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.     

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.     

Is semi-flocculation effective as pretreatment to ultrafiltration in wastewater treatment?

In this study, ferric chloride (FeCl(3)) flocculation was used as a pretreatment to ultrafiltration (UF) in treating synthetic wastewater containing synthetic organic matter (SOM). The effect of flocculant dose was studied in terms of organic removal and membrane flux decline. The UF with optimum dose of FeCl(3) (68 mg L(-1)) did not experience any flux decline during the whole operation of 6 h. The preflocculation with a smaller dose of 20 mg L(-1) of FeCl(3) led to a severe flux decline in the UF (more than 65% in 6 h). To understand the phenomenon of the flux decline of UF, the MW ranges of SOM removed by different doses of FeCl(3) and by the post treatment of UF were studied. Flocculation with at least 50 mg L(-1) of FeCl(3) dose was found to be necessary to avoid any significant flux decline and to obtain superior DOC removal.     

Performance of selected anion exchange resins for the treatment of a high DOC content surface water

The objective of this study was first to compare the performance of four strong anion exchange resins (AERs) (MIEX from Orica Pty Ltd, DOWEX-11 and DOWEX-MSA from DOW chemical and IRA-938 from Rohm and Haas) for their application in drinking water treatment (natural organic matter (NOM), mineral anions (nitrate, sulfate and bromide) and pesticide removal) using bench-scale experimental procedures on a high DOC content surface water. The efficiency of MIEX for NOM and mineral anions removal was furthermore evaluated using bench-scale dose-response experiments on raw, clarified and post-ozonated waters. NOM removal was assessed using the measurement of dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254) and the use of high-performance size exclusion chromatography with UV (HPSEC/UV) and fluorescence detection (HPSEC/FLUO). The MIEX and IRA938 anionic resins exhibit a faster removal of NOM and mineral anions compared to the DOWEX11 and MSA AERs. All the resins were found to be very effective with similar performances after 30 to 45 min of contact time. As expected, only limited sorption of atrazine and isoproturon (C0=1 microg/L) occurred with MIEX, DOWEX11 and MSA AERs. MIEX resin proved to be very efficient in eliminating NOM of high-molecular weight but also a large part of the smallest UV absorbing organic compounds which were refractory to coagulation/flocculation treatment. Remaining DOC levels after 30 min of contact with MIEX were found similar in raw water, clarified water and even post-ozonated water implying no DOC benefit can be gained by employing conventional treatment prior to MIEX treatment. Removal of bromide (initial concentration 110 microg/L) was also observed and ranged from 30% to 65% for resin dose increasing from 2 to 8 mL/L. T     

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.     

超滤膜处理净水厂沉淀池出水的中试研究

采用中试规模的内压式超滤膜系统处理水厂沉淀池出水,考察超滤膜系统长期运行的出水水质情况。结果表明,超滤膜系统在处理不同水质期沉淀池出水时具有较高的除浊率,平均除浊率达到93.4%,且99.4%的出水浊度<0.1 NTU,去除效果明显优于同期传统的滤池工艺。超滤膜系统对沉淀池出水中有机物的去除效果有限,对CODMn和UV254的平均去除率分别为17.2%和8.2%,出水CODMn≤2.0 mg/L的保证率在98%以上,膜出水CODMn浓度受进水水质和运行条件的影响不大。膜进水中以小分子质量有机物为主,在MW<1 ku区间内的DOC和UV254占到整体有机物含量的57.3%和53.5%。超滤膜系统对微生物的去除效果良好,膜出水水质大部分时间无需经过消毒就能保证卫生要求,可降低后续消毒的加氯量,从而减少消毒副产物的生成量。     

Identification of effluent organic matter fractions responsible for low-pressure membrane fouling

Anion exchange resin (AER), powder activated carbon (PAC) adsorption and ozonation treatments were applied on biologically treated wastewater effluent with the objective to modify the effluent organic matter (EfOM) matrix. Both AER and PAC led to significant total organic carbon (TOC) removal, while the TOC remained nearly constant after ozonation. Liquid Chromatography-Organic Carbon Detection (LC-OCD) analysis showed that the AER treatment preferentially removed high and intermediate molecular weight (MW) humic-like structures while PAC removed low MW compounds. Only a small reduction of the high MW colloids (i.e. biopolymers) was observed for AER and PAC treatments. Ozonation induced a large reduction of the biopolymers and an important increase of the low MW humic substances (i.e. building blocks).Single-cycle microfiltration (MF) and ultrafiltration (UF) tests were conducted using commercially available hollow fibres at a constant flux. After reconcentration to their original organic carbon content, the EfOM matrix modified by AER and PAC treatments exhibited higher UF membrane fouling compared to untreated effluent; result that correlated with the higher concentration of biopolymers. On the contrary, ozonation which induced a significant degradation of the biopolymers led to a minor flux reduction for both UF and MF filtration tests. Based on a single filtration, results indicate that biopolymers play a major role in low pressure membrane fouling and that intermediate and low MW compounds have minor impact. Thus, this approach has shown to be a valid methodology to identify the foulant fractions of EfOM.     

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.     

Long-term performance of bicarbonate-form anion exchange: removal of dissolved organic matter and bromide from the St. Johns River, FL, USA

The goal of this research was to evaluate the long-term performance of magnetic ion exchange (MIEX) treatment using bicarbonate as the mobile counter ion (i.e., MIEX-HCO₃) and sodium bicarbonate for regeneration. This work is important because there are many unknowns concerning the affinity and regeneration efficiency of bicarbonate-form anion exchange, whereas chloride-form anion exchange (i.e., MIEX-Cl resin) is well-studied. Raw water samples were collected approximately two times per month for one year from a single location on the St. Johns River (SJR), FL, USA. The SJR is characterized by high concentrations of dissolved organic carbon (DOC; 12-26 mg C/L) and bromide (550-1100 μg/L), and is being considered as an alternative drinking water supply. Jar tests were conducted using MIEX-HCO₃ resin, and MIEX-Cl resin was used as a baseline for comparison. The same batch of MIEX-HCO₃ and MIEX-Cl resin was used for the entire study, which was accomplished by regenerating the resins after each jar test in concentrated solutions of sodium bicarbonate and sodium chloride, respectively, and resulted in 21 regeneration cycles. Maximum removal efficiency was achieved with fresh MIEX-HCO₃ resin and virgin MIEX-Cl resin. Both forms of fresh/virgin MIEX resin also had the same affinity sequence with sulfate ≈ UV-absorbing substance > DOC > bromide. The removal efficiency of both forms of MIEX resin decreased as the number of regeneration cycles increased, with MIEX-HCO₃ resin showing 7-18% lower removals than MIEX-Cl resin after 21 regeneration cycles. The affinity sequence of regenerated MIEX-HCO₃ and MIEX-Cl resins differed from fresh resin with UV-absorbing substances > DOC > sulfate > bromide. Scanning electron microscopy and simulated MIEX-HCO₃ treatment under rapidly changing water quality were also used to improve the understanding of bicarbonate-form anion exchange. The major contribution of this research is a systematic study of the extended use of bicarbonate-form anion exchange resin in the context of affinity, regeneration efficiency, and changing water quality.     

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.     

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.     

粉末活性炭/污泥回流工艺强化膜前预处理的研究

采用粉末活性炭(PAC)吸附/混凝沉淀/浸没式超滤膜组合工艺处理苏州市某河水,考察了PAC/污泥回流工艺对膜前预处理的强化效果及对膜污染的影响,并与常规混凝沉淀、污泥回流强化混凝沉淀、PAC吸附/混凝沉淀等3种预处理工艺进行了对比。结果表明,PAC/污泥回流强化预处理工艺对浊度、DOC、UV254和THMFP的去除率分别为80.2%、47.5%、42.3%和52.3%,均比其他预处理工艺的高,对MW30 ku和MW1 ku有机物的去除效果明显。PAC/污泥回流强化预处理和超滤膜组合工艺对浊度、DOC、UV254和THMFP的去除率分别可达到99.2%、54.1%、47.2%和60.2%;经过15 d的运行,超滤膜的跨膜压差基本保持稳定,而其他预处理工艺虽能在一定程度上减轻膜污染,但无法避免不可逆膜污染的发生。     

超滤膜/混凝生物反应器去除饮用水中有机物的效能

采用超滤膜/混凝生物反应器(UF-MCBR)处理模拟微污染源水,考察了对有机污染物的去除效能与机理.结果表明,当聚合氯化铝投加量为10mg/L时,UF-MCBR对DOC、UV254、TOC、CODMn、BDOC和AOC的去除率分别为44.0%、54.5%、49.0%、58.5%、72.8%和58.3%.UF-MCBR通过超滤、生物降解以及混凝三者之间的协同作用去除溶解性有机物,就DOC的去除而言,三种作用的贡献率分别为11.1%、6.2%和26.7%.UF-MCBR系统中的UF膜表面为污泥层所覆盖,该污泥层能有效强化UF膜对分子质量为300-6000u 有机物的截留,UF膜(连同污泥层)对僧水碱、憎水中性物、憎水酸、弱憎水酸和亲水性物质的截留率分别达到了37.0%、42.8%、52.7%、39.8%和19.0%.     

中桥水厂超滤膜深度处理工艺中试研究

分别以滤后水和沉后水作为进水,考察了超滤膜深度处理工艺的净水效能、膜通量、渗透性及清洗方式.结果表明,超滤膜深度处理工艺对浊度、总铁及色度具有较好的去除效果;以滤后水和沉后水作为超滤膜进水时,适宜的膜通量范围分别为(70 ～80)和(50～60) L/(m2·h);超滤膜-粉末活性炭组合工艺对浊度的去除效果很好,当PAC投加量为15 mg/L时,浊度去除率大于80.7％,TOC、CODMn 、UV254及氨氮去除率基本小于30％.     

Diclofenac removal in urine using strong-base anion exchange polymer resins

One of the major sources of pharmaceuticals in the environment is wastewater effluent of which human urine contributes the majority of pharmaceuticals. Urine source separation has the potential to isolate pharmaceuticals at a higher concentration for efficient removal as well as produce a nutrient byproduct. This research investigated the efficacy of using strong-base anion exchange polymer resins to remove the widely detected and abundant pharmaceutical, diclofenac, from synthetic human urine under fresh and ureolyzed conditions. The majority of experiments were conducted using a strong-base, macroporous, polystyrene resin (Purolite A520E). Ion-exchange followed a two-step removal rate with rapid removal in 1 h and equilibrium removal in 24 h. Diclofenac removal was >90% at a resin dose of 8 mL/L in both fresh and ureolyzed urine. Sorption of diclofenac onto A520E resin was concurrent with desorption of an equivalent amount of chloride, which indicates the ion-exchange mechanism is occurring. The presence of competing ions such as phosphate and citrate did not significantly impact diclofenac removal. Comparisons of three polystyrene resins (A520E, Dowex 22, Dowex Marathon 11) as well as one polyacrylic resin (IRA958) were conducted to determine the major interactions between anion exchange resin and diclofenac. The results showed that polystyrene resins provide the highest level of diclofenac removal due to electrostatic interactions between quaternary ammonium functional groups of resin and carboxylic acid of diclofenac and non-electrostatic interactions between resin matrix and benzene rings of diclofenac. Diclofenac was effectively desorbed from A520E resin using a regeneration solution that contained 4.5% (m/m) NaCl in an equal-volume mixture of methanol and water. The greater regeneration efficiency of the NaCl/methanol–water mixture over the aqueous NaCl solution supports the importance of non-electrostatic interactions between resin matrix and benzene rings of diclofenac. Experiments with ketoprofen, in addition to diclofenac, suggest that polystyrene anion exchange resins can be used to selectively remove other acidic pharmaceuticals from urine.     

Removal of THM precursors by coagulation or ion exchange

The removal of natural organic matter (NOM) from drinking water supplies can be achieved by different processes, among them coagulation and adsorption. Synthetic waters made from concentrates of humic substances from reservoir and river waters were tested in the laboratory for ease of removal of NOM by coagulation with cationic organic polymers and with alum, and by adsorption on anion exchangers. For polymers such as high molecular weight polydiallyldimethylammonium chloride (polyDADMAC) and cationic polyacrylamides of high charge, performance was nearly as effective as alum, with colour removals 86–100% of those obtained for alum. Ion exchange using the best commercially available resins designed for this purpose, a gel polystyrene and a macroporous acrylic resin, was more effective than alum treatment for two of the natural waters studied, but inferior for a third. The resins were overall superior to cationic polymers.

The NOM was separated into four fractions based on hydrophobic and hydrophilic properties. Alum was not as effective as ion exchange for the elimination of individual ionic NOM fractions. It was better than cationic polymers for removal of humic and fulvic acids, although polyDADMAC was as good for one water. For the removal of charged compounds alum then polyDADMAC were the best performers for that water. Unequivocal evidence was obtained that coagulants remove material that is not adsorbed by resins, and vice versa. A combination of coagulation with a cationic polymer and adsorption by an anion exchanger removed essentially all of the NOM. The preference of the coagulants was for the larger, more hydrophobic molecules, and of resins for smaller highly charged hydrophilic molecules. Each fraction had trihalomethane formation potentials in the range 11–24 μg/mg, except for one water that was more reactive. Hence, the actual amount of each fraction in the original water becomes a crucial factor.     

城市污水生化处理后水中溶解性有机物的特性研究

采用XAD树脂分离技术和超滤膜法对青岛市某城市污水处理厂生物化学处理后出水中溶解性有机物（DOM）进行了分类分离,研究了出水中DOM的亲疏水特性及分子量分布规律,探讨了各类DOM组分与芳香度之间的关系.研究结果表明,在DOM中,酸性物质（包括过渡亲水酸性物质和疏水酸性物质）所占比例最高,占总溶解性有机碳（DOC）的79.8%,疏水非酸性物质的芳香度最高,并依疏水酸性物质、过渡亲水酸性物质、亲水性物质的顺序递减,且羰基、羧基、羟基、脂类对芳环的取代程度表现为亲水性物质〈过渡亲水酸性物质〈疏水非酸性物质〈疏水酸性物质;该污水处理厂二级出水中的DOM以小分子量有机物（相对分子质量小于1kDa）为主,其占总DOC的59.13%,表明水中腐殖酸类等难降解有机物质含量较高,增加了消毒副产物的生成势.因此,若该种水体需要深度处理时,应重点考虑提高对腐殖酸类等难降解有机物质的处理程度,确保回用水水质的安全性.     

Modeling the removal of dissolved organic carbon by ion exchange in a completely mixed flow reactor

A mathematical model was developed to describe removal of dissolved organic carbon (DOC) by a macroporous, strong-base anion exchange resin in a completely mixed flow reactor with resin recycle and partial resin regeneration. The two-scale model consisted of a microscale model describing the uptake of DOC by the resin coupled with a macroscale model describing the continuous-flow process. Equilibrium and kinetic parameters were estimated from batch laboratory experiments. The model was validated using continuous-flow data from two pilot plant studies. Model predictions were found to be in good agreement with the observed pilot plant data.     

混凝方式对超滤膜出水水质的影响

采用混凝与浸没式超滤膜组合工艺处理深圳市某水库原水,对比了完全混凝-超滤工艺与在线混凝-超滤工艺出水水质的不同,考察了不同混凝方式对超滤膜出水水质的影响.结果表明,当混凝剂聚合氯化铝（PACl）的投加量为3 mg/L时,两种组合工艺对浊度的去除率均达到99％以上;完全混凝-超滤对CODMn、UV254、DOC的去除率分别为40.5％,63.1％和18.5％,而在线混凝-超滤的去除率分别为41.1％,60.4％和19.2％.在保证出水水质的前提条件下,采用在线混凝-超滤工艺可以简化工艺流程,降低工程建设和运行成本.     

颗粒活性炭吸附对预臭氧后微污染原水水质影响研究

在不同的预臭氧浓度条件下处理微污染原水,考察了颗粒活性灰（GAC）吸附对处理后水样水质的影响.选择化学需氧量（CODMn）、溶解性有机碳（DOC）、生物可降解溶解性有机碳（BDOC）、UV254和氨氮（NH;-N）含量及有机物分子量分布作为考察吸附效果的检测指标.结果表明,在静态吸附时间达到5天时,颗粒活性炭吸附曲线开始趋于平缓,吸附时间超过5天之后吸附趋于饱和;预臭氧含量为2.5 mg/L时,颗粒活性炭对有机物的吸附效果最佳,对CODMn、DOC、BDOC的去除率分别为53.2％,63.2％和36.2％;在不同预臭氧处理条件下,颗粒活性炭对NH;-N的吸附效果并未表现出较大的差异,吸附去除率约为5％;颗粒活性炭优先吸附水中分子量＞ 10kDa的有机物,其次为分子量＜1 kDa的有机物.