Studies on the effect of humic acids and phenol on adsorption-ultrafiltration process performance

Application of pressure-driven membrane processes, such as ultrafiltration (UF) and microfiltration (MF) for surface water treatment have become very popular during last decades. Membrane fouling by humic substances (HS) is one of the major limiting factors in these processes. In order to alleviate the unfavorable effects of the presence of HS in the feed on the process performance UF and MF are often combined with adsorption on powdered activated carbon (PAC). The main goal of the present study was to evaluate the effect of humic acid (HA) on membrane fouling during UF. Moreover, the effect of PAC addition to the feed on UF process, especially on flux decline was determined. The applicability of the adsorption-ultrafiltration (PAC/UF) system to purification of water containing low (phenol) and high molecular (HA) was also investigated. Three different polymer UF membranes, prepared from polysulfone (PSF), cellulose acetate (CA) or polyacrylonitrile (PAN) were applied. It was found that the membranes prepared from PSF and CA are very susceptible to fouling caused by HA. The permeate flux decreased for ca. 50% during UF of HA solution through the PSF membrane and for ca. 45%-through the CA membrane. In the case of the PAN membrane, a negligible effect of HA on the flux was observed. On the basis of the FTIR spectra it was found that the drop in the permeate flux through these membranes may result from interactions between the negatively charged functional groups present on the membrane surface, such as carboxyl groups (CA) and sulfone groups (PSF) with HA, which results in coating of the membrane surface with HA. When PAC was added to the feed containing HA, the permeate flux through the CA and PAN membranes was maintained on a practically unchanged level. However, in case of the PSF membrane, a 50% drop in the permeate flux in comparison with the flux value, when process was conducted without PAC addition was observed. That was supposed to be due to attractive forces among hydrophobic PAC particles, HA molecules and PSF membrane surface. The performed studies showed that the application of PAC/UF system was very effective in the removal of organic substances having both, low and high molecular weights. The role of PAC suspended in a feed in the PAC/UF system is the adsorption of low molecular organic compounds, which cannot be removed by UF alone.     

Assessing PAC contribution to the NOM fouling control in PAC/UF systems

This paper investigates the powdered activated carbon (PAC) contribution to the fouling control by natural organic matter (NOM) in PAC/UF hybrid process, as well as the foulant behaviour of the PAC itself. Solutions of NOM surrogates (humic acids, AHA, and tannic acid, TA) and AOM/EOM (algogenic organic matter/extracellular organic matter) fractions from a Microcystis aeruginosa culture were permeated through an ultrafiltration (UF) hollow-fibre cellulose acetate membrane (100 kDa cut-off). The greatest impairment on flux and the poorest rejection were associated with polysaccharide-like EOM substances combined with mono and multivalent ions. PAC, either in the absence or in the presence of NOM, did not affect the permeate flux nor the reversible membrane fouling, regardless of the NOM characteristics (hydrophobicity and protein content) and water inorganics. However, PAC controlled the irreversible membrane fouling, minimising the chemical cleaning frequency. Furthermore, PAC enhanced AHA and TA rejections and the overall removal of AOM, although it was apparently ineffective for the highly hydrophilic EOM compounds.     

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.     

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.     

Removal of organic matter from water by PAC/UF system

The laboratory-scale ultrafiltration (UF) experiments were conducted to determine the effect of the presence of powdered activated carbon (PAC) on the UF process performance, in terms of flux decline and the possibilities of membranes cleaning during backwashing. Poly(vinylidene fluoride) membranes formed by the phase inversion technique were used in the UF experiments. A model solution was prepared as a mixture of humic acids (HA) and phenol in concentration of 10 and 1 mg l(-1), respectively. Commercial powdered activated carbons CWZ 11 and CWZ 30 (Gryfskand Sp. z o. o., Hajnówka, Poland) were used as the adsorbents. PAC dosage was in the range of 10-100 mg PAC l(-1). The process was carried out in the cross-flow system. It was found that PAC addition to the distilled water leads to a small drop in the permeate flux, regardless of PAC dose and its type. Although PAC particles are too large to block the membrane pores inside, they deposit on the membrane surface and partially can plug the surface pores. The experimental results demonstrate that the backwashing process applied in combined PAC/UF system was especially effective when PAC dosages were <20mg PAC l(-1). However, a similar permeate flux was maintained for all carbon dosages used and reached the value of about 1 m3 m(-2) d(-1). Moreover, no further drop in the permeate flux for PAC addition to the solution containing foulants (HA) was observed. Effectiveness of the removal of HA and phenol from the model solutions was also investigated. In the PAC/UF system HA were removed in about 90%, whereas the complete removal of phenol was achieved for PAC dosage equal to 100 mg l(-1).     

Comparison of humic acid rejection and flux decline during filtration with negatively charged and uncharged ultrafiltration membranes

Increasingly stringent regulations for drinking water quality have stimulated the ultrafiltration (UF) to become one of the best alternatives replacing conventional drinking water treatment technologies. However, UF is not very effectively to remove humic acid due to the comparatively larger pore size compared to the size of humic acid. Fouling issue is another factor that restricts its widespread application. In this study, rejection of humic acid and flux decline were compared with essentially neutral, negatively charged version of a regenerated cellulose membrane, in which electrostatic interaction was explored for a better humic acid removal and less fouling. Solution environment, including ionic strength, pH and calcium ion concentration, affecting humic acid removal and flux decline on negatively charged and neutral membranes was also compared. Results indicated that the appropriate charge modification on the neutral UF membrane could be an effective way for better removal of NOM and reduction of the membrane fouling due to the electrostatic interactions with the combination effect of membrane pore size. Electrostatic interactions are significant important to achieve high humic acid removal and less fouling, and to improve the water quality and protect people’s health.     

Characterization of natural organic matter fractions separated by ultrafiltration using flow field-flow fractionation

Natural organic matter (NOM) from two sites in South Australia were separated by Amicon YM and YC ultrafiltration (UF) membranes into five nominal fractions (<0.5, 0.5-3, 3-10, 10-30 and >30 kDa). These nominal fractions were then characterized for size and molecular weight (MW) distributions using flow field-flow fractionation. The results show that separation by UF did not produce fractions with the expected MW and size. Electrophoretic mobility measurements of the NOM fractions adsorbed to colloidal goethite showed no significant difference between the fractions. However solid-state (13)C NMR of the NOM fractions showed that the separation was influenced by molecular structure as well as molecular size. The results suggest that great caution needs to be exercised when interpreting molecular size and speciation results for humic substances obtained by membrane UF.     

Identification and quantification of major organic foulants in treated domestic wastewater affecting filterability in dead-end ultrafiltration

Ultrafiltration (UF) membranes can be used after conventional wastewater treatment to produce particle free and hygienically safe water for reuse. However, membrane fouling affects the performance of UF to a large extent. Stirred cell tests with UF membrane show high flux decline filtering treated domestic wastewater. Investigation on the impact of size fractioned substances indicates that dissolved substances are major foulants affecting water filterability. Dissolved organic substances in feed and permeate samples of the stirred cell tests are analyzed by liquid chromatography with online organic carbon detection (LC-OCD). The resulting chromatograms displayed a significant difference of feed and permeate samples in the range of large molecules identified as biopolymer peak. The substances detected in this peak (mostly macro polysaccharide-like and protein-like molecules) are almost completely retained by UF membranes. Quantified investigation shows that biopolymer concentration influences filterability of corresponding water sample proportionally. The apparent magnitude of delivered biopolymer to membrane has a striking correlation with fouling resistance. The relationship was verified to be reproducible using different water samples. Mechanism analysis demonstrates that based on the delivered biopolymer load to membrane pore blocking or cake/gel fouling is the main fouling mechanism in the present experiment conditions.     

Spectroscopic characteristics of ultrafiltration fractions of fulvic and humic acids isolated from an eucalyptus bleached Kraft pulp mill effluent

In order to investigate the chemical heterogeneity of fulvic and humic acids previously isolated from a bleached Kraft pulp mill effluent, a sequential ultrafiltration (UF) scheme through four polyethersulphone membranes was applied. The unfractionated fulvic and humic acids and their fractions were characterized by UV-VIS, synchronous fluorescence (with Deltalambda=60 nm) and FTIR spectroscopies. The FTIR spectra were compared with those of lignin isolated from Eucalyptus globulus wood and from the black liquor of a Kraft pulping process. The results highlighted that fulvic acids fractions of low molecular sizes contain more lignin derived phenolic units, while those of higher molecular size exhibit a higher content of carbohydrate structures. However, the shift observed in the UV-VIS absorbance and fluorescence intensity towards higher wavelength, suggests a higher degree of conjugation of pi-bonds in the fractions of highest molecular sizes. In what concerns the humic acids size fractions, the FTIR spectra did not exhibit major differences but, as observed for the fulvic acids' fractions, UV-VIS and synchronous fluorescence spectra also suggest a higher degree of conjugation of pi-bonds in the fractions with the highest molecular sizes. It was also observed that the fulvic and humic acids fractions of the same molecular size, operationally defined by the UF process, exhibit major differences in their spectroscopic features.     

Phthalic acid esters in dissolved fractions of landfill leachates

The distribution of phthalic acid esters (PAEs) (including diisobutylphthalate (DIBP), di-n-butylphthalate (DnBP) and bis(2-ethyl)hexylphthalate (DEHP)) in dissolved organic matter (DOM) fractions of leachates from sanitary or bioreactor landfills was evaluated. The leachate DOM was fractionated into humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) fractions. Measurements showed that the PAEs were bound mostly to the HA fraction in leachate, regardless of their landfill age or the presence of leachate recirculation. The PAEs affinity for HA and FA differed considerably relative to the sorption coefficients reported for model compounds. Molecular weight of DOM correlated with PAEs partition in collected leachate samples fractions while aromaticity was a poor predictor. Based on the presence of phenolic, carboxyl or amide groups in DOM fractions, hydrogen bonding is likely to be involved in interactions between PAEs and leachate DOM. The peptide groups, particularly presented in HA fracion, might explain the strong affinity of PAEs for HA. The fluorescence excitation emission matrix contour plots showed that the HyI fractions shared certain similarities with humic substances in terms of molecular structure, which may be one reason why PAEs exhibited a clear sorption to the HyI fractions.     

Removal of humic substances (HS) from water by electro-microfiltration (EMF)

Humic substances (HS) represent the common agents contributing to flux decline during membrane filtration of natural water. In order to minimize the fouling during microfiltration (MF) of HS, modifying the operation of MF presents a promising alternative. A laboratory-scale electro-microfiltration (EMF) module was used to separate Aldrich HS from water by applying a voltage across the membrane. The presence of an electric field significantly reduced the flux decline. A flux comparable to that of ion-free water was attained when the voltage was near the critical electric field strength (Ecritical), i.e., the electrical field gradient that balances the advective and electrophoretic velocities of solute. At an applied voltage of 100 V (approximately 110 V/cm), it was able to reduce UV absorbance at 254 nm (UV254), total organic carbon (TOC) and trihalomethane formation potential (THMFP) by over 50% in the permeate. Results from 1H nuclear magnetic resonance (1H NMR) analysis suggest that the aromatic and functionalized aliphatic fractions decreased significantly in the permeate. The charged HS have large molecule weight compared with those passing through membrane. Results clearly indicate that a combination of electric force with MF can increase HS rejection and decrease flux decline. Electrophoretic attraction was the major mechanism for the improvement of flux and rejection over time.     

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.     

Metal ions removal from wastewater or washing water from contaminated soil by ultrafiltration-complexation

In the present paper a process for removal of ions from wastewater or from washing water of contaminated soil by using the weakly basic water-soluble polymer polyethylenimine (PEI) as chelating agent and the Cu(2+) ion as model in combination with an ultrafiltration process was investigated. The complexing agent was preliminarily tested to establish the best operative conditions of the process. Next, ultrafiltration tests by using five different membranes were realised to check membrane performance like flux and rejection. Finally, the possibility for recovering and recycling the polymer was tested in order to obtain an economically sustainable process. Obtained results showed that complexation conditions depends on pH: indeed, at a pH>6 PEI-Cu(2+) complexes are formed, while at pH<3 the decomplexation reaction takes place. Saturation condition is 0.333 mg Cu(2+)/mg PEI, meaning a ratio PEI/Cu(2+)=3(w/w). UF tests showed good results using the PAN 40 kDa membrane reaching an average copper concentration in the permeate of 2 mg/l and a flux of 135.4 and 156.5l/h.m(2) at 2 and 4 bar, respectively. Metal rejection, permeate flow rate, and possibility to regenerating and recycling the polymer makes the polymer-assisted ultrafiltration process (PAUF) very interesting for metal ion removal from waters.     

Effects of mass retention of dissolved organic matter and membrane pore size on membrane fouling and flux decline

Ultrafiltration (UF) fouling has been attributed to concentration polarization, gel layer formation as well as outer and inner membrane pore clogging. It is believed that mass of humic materials either retained on membrane surface or associated with membrane inner pore surface is the primary cause for permeate flux decline and filtration resistance build-up in water supply industries. While biofilm/biofouling and inorganic matter could also be contributing factors for permeability decline in wastewater treatment practices. The present study relates UF fouling to mass of dissolved organic matter (DOM) retained on membrane and quantifies the effect of retained DOM mass on filtration flux decline. The results demonstrate that larger pore membranes exhibit significant flux decline in comparison with the smaller ones. During a 24-h period, dissolved organic carbon mass retained in 10 kDa membranes was about 1.0 g m⁻² and that in 100 kDa membranes was more than 3 times higher (3.6 g m⁻²). The accumulation of retained DOM mass significantly affects permeate flux. It is highly likely that some DOMs bind or aggregate together to form surface gel layer in the smaller 10 kDa UF system; those DOMs largely present in inner pore and serving as pore blockage on a loose membrane (100 kDa) are responsible for severe flux decline.     

混凝-超滤去除腐殖酸的试验研究

进行了直接超滤和混凝－超滤组合工艺对腐殖酸的去除效果和膜污染状况的试验。结果表明，超滤前另混凝土预处理对腐殖酸的DOC和UV254的去除率分别从28％、40％提高到53％、78％。同时高效液相色普（HPLC）分析表明，混凝－超滤组合工艺对分子质量＜6000u的有机物的去除率提高幅度更为显著。混凝－超滤组合工艺的最佳pH值条件pH=7,通过卷扫混凝使小分子有机物结合成微絮体，降低了膜孔污染，使超滤保持了较同的渗透通量。     

Removal of humic substances from natural waters by reverse osmosis

An investigation of the potential use of reverse osmosis for the removal of humic substances in order to remove colour and haloform precursors in small waterworks has been carried out, using three different laboratory scale reverse osmosis units and several different membranes.Membrane pore size was found to be the most important factor that influenced both the permeate quality and the product water flux. Pressure was found to have no significant influence on permeate quality, but was linearly related to product water flux. The concentration of humic substances in the influent was not found to affect product water flux but the transport of humics across the membrane was found to be dependent upon influent concentration. For the selected membranes, the removal of humic substances amounted to 80–100% in terms of colour removal, and 50–99% in terms of permanganate value reduction. The most suitable membranes for the different available units were found to be Osmonics SEPA 89 (permeate flux 251 m⁻² h⁻¹ at 15 bars), DDS 865 (permeate flux, 1201 m⁻²h⁻¹ at 40 bars) and PCI T2A (permeate flux 901 m⁻²h⁻¹ at 20 bars). At suspended solids concentrations higher than 100 mg 1⁻¹ of bentonite, product water flux was significantly reduced.     

Decolorization of wastewater of a Baker's yeast plant by membrane processes

The aim of this study is to develop a membrane-based treatment scheme to remove colorants from the effluent of a baker's yeast plant. For this purpose microfiltration (MF), ultrafiltration (UF) and nanofiltraton (NF) membranes with differing molecular weight cut-offs (MWCOs) were tested. To evaluate the effectiveness of membrane processes in treating the waste stream, optical density (OD), COD, color measurements together with permeation fluxes were used. Effects of pretreatment methods (coagulation and coarse filtration) and feed composition on OD, color, COD were studied. In addition, gel filtration analysis was employed to characterize feed and permeate streams in terms of MW distribution of organics that are present. Maximum rejections obtained were 94%, 89% and 72% for OD, color and COD, respectively, when 0.8 microm microfiltration membrane and 400 Da NF membrane were used in series. It was also observed that addition of intermediate UF steps did not increase overall rejections and final permeate flux of NF membrane. Based on these observations, an efficient scheme was offered.     

Complexity of ultrafiltration membrane fouling caused by macromolecular dissolved organic compounds in secondary effluents

Recent investigations indicate the relevance of extracellular polymeric substances (EPS) in terms of fouling of low-pressure membranes in advanced wastewater treatment. In this study, the high impact of the macromolecular fraction of effluent organic matter on fouling was confirmed in cross-flow ultrafiltration experiments using secondary effluent with and without autochthonous biopolymers. A method for the extraction of a natural mixture of EPS derived from the bacterium Sinorhizobium sp. is presented. Ultrafiltration of solutions of this bacterial EPS extract revealed a correlation between the concentration of EPS and the loss of permeate flux. However, in ultrafiltration tests using extracted bacterial EPS in a model solution as well as in secondary effluent without autochthonous biopolymers, the extent of membrane fouling was not identical with the fouling provoked by secondary effluent organic matter, although the biopolymer concentrations were comparable. The differences in the fouling behaviour of the extracted bacterial EPS and effluent organic matter are considered to be due to different compositions of the biopolymer fraction in terms of proteins, polysaccharides, and other organic colloids, indicating a particular impact of proteins on ultrafiltration membrane fouling.     

Reversible and irreversible low-pressure membrane foulants in drinking water treatment: Identification by principal component analysis of fluorescence EEM and mitigation by biofiltration pretreatment

With the increased use of membranes in drinking water treatment, fouling - particularly the hydraulically irreversible type - remains the main operating issue that hinders performance and increases operational costs. The main challenge in assessing fouling potential of feed water is to accurately detect and quantify feed water constituents responsible for membrane fouling. Utilizing fluorescence excitation-emission matrices (EEM), protein-like substances, humic and fulvic acids, and particulate/colloidal matter can be detected with high sensitivity in surface waters. The application of principal component analysis to fluorescence EEMs allowed estimation of the impact of surface water constituents on reversible and irreversible membrane fouling. This technique was applied to experimental data from a two year bench-scale study that included thirteen experiments investigating the fouling potential of Grand River water (Ontario, Canada) and the effect of biofiltration pre-treatment on the level of foulants during ultrafiltration (UF). Results showed that, although the content of protein-like substances in this membrane feed water (= biofiltered natural water) was much lower than commonly found in wastewater applications, the content of protein-like substances was still highly correlated with irreversible fouling of the UF membrane. In addition, there is evidence that protein-like substances and particulate/colloidal matter formed a combined fouling layer, which contributed to both reversible and irreversible fouling. It is suggested that fouling transitions from a reversible to an irreversible regime depending on feed composition and operating time. Direct biofiltration without prior coagulant addition reduced the protein-like content of the membrane feed water which in turn reduced the irreversible fouling potential for UF membranes. Biofilters also decreased reversible fouling, and for both types of fouling higher biofilter contact times were beneficial.     

Post-treatment of banknote printing works wastewater ultrafiltration concentrate

A novel process of vortex settling and stage-2 ultrafiltration (UF) with alternating feed direction was used to further concentrate the concentrate produced by a stage-1 UF employed for treatment of banknote printing works wastewater. In this post-treatment process, the final concentrate volume for incineration was reduced by 4-5 times while the permeate of the stage-2 UF could be further reused in the banknote printing operation. It was noted vortex settling facilitated settling of the printing ink and the strategy of regularly alternating feed direction in the UF resulted in a higher permeate flux compared to the corresponding flux for operation without alternating feed direction. The hydraulic retention time (HRT) of the vortex settling tank (VST) used in the pilot-scale experiment was 14 min while feed direction to the stage-2 UF was alternated once every hour. Based on the pilot-scale experimental results, a full-scale system was set up. An economic analysis showed that the novel system was a cost-effective option for post-treatment of stage-1 UF concentrate. The treatment system has been successfully implemented at several Chinese banknote printing companies.