Natural organic matter (NOM) and pesticides removal using a combination of ion exchange resin and powdered activated carbon (PAC)

The combination of anion exchange resins (AERs) and powdered activated carbon (PAC) was studied to remove both natural organic matter (NOM) and pesticides. Experiments were conducted with high dissolved organic carbon (DOC) surface water (about 6.0mg DOC/L) spiked with both atrazine and isoproturon. AERs, like MIEX and IRA938, showed up to 75% removal of DOC after 30min contact time. The addition of PAC after treatment with these AERs only slightly decreased the residual DOC from 1.4 to 1.2mg/L. Experiments conducted with high (200microg/L) and low (1microg/L) initial pesticide concentrations showed that simultaneous and successive combinations of AER and PAC significantly improve the removal of both pesticides compared with PAC treatment on raw water. The improvement of short-term adsorption kinetics was explained by the adsorption of pesticides on AERs (about 5%) and the removal of high molecular weight (MW) NOM structures by AERs that reduce pore blockage phenomena. For 24h contact time with PAC (adsorption isotherms), the benefit of AER treatment was lower, which indicates that the refractory DOC to AER treatment still competes through direct site competition mechanism. MIEX resin had a distinct behavior since the simultaneous treatment with PAC showed no benefit on pesticide adsorption. The presence of fine residues of MIEX was shown to interfere with PAC adsorption.     

Combination of ferric and MIEX for the treatment of a humic rich water

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane (THM) standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by a new ion exchange process (MIEX) using both bulk and fractionated NOM. Initial results showed that in excess of 80% of the raw water dissolved organic carbon (DOC) and greater than 85% of the UV absorbance from the bulk raw water could be removed by the use of MIEX alone. It was also seen that the removal of the more recalcitrant isolated fractions was increased. When MIEX was combined with a significantly reduced dose of coagulant a slight improvement on the overall DOC and UV removals was observed, however a significant decrease in the amount of THM formation potential (THMFP) in the final water was seen. This combined with the reduction in coagulant would imply a more efficient process during the times when the water becomes increasingly difficult to treat.     

Long term case study of MIEX pre-treatment in drinking water; understanding NOM removal

Removal of natural organic matter (NOM) is a key requirement to improve drinking water quality. This study compared the removal of NOM with, and without, the patented magnetic ion exchange process for removal of dissolved organic carbon (MIEX DOC) as a pre-treatment to microfiltration or conventional coagulation treatment over a 2 year period. A range of techniques were used to characterise the NOM of the raw and treated waters. MIEX pre-treatment produced water with lower concentration of dissolved organic carbon (DOC) and lower specific UV absorbance (SUVA). The processes incorporating MIEX also produced more consistent water quality and were less affected by changes in the concentration and character of the raw water DOC. The very hydrophobic acid fraction (VHA) was the dominant NOM component in the raw water and was best removed by MIEX pre-treatment, regardless of the raw water VHA concentration. MIEX pre-treatment also produced water with lower weight average apparent molecular weight (AMW) and with the greatest reduction in complexity and range of NOM. A strong correlation was found between the VHA content and weight average AMW confirming that the VHA fraction was a major component of the NOM for both the raw water and treated waters.     

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.     

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.     

Impact of recycling filter backwash water on organic removal in coagulation-sedimentation processes

The overall purpose of this research was to examine the impacts of filter backwash water (FBWW) and membrane backwash water (MBWW) recycles on water quality in coagulation-sedimentation processes. Specifically, the impact of recycling 5 or 10% by volume of FBWW and MBWW with surface water on the removal of natural organic matter (NOM) was evaluated at bench-scale using a standard jar-test apparatus and measurement of specific water quality parameters including total organic carbon (TOC), dissolved organic carbon (DOC), UV254, turbidity, total aluminum and zeta potential. The results of jar test conducted on a source water with a specific UV absorbance (SUVA) value within the range of 2-4 mg/L m showed a significantly higher removal of DOC from the raw water that was blended with 5 and 10% by volume of FBWW as compared to control trials where backwash water was not added. Increasing rates of MBWW that did not contain destabilized hydroxide precipitates did not significantly change DOC concentrations in the settled water samples as compared to the control trials. For source waters that are characterized as having low turbidity with medium SUVA values, these results could hold particular significance for plants that have reached treatment ceilings in terms of dissolved NOM removal using conventional coagulation designs.     

地下水中天然有机物对生物除铁滤柱的影响研究

采用生物滤柱对地下水进行试验研究,用膜过滤法对其出水进行了分子量分析,考察了生物除铁滤柱对不同分子量区间天然有机物的去除效果。结果表明:有机物分子量大小对出水水质有较大的影响,有机物分子量越大,铁去除率越低,DOC和UV254去除率也越低。生物滤柱对原水中分子量1 kDa的有机物的去除率为82.4%,而对分子量30 kDa的有机物的去除率只有28.5%。     

MIEX/超滤一体化工艺净化长江原水的研究

水体中的天然有机物是造成超滤膜污染的重要因素。考察了磁性离子交换树脂(MIEX)/超滤膜一体化净水工艺处理长江原水的效果,并通过与超滤膜直接过滤进行比较,探讨了MIEX预处理对去除有机物的影响及控制膜污染的效果。结果表明,与原水直接进行超滤处理相比,组合工艺对CODMn、DOC、UV254的去除率分别提高了40.70%、38.20%和43.90%。MIEX/超滤工艺控制消毒副产物的优势更为明显,对THMFP和HAAFP的去除率分别达62.54%和55.83%。由于MIEX预处理去除了原水中56.72%的疏水性有机物,降低了超滤膜的负荷,延缓了膜表面致密凝胶层的形成,因而减少了膜孔堵塞,可有效控制运行压力的增长速度,延长过滤时间。     

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.     

Effects of magnetic ion exchange pretreatment on low pressure membrane filtration of natural surface water

Magnetic ion exchange (MIEX) pretreatment has been increasingly employed by water treatment plants for removal of dissolved organic carbon (DOC). In this study, the effects of MIEX pretreatment on low pressure membrane filtration of natural surface water were investigated under different feedwater qualities, membrane properties, and MIEX dosing conditions. Regardless of feedwater DOC, moderate decrease in the total and hydraulically irreversible fouling was observed for a polyvinylidene fluoride (PVDF) microfiltration membrane and a polyethersulfone ultrafiltration (UF) membrane after MIEX pretreatment, which was coincident with moderate removals of high molecular weight DOC in the feedwaters. Comparatively, the fouling of a PVDF UF membrane did not decrease after MIEX pretreatment, revealing the impact of membrane properties on membrane fouling in the presence of MIEX pretreatment. Reuse of virgin or regenerated MIEX resulted in similar membrane fouling as observed with single use of the virgin MIEX. The level of DOC removal by MIEX was similar to the removal of MS2 bacteriophage spiked in the feedwater, suggesting a potential similarity in the removal of organic and microbial particles. In conclusion, MIEX pretreatment was effective for DOC removal, but less effective in controlling short-term membrane fouling or removing viruses.     

Preliminary laboratory investigation of disinfection by-product precursor removal using an advanced oxidation process

Natural organic matter (NOM) is ubiquitous in surface and ground waters throughout the world. During drinking water treatment, the NOM that remains in treated water can react with chlorine to form disinfection by‐products. It has been shown that titanium dioxide photocatalysis can achieve over 96% reduction in ultraviolet (UV)₂₅₄ absorbing species such as hydrophobic NOM and over 81% reduction in dissolved organic carbon (DOC). However, an additional filtration stage is required to recover the suspended catalyst before it is suitable for municipal drinking water application. To overcome this problem, we have used immobilised catalysts prepared using chemical sol–gels, and their performance has been assessed during bench‐scale experiments. An immobilised catalyst enables in situ regeneration using UV light and subsequent reuse of the catalyst. In this research, titanium dioxide sol–gels have been used to coat substrates at a laboratory scale. Results showed that the various coatings prepared had different removal efficiencies for both DOC and UV₂₅₄ absorbance. Maximum removals were 1.336 g/m² and 89%, respectively.     

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.     

The effect of ozonation on natural organic matter removal by alum coagulation

Natural organic matter (NOM) was extracted from a moderately colored, eutrophic surface water source (Forge Pond, Granby, MA), and fractionated into quasi-homogeneous fractions. Fulvic acid (FA) and hydrophilic neutrals (HN) were the two most abundant NOM fractions that were isolated. Adsorption affinity of the isolated NOM fractions on preformed aluminum hydroxide flocs increased with increase in specific organic charge of the fractions, except for the two most highly charged fractions, FA and hydrophilic acids (HAA), which showed less adsorption affinity than expected based on their specific organic charge. Prior ozonation of FA and HN fractions resulted in a decline and an increase, respectively, in their adsorption affinity on aluminum hydroxide surface. Prior ozonation of Forge Pond raw water resulted in a progressive decline in dissolved organic carbon (DOC) removal by alum coagulation with increase in ozone dose. It appeared that ozone applied to raw water reacted preferentially with the humic fraction of NOM, resulting in the detrimental effects of ozonation on subsequent NOM removal by alum coagulation being magnified. Forge Pond raw water was pre-coagulated to remove humic substances. Ozonation of the pre-coagulated water demonstrated the beneficial effects of ozonation on the removal of non-humic NOM through alum coagulation. A strategy for staged coagulation with intermediate ozonation was proposed for waters containing both humic and non-humic NOM for maximum DOC and specific UV absorbance at 254nm (SUVA) removal.     

磁性离子交换树脂与超滤膜联用处理淮河原水

采用磁性离子交换树脂(MIEX)/混凝沉淀/超滤膜(UF)工艺处理淮河原水,考察了对有机物的去除特性以及MIEX预处理控制膜污染的效果.结果表明:UF出水浊度稳定在0.1NTU以下,粒径>2 μm的颗粒数平均为11个/mL,粒径>10μm的颗粒物被完全去除;组合工艺对CODMn和UV254的去除率分别为75.3%和90%,且能有效去除不同分子质量区间的有机物;系统对疏水性有机物(HOM)、弱疏水性有机物(WHOM)、荷电亲水有机物(HIC)的去除效果均较好,去除率分别为94.6%、82.7%和81.3%;组合工艺对三卤甲烷生成势(THMFP)和卤乙酸生成势(HAAFP)的去除率分别为90.7%和87.6%;MIEX预处理可有效减缓膜污染,运行期间超滤膜的跨膜压差上升缓慢,经水力反冲洗后跨膜压差就基本得到恢复.     

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.     

Magnetic ion-exchange resin treatment: impact of water type and resin use

Three raw waters of fundamentally different natural organic matter (NOM) character were treated by magnetic resin using a bench-scale method designed to mimic how the resin is used in continuous operation. Increasing water hydrophobicity resulted in reduced dissolved organic carbon (DOC) removal with removal of 56%, 33% and 25% for waters containing 21%, 50% and 75% hydrophobic NOM, respectively. Study of consecutive resin uses showed that the NOM in the hydrophobic water had high affinity for the resin shown by DOC removal of 65% after the first use of the resin. This dropped to 25% DOC removal after 15 consecutive resin uses. For the more hydrophilic waters, NOM removal remained consistent after each resin use. The hydrophobic sample contained higher MW NOM that was capable of blocking resin sites that prevented continual adsorption of organics on to the resin. The hydrophilic NOM containing a large proportion of hydrophilic acids was consistently removed to around 60%. The water containing algogenic-derived NOM was poorly removed by magnetic resin. Subsequent coagulation showed higher removal with increasing hydrophobicity.     

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

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

Seasonal variations of disinfection by-product precursors profile and their removal through surface water treatment plants

A sampling program has been undertaken to investigate the variations of disinfection by-products (DBPs) formation and nature and fate of natural organic matter (NOM) through water treatment plants in Istanbul. Specific focus has been given to the effect seasonal changes on the formation of DBPs and organic precursors levels. Water samples were collected from the three reservoirs inlet and within three major water treatment plants of Istanbul, Turkey. Changes in the dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm (UV(254)), specific ultraviolet absorbance (SUVA), trihalomethane formation potential (THMFP), and haloacetic acids formation potential (HAAFP) were measured for both the treated and raw water samples. The variations of THM and HAA concentrations within treatment processes were monitored and also successfully assessed. The reactivity of the organic matter changed throughout the year with the lowest reactivity (THMFP and HAAFP) in winter, increasing in spring and reaching a maximum in fall season. This corresponded to the water being easier to treat in fall and an increase in the proportion of hydrophobic content. Understanding the seasonal changes in organic matter character and their reactivity with treatment chemicals should lead to a better optimization of the treatment processes and a more consistent water quality.     

Evaluating fluorescence and ultraviolet photometry to assess dissolved organic matter removal during coagulation–flocculation

Ultraviolet absorption at 254 nm (UV₂₅₄) and peaks (A, C and T) fluorescence intensities were evaluated to assess dissolved organic carbon (DOC) removal during coagulation–flocculation. The consistency of fluorescence data was checked to ensure that no inner filter effect, quenching or enhanced intensities affected the data. The decreases in UV₂₅₄ and peak intensities were calculated in percentage terms between raw and clarified water and compared with measured DOC removal. The results indicate that peak A, peak C, peak T and UV₂₅₄ exhibit strong linear relationships (R²: 0.91, 0.89, 0.92 and 0.99, respectively) with DOC removal, implying that these parameters are useful indicators of DOC removal.     

Fractionation of dissolved organic matter from surface waters using macroporous resins

To obtain fractions enriched with biodegradable dissolved organic carbon (BDOC) or with organic compounds responsible for the chlorine demand (CID) and for trihalomethane formation potential (THMFP), Seine river water samples were percolated on various macroporous resins (anionic, cationic and non-ionic) and compared with granulated activated carbon (GAC). In addition, measurement of UV absorbance at 254 nm and the fluorescence index (λ_excitation 320 nm) had allowed to follow up the retention of dissolved organic matter by the different adsorbants. In contrast to cationic and non-ionic resins, anionic resins confirm their excellent retention capacity of organic compounds responsible for UV 254 absorbance and fluorescence index. The relative values of BDOC/DOC ratio (mg-C/mg-C) are slightly increased in the effluents of anionic resins, indicating that they retain a little preferentially the refractory fraction instead of the biodegradable fraction. There is no significant difference between the ratio of CID/DOC (mg-Cl₂/mg-C) in influent and effluent of anionic resins. Cationic resin has a low capacity for retention of DOC, but they seem to retain significantly the organic compounds responsible for CID. The capability of anionic resins to retain THMFP is similar to that of GAC.