Cyclophosphamide removal from water by nanofiltration and reverse osmosis membrane

The rejection of cyclophosphamide (CP) by nanofiltration (NF) and reverse osmosis (RO) membranes from ultrapure (Milli-Q) water and membrane bioreactor (MBR) effluent was investigated. Lyophilization-extraction and detection methods were first developed for CP analysis in different water matrices. Experimental results showed that the RO membrane provided excellent rejection (>90%) under all operating conditions. Conversely, efficiency of CP rejection by NF membrane was poor: in the range of 20-40% from Milli-Q water and around 60% from MBR effluent. Trans-membrane pressure, initial CP concentration and ionic strength of the feed solution had almost no effect on CP retention by NF. On the other hand, the water matrix proved to have a great influence: CP rejection rate by NF was clearly enhanced when MBR effluent was used as the background solution. Membrane fouling and interactions between the CP and water matrix appeared to contribute to the higher rejection of CP.     

反渗透膜截留二级出水中重金属离子试验研究

为了考察反渗透膜对污水中重金属离子的去除效果,采用MCM-RO（微滤-活性炭-微滤-反渗透）工艺对邯郸市东郊污水厂氧化沟工艺二沉池出水进行了深度处理,实验结果表明,该工艺对砷、镉、铅三种重金属的去除效果非常明显,出水水质稳定。     

Removal of natural hormone estrone from secondary effluents using nanofiltration and reverse osmosis

The rejection of steroid hormone estrone by nanofiltration (NF) and reverse osmosis (RO) membranes in treated sewage effluent was investigated. Four NF/RO membranes with different materials and interfacial characteristics were utilized. To better understand hormone removal mechanisms in treated effluent, effluent organic matters (EfOM) were fractionated using column chromatographic method with resins XAD-8, AG MP-50 and IRA-96. The results indicate that the presence of EfOM in feed solution could enhance estrone rejection significantly. Hydrophobic acid (HpoA) organic fraction made a crucial contribution to this “enhancement effect”. Hydrophobic base (HpoB) could also improve estrone rejection while hydrophobic neutral (HpoN) and hydrophilic acid (HpiA) with low aromaticity had little effects. The increment in estrone rejection was predominantly attributed to the binding of estrone by EfOM in feed solutions, which led to an increase in molecular weight and appearance of negative charge (for the HpoA case) and thus an increased level of estrone rejection. However, the improvement of estrone rejection by HpoA decreased with increasing calcium ion concentration. The important conclusion of this study is, first, hydrophobic acid macromolecules are recommended to be added into feed water to improve the rejection of trace hormone during NF/RO membrane process, and, second, removal of calcium ions via pretreatment and application of membrane with more negative charge at its interface can greatly intensify this “enhancement effect”.     

Pre-treatment optimisation studies for secondary effluent reclamation with reverse osmosis

Physical-chemical pre-treatment was used for the reverse osmosis unit for reclamation of secondary effluents. The pilot plant was equipped with a variety of tertiary treatment units to prevent fouling and biofouling of the cellulose-acetate reverse osmosis membranes used. The optimisation of pre-treatment involved application of various concentrations of lime to raise the pH to 10.3-12.1, and to stabilise the sludge generated, as well as different dosages of ferric chloride (15, 20, and 25 mg/L) for the coagulation and solid-liquid separation. Sodium hypochlorite (8 mg/L) and UV disinfection are used for microbiological control. The water quality obtained, under the optimum conditions (pH=10.5; FeCl(3): 25 mg/L; anionic flocculant: 0.5 mg/L; sodium hypochlorite: 8 mg/L) was high, showing an average conductivity of 66 microS/cm and low COD values 4 mg O(2)/L. The product water is suitable for injection into a groundwater aquifer to counteract seawater intrusion.     

Impact of microfiltration treatment of secondary wastewater effluent on biofouling of reverse osmosis membranes

The effects of microfiltration (MF) as pretreatment for reverse osmosis (RO) on biofouling of RO membranes were analyzed with secondary wastewater effluents. MF pretreatment reduced permeate flux decline two- to three-fold, while increasing salt rejection. Additionally, the oxygen uptake rate (OUR) in the biofouling layer of the RO membrane was higher for an RO system that received pretreated secondary wastewater effluent compared to a control RO system that received untreated secondary effluent, likely due to the removal of inert particulate/colloidal matter during MF. A higher cell viability in the RO biofilm was observed close to the membrane surface irrespective of pretreatment, which is consistent with the biofilm-enhanced concentration polarization effect. Bacterial 16S rRNA gene clone library analysis revealed dominant biofilm communities of Proteobacteria and Bacteroidetes under all conditions. The Cramer-von Mises test statistic showed that MF pretreatment did not significantly change the bacterial community structure of RO membrane biofilms, though it affected bacterial community structure of non-membrane-associated biofilms (collected from the feed tank wall). The finding that the biofilm community developed on the RO membrane was not influenced by MF pretreatment may imply that RO membranes select for a conserved biofilm community.     

Integrated pretreatment with capacitive deionization for reverse osmosis reject recovery from water reclamation plant

Reverse osmosis (RO) reject recovery from the water reclamation process was demonstrated feasible using an integrated pretreatment scheme followed by the Capacitive Deionization (CDI) process. The RO reject had an average total dissolved solids (TDS) of 1276 ± 166 mg/L. Water recovery of 85% with water quality comparable with the RO feed was achieved. Pretreatments using biological activated carbon (BAC) and BAC–ultrafiltration (UF) attained total organic carbon (TOC) removal efficiencies of 23.5 ± 6.0% and 39.9 ± 9.0%, respectively. Organics removal of RO reject was attributed to simultaneous adsorption and biodegradation in the BAC pretreatment, while further biodegradation in the submerged UF membrane tank provided additional organics removal. Membrane and CDI fouling was reduced by pH adjustment of the pretreated RO reject to approximately 6.5, which prolonged the CDI operation time by at least two times. The CDI process was able to achieve more than 88 and 87% TDS and ion removals, respectively, while PO₄³⁻ and TOC removals were at 52–81% and 50–63%, respectively.     

Coupling reverse osmosis with electrodialysis to isolate natural organic matter from fresh waters

Reverse osmosis (RO) has proven to be an effective method for the concentration of natural organic matter (NOM) from fresh waters, but an undesirable consequence of this process is the co-concentration of some inorganic solutes. Accordingly, current practice yields solutions of NOM that, upon desalting and freeze-drying, are converted into dry solids containing finely dispersed sulfuric acid and silicic acid (H(4)SiO(4)). These acids will contribute to the apparent carboxylic and phenolic contents of NOM, leading to an overestimation of both. NOM may also be chemically altered by sulfuric acid, which reacts strongly with many classes of organic compounds. The sulfur content and ash content of NOM will be elevated in the presence of sulfuric acid and H(4)SiO(4). The goal of this study is to develop and test a method in which the removal of water by RO is coupled with the removal of salts by electrodialysis (ED). Like RO, ED is a relatively mild treatment that enables the desalting of NOM solutions without subjecting those samples to conditions of extremely high or low pH. The end product of the coupled process is a desalted, concentrated liquid sample from which low-ash NOM can be obtained as a freeze-dried solid material. In this study, the efficacy of ED for desalting NOM is evaluated using concentrated synthetic river waters and actual concentrated (by RO) river waters. Under optimal operating conditions, both sulfate and silica can be largely removed from RO-concentrated solutions of riverine NOM with only an average loss of 3% of total organic carbon.     

Comparison of the removal of hydrophobic trace organic contaminants by forward osmosis and reverse osmosis

We compared the rejection behaviours of three hydrophobic trace organic contaminants, bisphenol A, triclosan and diclofenac, in forward osmosis (FO) and reverse osmosis (RO). Using erythritol, xylose and glucose as inert reference organic solutes and the membrane pore transport model, the mean effective pore size of a commercial cellulose-based FO membrane was estimated to be 0.74 nm. When NaCl was used as the draw solute, at the same water permeate flux of 5.4 L/m² h (or 1.5 μm/s), the adsorption of all three compounds to the membrane in the FO mode was consistently lower than that in the RO mode. Rejection of bisphenol A and diclofenac were higher in the FO mode compared to that in the RO mode. Because the molecular width of triclosan was larger than the estimated mean effective membrane pore size, triclosan was completely rejected by the membrane and negligent difference between the FO and RO modes could be observed. The difference in the separation behaviour of these hydrophobic trace organics in the FO (using NaCl the draw solute) and RO modes could be explained by the phenomenon of retarded forward diffusion of solutes. The reverse salt flux of NaCl hinders the pore diffusion and subsequent adsorption of the trace organic compounds within the membrane. The retarded forward diffusion effect was not observed when MgSO₄ and glucose were used as the draw solutes. The reverse flux of both MgSO₄ and glucose was negligible and thus both adsorption and rejection of BPA in the FO mode were identical to those in the RO mode.     

Isolation of dissolved organic matter from the suwannee river using reverse osmosis

A portable reverse osmosis (RO) system was constructed and used to concentrate dissolved organic matter (DOM) from the Suwannee River in southeastern Georgia. Using this RO system, 150–180 1/h of river water could be processed with 90% recovery of DOM. After further cation exchange and lyophilization of the concentrated river water samples, large quantities of low-ash freeze-dried products were isolated. We highly recommend this RO method for concentration of DOM in fresh waters because (1) a very high percentage of DOM is recovered, which indicates minimal fractionation of the original sample; and (2) the process is quite rapid, which permits large quantities of DOM to be concentrated in a reasonable length of time.     

Effects of reverse osmosis isolation on reactivity of naturally occurring dissolved organic matter in physicochemical processes

A field reverse osmosis system was used to isolate dissolved organic matter (DOM) from two lacustrine and two riverine surface water sources. The rejection of DOM was on the order of 99% and did not vary significantly with pressure. A simple mass balance model using a single measured value of rejection predicted the concentration within the closed-loop isolation system. The effect of operating pressure and solution flux on mass recovery of DOM was evaluated in laboratory and field trials. Under controlled laboratory conditions, >99% of a lacustrine DOM could be accounted for. A fraction of the isolated DOM was not recoverable using hydrodynamic cleaning; however, this fraction was recovered by using a pH 10 NaOH wash solution. The mass recovered in the NaOH solution increased from <1% to >6% with increasing transmembrane pressures from 414 kPa (60 psi) to1000 kPa (145 psi), respectively. This is consistent with fouling that results from an increase in solution flux, and a decrease in tangential crossflow velocity. Under field conditions, mass balances were generally >95% and mass recovery was >90% in all cases. The effects of temperature on solution flux were consistent with changes in fluid viscosity; effects of temperature on membrane diffusivity or morphological properties were small. RO isolation under low pressure conditions designed to maximize DOM recovery had little effect on DOM reactivity evaluated in terms of nanofiltration membrane fouling, XAD-8 resin adsorption, activated carbon adsorption, competition with trichloroethylene for adsorption sites on activated carbon, and molecular weight distribution measured using size exclusion chromatography.     

Advanced treatment of the reverse osmosis concentrate produced during reclamation of municipal wastewater

The work investigated the treatment of the concentrate produced from the reverse osmosis treatment of an MBR effluent. Two conventional chemical processes, coagulation and activated carbon adsorption, and three advanced oxidation processes (electrochemical treatment, photocatalysis and sonolysis) were applied. Coagulation with alum gave dissolved organic carbon (DOC) removals up to 42%, while FeCl(3) achieved higher removals (52%) at lower molar doses. Adsorption with granular activated carbon showed the highest DOC removals up to 91.3% for 5 g/L. The adsorption isotherm was linear with a non-adsorbable organic fraction of around 1.2 mg/L DOC. The three oxidation methods employed, electrolytic oxidation over a boron-doped diamond electrode, UVA/TiO2 photocatalysis and sonolysis at 80 kHz, showed similar behavior: during the first few minutes of treatment there was a moderate removal of DOC followed by further oxidation at a very slow rate. Electrolytic oxidation was capable of removing up to 36% at 17.8A after 30 min of treatment, sonolysis removed up to 34% at 135W after 60 min, while photocatalysis was capable of removing up to 50% at 60 min.     

Rejection of micropollutants by clean and fouled forward osmosis membrane

As forward osmosis (FO) gains attention as an efficient technology to improve wastewater reclamation processes, it is fundamental to determine the influence of fouling in the rejection of emerging contaminants (micropollutants). This study focuses on the rejection of 13 selected micropollutants, spiked in a secondary wastewater effluent, by a FO membrane, using Red Sea water as draw solution (DS), differentiating the effects on the rejection caused by a clean and fouled membrane. The resulting effluent was then desalinated at low pressure with a reverse osmosis (RO) membrane, to produce a high quality permeate and determine the rejection with a coupled forward osmosis - low pressure reverse osmosis (FO-LPRO) system. When considering only FO with a clean membrane, the rejection of the hydrophilic neutral compounds was between 48.6% and 84.7%, for the hydrophobic neutrals the rejection ranged from 40.0% to 87.5%, and for the ionic compounds the rejections were between 92.9% and 96.5%. With a fouled membrane, the rejections were between 44.6% and 95.2%, 48.7%-91.5% and 96.9%-98.6%, respectively. These results suggest that, except for the hydrophilic neutral compounds, the rejection of the micropollutants is increased by the presence of a fouling layer, possibly due to the higher hydrophilicity of the FO fouled membrane compared to the clean one, the increased adsorption capacity of hydrophilic compounds and reduced mass transport capacity, membrane swelling, and the higher negative charge of the membrane surface, related to the foulants composition, mainly NOM acids (carboxylic radicals) and polysaccharides or polysaccharide-like substances. However, when coupled with RO, the rejections in both cases increased above 96%. The coupled FO-LPRO system was an effective double barrier against the selected micropollutants.     

Rejection of pharmaceuticals in nanofiltration and reverse osmosis membrane drinking water treatment

This paper investigates the removal of a broad range of pharmaceuticals during nanofiltration (NF) and reverse osmosis (RO) applied in a full-scale drinking water treatment plant (DWTP) using groundwater. Pharmaceutical residues detected in groundwater used as feed water in all five sampling campaigns were analgesics and anti-inflammatory drugs such as ketoprofen, diclofenac, acetaminophen and propyphenazone, beta-blockers sotalol and metoprolol, an antiepileptic drug carbamazepine, the antibiotic sulfamethoxazole, a lipid regulator gemfibrozil and a diuretic hydrochlorothiazide. The highest concentrations in groundwater were recorded for hydrochlorothiazide (58.6-2548ngL(-1)), ketoprofen (85%). Deteriorations in retentions on NF and RO membranes were observed for acetaminophen (44.8-73 %), gemfibrozil (50-70 %) and mefenamic acid (30-50%). Furthermore, since several pharmaceutical residues were detected in the brine stream of NF and RO processes at concentrations of several hundreds nanogram per litre, its disposal to a near-by river can represent a possible risk implication of this type of treatment.     

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.     

Comparing microfiltration-reverse osmosis and soil-aquifer treatment for indirect potable reuse of water

Microfiltration (MF) followed by reverse osmosis (RO) and soil-aquifer treatment (SAT) are the two principal technologies considered for indirect potable reuse of wastewater. This study, conducted at the Northwest Water Reclamation Plant, Mesa (Arizona), evaluated MF/RO and SAT (>6 months residence time) treated tertiary effluent with respect to organics removal. Effluent organic matter was characterized as total organic carbon (TOC), by UV absorbance (UVA), solid-state carbon-13 nuclear magnetic resonance spectroscopy, and size exclusion chromatography. Several trace organic micropollutants, including EDTA, NTA, and alkylphenolethoxylate residues, were analyzed by GC/MS. The study revealed that final TOC concentrations of MF/RO and SAT are 0.3 and 1.0 mgl(-1), respectively. Based on the characterization techniques used, the character of bulk organics present in final SAT water resembles the character of natural organic matter present in drinking water. Depending on the molecular weight cut-off, RO membranes can efficiently reject high molecular weight organic matter (characterized as humic and fulvic acids). However, approximately 40-50 percent of the remaining TOC in permeates consists of low molecular weight acids and neutrals representing a molecular weight range of approximately 500Da and less. In the SAT treated effluent, EDTA and APECs were removed to approximately 4.3 and 0.54 microg/l, respectively, but were below the detection limit in the MF/RO treated effluent.     

Full-scale simulation of seawater reverse osmosis desalination processes for boron removal: Effect of membrane fouling

The objective of this study is to further develop previously reported mechanistic predictive model that simulates boron removal in full-scale seawater reverse osmosis (RO) desalination processes to take into account the effect of membrane fouling. Decrease of boron removal and reduction in water production rate by membrane fouling due to enhanced concentration polarization were simulated as a decrease in solute mass transfer coefficient in boundary layer on membrane surface. Various design and operating options under fouling condition were examined including single- versus double-pass configurations, different number of RO elements per vessel, use of RO membranes with enhanced boron rejection, and pH adjustment. These options were quantitatively compared by normalizing the performance of the system in terms of E_min, the minimum energy costs per product water. Simulation results suggested that most viable options to enhance boron rejection among those tested in this study include: i) minimizing fouling, ii) exchanging the existing SWRO elements to boron-specific ones, and iii) increasing pH in the second pass. The model developed in this study is expected to help design and optimization of the RO processes to achieve the target boron removal at target water recovery under realistic conditions where membrane fouling occurs during operation.     

An autopsy study of a fouled reverse osmosis membrane element used in a brackish water treatment plant

The fouling of a spiral wound reverse osmosis (RO) membrane after nearly 1 year of service in a brackish water treatment plant was investigated using optical and electron microscopic methods, Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Both the top surface and the cross-section of the fouled membrane were analysed to monitor the development of the fouling layer. It has been found that the extent of fouling was uneven across the membrane surface with regions underneath or in the vicinity of the strands of the feed spacer being more severely affected. Fouling appeared to have developed through different stages. In particular, it consisted of an initial thin fouling layer of an amorphous matrix with embedded particulate matter. The amorphous matrix comprised organic-Al-P complexes and the particulate matter was mostly aluminium silicates. Subsequently, as the fouling layer reached a thickness of about 5-7microm, further amorphous material, which is suggested to include extracellular polymeric substances such as polysaccharides, started to deposit on top of the existing fouling layer. This secondary amorphous material did not seem to contain any particulate matter nor any inorganic elements within it, but acted as a substrate upon which aluminium silicate crystals grew exclusively in the absence of other foulants, including natural organic matter (NOM).     

Fatty acid fouling of reverse osmosis membranes: implications for wastewater reclamation

Effluent organic matter (EfOM) contributes significantly to organic fouling of reverse osmosis (RO) membranes in advanced wastewater reclamation. In this study, the effect of feed solution chemistry (solution pH and Ca²⁺ concentration) on the fouling of RO membranes by octanoic acid—selected to represent fatty acids in EfOM—is investigated. Crossflow fouling experiments demonstrate that RO membrane fouling is much more significant at solution pH below the pK_a of the octanoic acid (pK_a = 4.9) than at an elevated pH. Octanoic acid permeates across the membranes more readily at solution pH below its pK_a than at elevated pH. At pH below the octanoic acid pK_a, fouling behavior is not affected by calcium ions, whereas at elevated pH, the rate of flux decline decreases with higher calcium ion concentration. The effect of calcium on the fouling behavior was further verified from foulant-foulant adhesion forces, determined by atomic force microscopy (AFM) force measurements under solution chemistries identical to those of the crossflow fouling experiments. To investigate the implications of octanoic acid fouling for wastewater reclamation, the effect of octanoic acid on membrane fouling by a combination of organic foulants in the presence of calcium ions is studied. At a solution chemistry simulating that of typical wastewater effluents, the addition of octanoic acid to a feed solution containing alginate, bovine serum albumin, and Suwannee River natural organic matter, does not enhance membrane fouling behavior. This observation could be attributed to the significant contribution of the alginate-calcium complexes within the fouling layer to the total membrane resistance.     

Removal of biological and non-biological viral surrogates by spiral-wound reverse osmosis membrane elements with intact and compromised integrity

The removal of bacteriophage MS2 and fluorescent-dyed polystyrene microspheres with intact and purposely compromised spiral-wound RO membrane elements was investigated. MS2 rejection with intact membrane elements was >99.9995%. A model developed for data evaluation revealed that the advective passage of MS2 through imperfections of intact membrane elements was <2 x 10(-5)% of the overall product water flow produced. The advective passage of MS2 and microspheres through a pinhole induced in one of the elements was 0.05-0.1% of the overall product water flow. Prolonged testing of both intact and compromised elements resulted in increased MS2 rejection corresponding to advective MS2 passage through membrane imperfections of <3 x 10(-7)% of the overall product water flow. The permeate flow rate obtained with an element with a larger pinhole was 5-13% greater than that of the intact element, and the corresponding rejection of MS2 and microspheres was similar to that observed for sodium chloride. The use of a cracked o-ring in the connection of the permeate tube to the element vessel end-cup resulted in advective passage of MS2 through the crack of <0.0001% of the overall permeate flow.     

Pilot-scale investigation on the removal of organic foulants in secondary effluent by slow sand filtration prior to ultrafiltration

Natural biofiltration processes have been verified as effective pre-treatment choice improving the performance of low-pressure membranes (MF/UF) in wastewater reclamation. In the present work, pilot-scale slow sand filtration (SSF) was used to simulate bank filtration at high filtration rates (from 0.25 m/h to 0.5 m/h) to filter secondary effluent prior to UF. The results showed that SSF improved the performance of UF to a large extent. Related to previous work biopolymers are considered as major dissolved organic foulants in treated wastewater. The removal of these organic foulants in slow sand filters and factors affecting the performance of SSF were investigated. It was observed that the removal of biopolymers took place mainly at the upper sand layer and was related to biological degradation. Tests on the degradability of biopolymers verified that they are biodegradable. Sixteen months monitoring of biopolymer concentration in the secondary effluent indicated that it varied seasonally. In winter season the concentration was much higher than during the summer months. Higher temperature and lower biopolymer concentration led to more effective foulants removal and more sustainable operation of SSF. During the whole experimental period, the performance of SSF was always better at filtration rate of 0.25 m/h than at 0.5 m/h. Under the present experimental conditions, SSF exhibited stable and effective biopolymer removal at temperatures higher than 15 °C, at biopolymer concentrations lower than 0.5 mg C/L and with sufficient oxygen available.