Bench-scale testing of a magnetic ion exchange resin for removal of disinfection by-product precursors

The objective of this research was to compare enhanced coagulation with anion exchange for removal of disinfection by-product (DBP) precursors (i.e. natural organic matter (NOM) and bromide). Treatment with a magnetic ion exchange resin (MIEX((R))) was the primary focus of this study. Raw waters from four utilities in California were evaluated. The waters had low turbidity, low to moderate organic carbon concentrations, a wide range of alkalinities, and moderate to high bromide ion concentrations. The treated waters were compared based on removal of ultraviolet (UV) absorbance, dissolved organic carbon (DOC), trihalomethane formation potential (THMFP), and haloacetic acid formation potential (HAAFP). The results indicated that treatment with MIEX is more effective than coagulation at removing UV-absorbing substances and DOC. Treatment with MIEX and treatment with MIEX followed by coagulation yielded similar results, suggesting that coagulation of MIEX-treated water does not provide additional removal of organic carbon. MIEX treatment reduced the THMFP and HAAFP in all waters, and did so to a greater extent than coagulation. Treatment with MIEX was most effective in raw waters having a high specific UV absorbance and a low anionic strength. Following MIEX treatment, subsequent chlorination resulted in a shift to the more brominated THM and HAA species as compared to chlorination of the raw water. MIEX also removed bromide to varying degrees, depending on the raw water alkalinity and initial bromide ion concentration.     

Removal of bromide and natural organic matter by anion exchange

Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 μg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC.     

A pilot-scale evaluation of magnetic ion exchange treatment for removal of natural organic material and inorganic anions

The objective of this research was to evaluate a magnetic ion exchange process (MIEX) for the removal of natural organic material (NOM) and bromide on a continuous-flow pilot-scale basis under different operating conditions and raw water characteristics. The most important operating variable was the effective resin dose (ERD), which is the product of the steady-state resin concentration in the contactor and the regeneration ratio. The raw water employed in this study had a moderate concentration of ultraviolet (UV)-absorbing substances and dissolved organic carbon (DOC), and a low turbidity, alkalinity, and concentration of competing anionic species. Experiments were conducted using the ambient raw water and raw water spiked with bromide, chloride, and sulfate. Substantial removal of UV-absorbing substances and DOC was achieved at ERDs as low as 0.16mL/L. Moderate bromide removal was achieved, depending on the ERD. Increasing the sulfate concentration resulted in decreased removal of UV-absorbing substances, DOC, and bromide. Consistent results were observed between the continuous-flow pilot plant tests and batch equilibrium studies.     

Removal of natural organic matter by ion exchange

Ion exchange is an effective method for removing humic substances from drinking water supplies. We have explored a range of anion exchangers for removal of natural organic matter (NOM), both as isolated from surface waters and after fractionation into four fractions based on hydrophobic and hydrophilic properties. Resins of open structure and high water content are confirmed as the better performers, being very efficient at removal of any charged material, especially that of smaller molecular size. Quaternary ammonium resins containing polar groups are especially effective. The presence of a neighbouring OH group close to the quaternary nitrogen, heteroatoms in the bridge between the exchange site and the polymer backbone, a secondary amino group as the exchange site, or a low ratio of carbon to quaternary nitrogen is beneficial. A suitable balance of polar and non-polar regions in the resin structure appears to be required. Weakly basic amino groups may have a greater affinity for hydrophilic counter ions than quaternary ammonium groups, but generally there are fewer charged sites in the resin at neutral pH. Nevertheless, weak base resins have NOM uptakes nearly as high as strong base resins of similar water content. Water content was found to be the most important parameter, though the effect was less pronounced for strong base resins. For weak base resins of low charge density a non-electrostatic mechanism involving hydrogen bonding of the undissociated acidic species in the NOM to the unprotonated amino groups on the resins is proposed.     

Combination of coagulation and ion exchange for the reduction of UF fouling properties of a high DOC content surface water

The treatment of a high DOC content surface water (about 6mg DOC/L) using anion exchange resins (MIEX resin from Orica or IRA958 resin from Rohm and Haas) can remove up to 80% of DOC in less than 45min. The combination of coagulation prior to or after resin treatment only slightly improves the removal of DOC (0.2-0.3mg/L) but eliminates the high MW organic compounds (MW >20kDa) attributed to biopolymers (proteins and polysaccharides) that were not removed using anion exchange resins alone and that were found to be responsible for reversible fouling of UF membranes (YM 100 UF membrane from Millipore with MW cut-off of 100kDa). The combination of treatments then significantly improves the permeability of the UF membrane. Also, the combination of both treatments allows a reduction of the coagulant doses by a factor of 6 with no impact on the DOC removal and the filterability of produced waters.     

Effects of blending of desalinated water with treated surface drinking water on copper and lead release

This study examined effects of desalinated water on the corrosion of and metal release from copper and lead-containing materials. A jar test protocol was employed to examine metal release from copper and lead-tin coupons exposed to water chemistries with varying blending ratios of desalinated water, alkalinities, pHs and orthophosphate levels. Increasing fractions of desalinated water in the blends resulted in non-monotonic changes of copper and lead release, with generally lower metal concentrations in the presence of desalinated water, especially when its contribution increased from 80% to 100%. SEM examination showed that the increased fractions of desalinated water were associated with pronounced changes of the morphology of the corrosion scales, likely due to the influence of natural organic matter. This hypothesis was corroborated by the existence of correlations between changes of the ζ-potential of representative minerals (malachite and hydrocerussite) and metal release. For practical applications, maintaining pH at 7.8 and adding 1 mg/L orthophosphate as PO₄ were concluded to be adequate to decrease copper and lead release. Lower alkalinity of desalinated water was beneficial for blends containing 50% or more desalinated water.     

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

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

Secondary effects of anion exchange on chloride, sulfate, and lead release: systems approach to corrosion control

Water treatment processes can cause secondary changes in water chemistry that alter finished water quality including chloride, sulfate, natural organic matter (NOM), and metal release. Hence, the goal of this research was to provide an improved understanding of the chloride-to-sulfate mass ratio (CSMR) with regards to chloride and sulfate variations at full-scale water treatment plants and corrosion potential under simulated premise plumbing conditions. Laboratory corrosion studies were conducted using Pb-Sn solder/Cu tubing galvanic cells exposed to model waters with low (approx. 5 mg/L Cl⁻ and 10 mg/L SO₄^2-) and high (approx. 50 mg/L Cl⁻ and 100 mg/L SO₄^2-) concentrations of chloride and sulfate at a constant CSMR of ∼0.5. The role of NOM during corrosion was also evaluated by changing the type of organic material. In addition, full-scale sampling was conducted to quantify the raw water variability of chloride, sulfate, and NOM concentrations and the changes to these parameters from magnetic ion exchange treatment. Test conditions with higher concentrations of chloride and sulfate released significantly more lead than the lower chloride and sulfate test waters. In addition, the source of NOM was a key factor in the amount of lead released with the model organic compounds yielding significantly less lead release than aquatic NOM.     

Bicarbonate-form anion exchange: affinity, regeneration, and stoichiometry

Magnetic ion exchange (MIEX) is an effective process for removing dissolved organic carbon (DOC) from natural waters, but its implementation has been limited due to production of waste sodium chloride solution (i.e., brine) from the regeneration process. Chloride is of concern because elevated concentrations can have adverse effects on engineered and natural systems. The goal of this research was to explore the efficacy of using anion exchange resin with bicarbonate as the mobile counter ion, which would produce a non-chloride regeneration solution. It was found that bicarbonate-form MIEX resin had a similar affinity as chloride-form MIEX resin for sulfate, nitrate, DOC, and ultraviolet-absorbing substances. Both bicarbonate-form and chloride-form MIEX resins showed the greatest removal efficiencies as fresh resin, and removal efficiency decreased with multiple regeneration cycles. Nevertheless, sodium bicarbonate solution was as effective as sodium chloride solution at regenerating MIEX resin. Regeneration of the bicarbonate-form MIEX resin was illustrated by sparging carbon dioxide gas in a water/resin slurry. This regeneration process would eliminate the need for the addition of salts such as sodium chloride or sodium bicarbonate. The stoichiometry of the bicarbonate-form resin revealed that the bicarbonate was deprotonating within the resin matrix leading to a mixture of both carbonate and bicarbonate mobile counter ions. This work makes an important contribution to ion exchange applications for water treatment by evaluating the affinity, regeneration, and stoichiometry of bicarbonate-form anion exchange.     

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.     

Transition in fouling mechanism in microfiltration of a surface water

The main disadvantage of membrane filtration is membrane fouling, which remains as the major obstacle for more efficient use of this technology. Information about the constituents that cause fouling is indispensable for more efficient operation. We examined the changes in both foulant characteristics and membrane morphology by performing the pilot-scale filtration test using one microfiltration membrane. During the operation, we cut the membrane fibers three times, and the components that caused irreversible fouling were extracted by acid or alkaline solution. We found that the characteristic of inorganic matter extracted by acid solution completely differed depending on the filtration period. A large amount of iron was extracted in the second chemical cleaning, while manganese was the dominant component of the extracted inorganic matter in the third chemical cleaning. The analysis of Fourier transform infrared (FTIR) and cross polarization magic angle spinning carbon-13 (CPMAS (13)C) nuclear magnetic resonance (NMR) demonstrated that the contribution of humic substances and carbohydrate in the organic foulant had increased as fouling developed. The changes in the major foulant have no relation with the fluctuation in feed water. The analysis of membrane morphology illustrated that the cake layer started to build up after the blockage of membrane pores. Based on the above results, we hypothesized the following fouling mechanism: the pores were covered or narrowed with relatively large particles such as iron, carbohydrate or protein; small particles such as manganese or humic substances blocked the narrowed pores; and finally an irreversible cake layer started to build up on the membrane surface.     

Impact of a magnetic ion exchange resin on ozone demand and bromate formation during drinking water treatment

The objective of this research was to examine the impact of a magnetic ion exchange resin (MIEX) on ozone demand and bromate formation in two different ozonated waters at bench scale. The first raw water had a high bromide ion concentration, a high ozone demand, and was highly colored. Based on experimental findings from the first water, the second water was selected as a model water in which more controlled experiments were performed. The waters were treated with the MIEX resin using jar test procedures to find the optimal MIEX dosage based upon the removal of ultraviolet (UV)-absorbing substances, dissolved organic carbon (DOC), and bromide. The optimal resin dosage was chosen for bulk MIEX treatment and subsequent ozonation in a semi-batch reactor. The ozone demand and formation of bromate were analyzed as a function of ozone dosage and dissolved ozone concentration for the MIEX pre-treated water, and compared to the results obtained by ozonating the water without MIEX pre-treatment. The results indicate that pre-treatment of the water with the MIEX resin significantly reduces total organic carbon, DOC, UV absorbance, color, and to some extent, bromide. MIEX pre-treatment of the water prior to ozonation substantially lowered the ozone demand and formation of bromate during subsequent ozonation.     

A polishing hybrid AER/UF membrane process for the treatment of a high DOC content surface water

The efficacy of a combined AER/UF (Anion Exchange Resin/Ultrafiltration) process for the polishing treatment of a high DOC (Dissolved Organic Carbon) content (>8 mgC/L) surface water was investigated at lab-scale using a strong base AER. Both resin dose and bead size had a significant impact on the kinetic removal of DOC for short contact times (i.e. <15 min). For resin doses higher than 700 mg/L and median bead sizes below 250 μm DOC removal remained constant after 30 min of contact time with very high removal rates (80%). Optimum AER treatment conditions were applied in combination with UF membrane filtration on water previously treated by coagulation-flocculation (i.e. 3 mgC/L). A more severe fouling was observed for each filtration run in the presence of AER. This fouling was shown to be mainly reversible and caused by the progressive attrition of the AER through the centrifugal pump leading to the production of resin particles below 50 μm in diameter. More important, the presence of AER significantly lowered the irreversible fouling (loss of permeability recorded after backwash) and reduced the DOC content of the clarified water to l.8 mgC/L (40% removal rate), concentration that remained almost constant throughout the experiment.     

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.     

Natural organic matter fouling of low-pressure, hollow-fiber membranes: Effects of NOM source and hydrodynamic conditions

Effects of natural organic matter (NOM) source and hydrodynamic conditions on both hydraulically reversible and irreversible fouling of low-pressure, hollow-fiber (LPHF) membranes were systematically investigated using representative sources of natural waters and wastewater effluents. It was found that NOM source plays a primary role in determining the fouling of these membranes. Increase in permeate flux promoted membrane fouling, but to a lesser extent than NOM source. Permeate backwash flux appeared to restore permeability more effectively for the polyether sulfone (PES) membranes than to the polyvinylidene fluoride (PVDF) membranes used. NOM characterization revealed that organic colloids contributed predominantly to the hydraulically reversible fouling, and potentially to the irreversible fouling. Overall, this study demonstrated the importance of NOM source and the presence of organic colloids in the fouling of LPHF membranes, as well as the relevance of hydrodynamic operating conditions on the hydraulic reversibility of the fouling.     

Combined coagulation-disk filtration process as a pretreatment of ultrafiltration and reverse osmosis membrane for wastewater reclamation: an autopsy study of a pilot plant

The effects of the combined coagulation-disk filtration (CC-DF) process on the fouling characteristics and behavior caused by interactions between effluent organic matter (EfOM) and the membrane surfaces of the ultrafiltration (UF) and reverse osmosis (RO) membranes in a pilot plant for municipal wastewater reclamation (MWR) were investigated. The feed water from secondary effluents was treated by the CC-DF process used as a pretreatment for the UF membrane to mitigate fouling formation and the permeate from the CC-DF process was further filtered by two UF membrane units in parallel arrangement and fed into four RO modules in a series connection. The CC-DF process was not sufficient to mitigate biofouling but the UF membrane was effective in mitigating biofouling on the RO membrane surfaces. Fouling of the UF and RO membranes was dominated by hydrophilic fractions of EfOM (e.g., polysaccharide-like and protein-like substances) and inorganic scaling (e.g., aluminum, calcium and silica). The desorbed UF membrane foulants included more aluminum species and hydrophobic fractions than the desorbed RO membrane foulants, which was presumably due to the residual coagulants and aluminum-humic substance complexes. The significant change in the surface chemistry of the RO membrane (a decrease in surface charge and an increase in contact angle of the fouled RO membranes) induced by the accumulation of hydrophilic EfOM onto the negatively charged RO membrane surface intensified the fouling formation of the fouled RO membrane by hydrophobic interaction between the humic substances of EfOM with relatively high hydrophobicity and the fouled RO membranes with decreased surface charge and increased contract angle.     

High-performance thin-layer hydrogel composite membranes for ultrafiltration of natural organic matter

Thin-layer hydrogel composite (TLHC) ultrafiltration (UF) membranes were synthesized by photo-grafting of either poly(ethylene glycol) methacrylate (PEGMA) or N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium betaine (SPE) onto commercial polyethersulfone (PES) UF membranes. The performance of TLHC UF membranes was evaluated for natural organic matter (NOM) filtration and compared to commercial PES UF membranes. The fouling evaluation was done by investigation of membrane-solute interactions (adsorptive fouling) and membrane-solute-solute interactions (UF). The results suggest that the TLHC membranes convincingly displayed a higher adsorptive fouling resistance than unmodified PES UF membranes. In long-term stirred dead-end UF, a much lower fouling was observed for TLHC membranes than for commercial membranes with the same flux and rejection. Further, water flux recovery was also much higher. An analysis using an existing blocking model was performed in order to elucidate the effect of a polymer hydrogel layer on fouling mechanism as well as cake layer characteristics. The TLHC membranes synthesized by photo-grafting of PEGMA (40 g/L) and PEGMA with a low concentration of cross-linker monomer in the reaction mixture (ratio: 40/0.4 (g/L)/(g/L)) showed a much better performance than the other composite membranes. Those membranes could reduce the cake resistance on the membrane surface. This work has relevance for the design of high-performance UF membranes for applications in water treatment.     

Impact of polymer flocculants on coagulation-microfiltration of surface water

Organic polymers are widely used as flocculants in pretreatment for microfiltration. However, their impact on microfiltration system performance was not well understood. In this study, the effects of three types of polymer flocculants on microfiltration permeate water quality and membrane fouling were evaluated using a hollow fiber membrane under two different operation modes, coagulation/flocculation-sedimentation-microfiltration (CFSM) and coagulation/flocculation-microfiltration (CFM). Interestingly, the effect of polymers on membrane fouling did not appear to reflect their impact on dissolved organic matter content or floc particle properties in the membrane feed water. The addition of polymer flocculants resulted in floc particles of larger size and smaller fractal dimension and slightly enhanced the removal of dissolved organic matter, both of which were expected to reduce membrane fouling. However, it significantly aggravated membrane fouling in all cases except when the positively charged poly(diallyldimethylammonium) chloride was used in the CFSM process. In particular, all polymers greatly increased hydraulically irreversible fouling in the CFM mode. The increased fouling in the CFSM mode is attributed to the residual polymer, while that in the CFM mode is attributed to the enhanced irreversible floc particle attachment on the membrane surface. Considering the potential severe membrane fouling and the small improvement in treated water quality when polymers are used, the application of polymers in microfiltration pretreatment needs to be carefully evaluated.     

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.     

Comparison of low-cost and engineered materials for phosphorus removal from organic-rich surface water

Excess phosphorus (P) in lakes and rivers remains a major water quality problem on a global scale. As a result, new materials and innovative approaches to P remediation are required. Natural materials and waste byproduct materials from industrial processes have the potential to be effective materials for P removal from surface water. Advantages of natural and waste byproduct materials include their low-cost, abundant supply, and minimal preparation, especially compared with engineered materials, such as ion exchange resins and polymeric adsorbents. As a result, natural and waste byproduct materials are commonly referred to as low-cost materials. Despite the potential advantages of low-cost materials, there are critical gaps in knowledge that are preventing their effective use. In particular, there are limited data on the performance of low-cost materials in surface waters that have high concentrations of natural organic matter (NOM), and there are no systematic studies that track the changes in water chemistry following treatment with low-cost materials or compare their performance with engineered materials. Accordingly, the goal of this work was to evaluate and compare the effectiveness of low-cost and engineered materials for P removal from NOM-rich surface water. Seven low-cost materials and three engineered materials were evaluated using jar tests and mini-column experiments. The test water was a surface water that had a total P concentration of 132-250 μg P/L and a total organic carbon concentration of 15-32 mg C/L. Alum sludge, a byproduct of drinking water treatment, and a hybrid anion exchange resin loaded with nanosize iron oxide were the best performing materials in terms of selective P removal in the presence of NOM and minimum undesirable secondary changes to the water chemistry.