorption of PNT and TCE in the presence of hydrophobic (HPO) and hydrophilic (HPI) NOM solutions increased for all adsorbents (except for GO). In general, both NOM showed similar impacts on the adsorption rates of PNT and TCE. Aggregation of both GNS and CNTs rapidly occurred during initial couple hours of contact time during preloading, and spiking both PNT and TCE further increased their aggregation.

Complexation of Antimony with Natural Organic Matter: Performance Evaluation during Coagulation-Flocculation Process.

The presence of natural organic matter (NOM) in drinking water sources can stabilize toxic antimony (Sb) species, thus enhancing their mobility and causing adverse effects on human health. Therefore, the present study aims to quantitatively explore the complexation of hydrophobic/hydrophilic NOM, i.e., humic acid (HA), salicylic acid (SA), and L-cysteine (L-cys), with Sb in water. In addition, the removal of Sb(III, V) species and total organic carbon (TOC) was evaluated with ferric chloride (FC) as a coagulant. The results showed a stronger binding affinity of hydrophobic HA as compared to hydrophilic NOM. The optimum FC dose required for Sb(V) removal was found to be higher than that for Sb(III), due to the higher complexation ability of hydrophobic NOM with antimonate than antimonite. TOC removal was found to be higher in hydrophobic ligands than hydrophilic ligands. The high concentration of hydrophobic molecules significantly suppresses the Sb adsorption onto Fe precipitates. An isotherm study suggested a stronger adsorption capacity for the hydrophobic ligand than the hydrophilic ligand. The binding of Sb to NOM in the presence of active Fe sites was significantly reduced, likely due to the adsorption of contaminants onto precipitated Fe. The results of flocs characteristics revealed that mechanisms such as oxidation, complexation, charge neutralization, and adsorption may be involved in the removal of Sb species from water. This study may provide new insights into the complexation behavior of Sb in NOM-laden water as well as the optimization of the coagulant dose during the water treatment process.

The Removal of CuO Nanoparticles from Water by Conventional Treatment C/F/S: The Effect of pH and Natural Organic Matter.

The increased use of engineered nanoparticles (ENPs), such as copper oxide nanoparticles (CuO NPs), in commercial products and applications raises concern regarding their possible release into freshwater sources. Therefore, their removal from water is important to eliminate adverse environmental and human health effects. In this study, the effects of pH and natural organic matter (NOM), i.e., humic acid (HA) and salicylic acid (SA) on the removal of CuO NPs by coagulation/flocculation/sedimentation (C/F/S) were evaluated. The results indicated that pH significantly affects the coagulation efficiency, where 10–60% CuO NPs removal was achieved under extreme acidic/alkaline conditions. However, at neutral pH, removal of up to 90% was observed with a lower ferric chloride (FC) dosage (0.2 mM). The coagulation efficiency and mechanism were strongly affected by the type of Fe species present in the aqueous phase, which is mainly controlled by pH. Higher concentrations of both HA and SA decrease the CuO NPs agglomeration rate, and thereby improve the colloidal stability due to the NOM molecules adsorbed onto the NPs surface. The presence of hydrophobic HA needs a higher FC dosage of 0.5–0.8 mM than a dosage of hydrophilic SA of 0.25–0.35 mM, to obtain a similar CuO coagulation efficiency. Moreover, higher removals of dissolved organic carbon (DOC) and UV254 were observed more in hydrophobic NOM than in hydrophilic. The results of the Fourier transform infrared (FT-IR) analysis of FC composite flocs confirm that the charge neutralization and enmeshment of coagulant might be a possible removal mechanism. The findings of the current study may provide critical information in the prediction of the fate, mobility, and removal of CuO NPs during C/F/S in water treatment.

A novel photodegradation approach for the efficient removal of natural organic matter (NOM) from water

The presence of natural organic matter (NOM) in water can negatively affect water quality if NOM is present in excessive amounts during certain stages of water treatment. It is known that NOM constituents serve as precursors for DBPs (disinfection by-products) during the disinfection step of the water treatment process. Removal of natural organic matter (NOM) before disinfection is therefore essential to control DBP formation; however, owing to the heterogeneity and complexity of NOM, most water treatment processes are unable to attain complete removal of NOM from water sources. There is therefore a great need to develop methods that can effectively degrade NOM into smaller and relatively harmless compounds that are easily removed during water treatment processes. In this study, multi-walled carbon nanotubes/nitrogen, palladium co-doped titanium dioxide (MWCNT/N, Pd co-doped TiO2) (0.5–5% MWCNTs) were fabricated for the enhancement of NOM degradation under visible-light illumination. Different MWCNT/N, Pd co-doped TiO2 (also referred to as CT) nanocomposites were synthesised via a modified sol-gel method and characterised using ultraviolet visible (UV-Vis), X-ray diffraction spectroscopy (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) Spectroscopy and energy-dispersive X-ray spectroscopy (EDS) analysis. The UV-Vis results showed that introducing the MWCNTs on the nanocomposites was accompanied by a red shift, with CT (0.5% MWCNTs) occurring at a longer wavelength than the others. The efficiency and effectiveness of the synthesised nanocomposites was quantified through measuring the NOM degradation rate in raw water samples collected from two South African water treatment plants. These two drinking water treatment plants were selected as the raw water treated in these plants contains different NOM fractions: the raw water treated at Midvaal (MV) Water Company contains transphilic NOM fractions, while that treated at Plettenberg Bay (P) Water Treatment Plant contains high amounts of hydrophobic NOM. The changes in the amount of NOM in a sample were monitored by measuring the UV absorbance at 254 nm (UVA254) as there is a strong correlation between absorbance at this wavelength and the aromatic content. The highest photocatalytic activity was observed with CT (0.5% MWCNTs) which attained 69.4% UVA254 reduction for MV and 97.7% UVA254 reduction for P raw waters. Compared to conventional methods applied by the two water treatment plants of interest, NOM removal efficiency (in terms of UVA254 reduction) by CT (0.5% MWCNTs) increased by up to 9.4% and 11.5% for MV and P water treatment plants, respectively. The enhanced photocatalytic activity of this CT nanocomposite (0.5% MWCNTs) is attributable to the large surface area of the synthesised nanocomposites which allows huge amounts of NOM to be adsorbed onto the surface of the TiO2, thereby increasing their photodegradation. It is also due to the synergistic effect of N and Pd which enhanced the photoactivity of the TiO2 in the MWCNT/N, Pd co-doped TiO2 composite. Overall, it is clear that the use of the conventional processes is not effective in removing NOM from water. Findings obtained show that CT (0.5% MWCNTs) nanocomposite is a promising future NOM removal method that could complement the available water treatment processes in enhancing the removal of the aromatic component of NOM in water.

Ferrate(VI) decomposition in water in the absence and presence of natural organic matter (NOM)

The kinetics of ferrate(VI) decomposition in natural water were assessed in the absence and presence of natural organic matter (NOM) (pH = 7.50, [Fe(VI)] = 54 µM, DOC = 0.00–10.00 and 1.00–8.57 mg/L for a simulated natural water and six real natural waters, respectively). Without NOM, Fe(VI) decomposition in simulated natural water exhibited a biphasic kinetics pattern, i.e. a 2nd-order reaction with respect to Fe(VI) concentration followed by a 1st-order reaction. However, an additional instant Fe(VI) loss was observed at the onset in the presence of NOM for both simulated and real natural waters, thereby rendering Fe(VI) decay with NOM a unique three-stage kinetics pattern. The initial instant Fe(VI) loss was caused due to the homogenous Fe(VI) self-decay and the rapid reactions between Fe(VI) and NOM. The latter accounted for a major fraction of the initial Fe(VI) loss and was in direct proportion with the initial DOC (DOC0) (Δ[Fe(VI)]0DOC = αNOM DOC0; αNOM = 1.45 µM Fe(VI)·L/mg DOC for the simulated natural water, and 0.66–1.35 µM Fe(VI)·L/mg DOC for the six natural waters). Fe(VI) decomposition experiments with different Suwannee River NOM isolates revealed that hydrophobic NOM fractions (i.e. fulvic acid (FA) and humic acid (HA)) caused a more significant initial Fe(VI) loss than the hydrophilic group (HPI), suggesting that Fe(VI) preferentially reacted with hydrophobic NOM molecules rather than hydrophilic compounds. Furthermore, an approach developed for the estimation of αNOM revealed a linear correlation between αNOM and specific UV absorbance (SUVA) (αNOM = 0.27SUVA + 0.18, R2 = 0.71). This study provides essential information regarding Fe(VI) decomposition for the determination of Fe(VI) dose and exposure for effective water treatment.

Feasibility of bubble surface modification for natural organic matter removal from river water using dissolved air flotation

A novel, functionalized bubble surface can be obtained in dissolved air flotation (DAF) by dosing chemicals in the saturator. In this study, different cationic chemicals were used as bubble surface modifiers, and their effects on natural organic matter (NOM) removal from river water were investigated. NOM in the samples was fractionated based on molecular weight and hydrophobicity. The disinfection byproduct formation potentials of each fraction and their removal efficiencies were also evaluated. The results showed that chitosan was the most promising bubble modifier compared with a surfactant and a synthetic polymer. Tiny bubbles in the DAF pump system facilitated the adsorption of chitosan onto microbubble surfaces. The hydrophobic NOM fraction was preferentially removed by chitosan-modified bubbles. Decreasing the recycle water pH from 7.0 to 5.5 improved the removal of hydrophilic NOM with low molecular weight. Likewise, hydrophilic organic compounds gave high dihaloacetic acid yields in raw water. An enhanced reduction of haloacetic acid precursors was obtained with recycle water at pH values of 5.5 and 4.0. The experimental results indicate that NOM fractions may interact with bubbles through different mechanisms. Positive bubble modification provides an alternative approach for DAF to enhance NOM removal.

Investigation of natural organic matter (NOM) character and its removal in a chlorinated and chloraminated system at Rand Water, South Africa

In its natural environment, natural organic matter (NOM) is not problematic. However, during water treatment NOM does affect water quality specifically during the disinfection step, where if NOM is present it reacts with disinfectants resulting in the formation of disinfection by-products. To emphasize the importance of NOM monitoring during potable water treatment this study aimed to characterize NOM and evaluate NOM removal by a conventional water treatment plant considering seasonal trends. NOM was characterized by making use of NOM polarity and specific ultraviolet absorbance. NOM removal was monitored with high-performance size exclusion chromatography, dissolved organic carbon (DOC) and UV254 analyses. The polarity rapid assessment method indicated that the hydrophobic and hydrophilic NOM fractions within the surface water increased during a period of heavy rain when floods occurred, but conversely decreased during an average rain season. Although NOM character showed variability during the 5-year study period, seasonal relationship during high and low flow seasons between aromatic NOM and total trihalomethane (TTHM) formation was not evident. Aromatic NOM was not the only precursor to TTHM formation, which stresses the need to implement advanced NOM characterization techniques during NOM monitoring to study reactivity of the individual NOM fraction with the disinfectant used at the water treatment plant.

Formation of known and unknown disinfection by-products from natural organic matter fractions during chlorination, chloramination, and ozonation

Natural organic matter (NOM) is the main precursor of disinfection by-products (DBPs) formed during drinking water treatment processes. Previous studies of the relationships between DBP formation and NOM fractionation have mainly been focused on currently regulated DBPs and a few certain emerging DBPs. In this work, the Suwannee River NOM solution was fractionated into groups with different hydrophobicities using DAX-8 resins, and volatile and semi-volatile DBPs formed during the chlorination, chloramination and ozonation of the NOM fractions were examined by a nontargeted screening of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry procedure. The results showed that a total of 302 DBPs representing nine chemical classes were detected, of which 266 were possibly newly detected, based on library searching with NIST 08 library (using similarity and reverse values of at least 600 and 700, respectively) and linear retention indices. The characterization of DBP precursors suggests that hydrophobic (HPO) NOM contains the major fraction of precursor for the formation of nitrogenous DBPs (contributing about 60% of the total nitrogenous DBPs) during all three disinfection processes. Much larger amounts of heterocyclic DBPs were formed from the HPO fraction than from the hydrophilic fraction during chlorination. During chloramination and ozonation, 5–15 times more ketones were formed from the hydrophilic fraction than from the HPO fraction. During ozonation, more than twice the amounts of esters and alcohols were formed from the hydrophilic fraction than from the HPO fraction. Three-dimensional excitation-emission matrix spectra suggest that similar to the formation of regulated DBPs, humic acid-like substances are probably the precursors of halogen-containing DBPs. Relatively higher nitrogenous DBPs formation from the HPO fraction might be because of the existence of protein-like materials.

Improved membrane pretreatment of high hydrophobic natural organic matter (NOM) waters by floatation

Pretreatment by coagulation/flocculation/sedimentation is often used to alleviate membrane fouling; however there has been limited research on floatation as the pretreatment separation process. The main objective of this study is to compare sedimentation with floatation as part of the pretreatment for ultrafiltration (UF) of river water with relatively high hydrophobic (HPO) natural organic matter (NOM) content. Water samples pretreated at full-scale plants were subjected to multiple-day UF membrane fouling tests (constant flux with backwash and chemical cleaning) using an automated bench-scale UF hollow fiber membrane system. Based on the samples tested, coagulation/floatation pretreatment resulted in less fouling than coagulation/sedimentation during both summer and winter testing. The improved performance appears to be linked to greater HPO NOM removal by the pretreatment. Most fouling could be reversed by hydraulic backwashing and chemical cleaning. Enhanced chemical backwash with 100mgL−1 chlorine and chemical clean with 0.1N NaOH and 200mgL−1 chlorine were found to be very effective at reducing fouling for pretreated water. As expected, longer filtration cycles resulted in greater fouling.

Bench-scale study of ultrafiltration membranes for evaluating membrane performance in surface water treatment

Currently, there is no standard bench-scale dead-end ultrafiltration (UF) testing system. The aim of the present study was to design and build a bench-scale hollow fiber UF system to assess the impact of operational parameters on membrane performance and fouling. A bench-scale hollow fiber UF system was built to operate at a constant flux (±2% of the set-point flux) and included automated backwash cycles. The development of the bench-scale system showed that it is very difficult to maintain a constant flux during the first minute of the filtration cycles, that digital flow meters are problematic, and that the volume of the backwash waste lines should be minimized. The system was evaluated with Ottawa River water, which has a relatively high hydrophobic natural organic matter content and is typical of Northern Canadian waters. The testing using different permeate fluxes, filtration cycle duration and backwash cycle duration showed that this system mimics the performance of larger systems and may be used to assess the impact of operating conditions on membrane fouling and alternative pretreatment options. Modeling the first, middle, and last filtration cycles of the six runs using single and dual blocking mechanisms yielded inconsistent results regarding the controlling fouling mechanisms.

Preparation of engineered carbon nanotube materials and its application in water treatment for removal of hydrophobic natural organic matter (NOM)

Organic matters in drinking water are composed of soluble and particulate fractions. Soluble organic matters generally originated from allochthonous, autochthonous, and synthetic organic. Silica sand filters, which are utilized in water treatment, have a low potential of removing the soluble organic matters. Traditional carbon-based media such as activated carbon and anthracite are among the choices for the removal of soluble organic. Carbon nanotubes (CNTs) have a higher potential in removing synthetic and natural organic materials than the other traditional carbon based media. Utilization of CNTs at the slurry state requires the removal of the nanotubes themselves at the end of the process which leads to yet another problem to take care of. The present study, therefore, aims at solving this problem. In so doing, oxidized CNTs (140°C, 5 h, Nitric acid) were bound to the surface of silica sand through 3-(triethoxysilyl)propylamine to act as a bonding agent. Humic acid was used as the index of natural organic matters. The removal potential of humic acid with the new adsorbent (CNTsand) was studied under various operational conditions (contact time, temperature, and initial concentration). According to the obtained data, CNTsand has a good potential in the removal of humic acid (qmax = 81.96 mg/g CNT). Additionally, the kinetic, isotherm, and thermodynamic of adsorption were investigated, for which the data followed the pseudo-second-order kinetic model and Langmuir isotherm. Evaluation of enthalpy change (ΔH = 11.02 kJ/mol) and free energy change (ΔG = –7.32 to –9.20 kJ/mol) indicated that the reaction is spontaneous, endothermic, and thermodynamically favorable. Regeneration study showed that the desorption step of humic acid was faster than its adsorption step. It was observed that after five cycles, the adsorption capacity amounted to roughly 50% of the initial adsorption capacity. The above data depict that the new engineered material is a good reusable adsorbent in water treatment.