Effect of dissolved organic compounds on the photodegradation of the herbicide MCPA in aqueous solution

This work shows that the addition of phenol and 2-propanol as model organic compounds significantly decreases the direct photolysis quantum yield of 4-chloro-2-methylphenoxyacetic acid (MCPA) upon UVB irradiation in aqueous solution. Laser flash photolysis data suggest that 2-propanol is able to decrease the formation of the MCPA excited states under irradiation. A decrease from 0.54 to 0.34 of the photolysis quantum yield of the anionic form of MCPA (which prevails over the undissociated one in surface waters) could have a considerable impact on the MCPA lifetime in ecosystems where the direct photolysis is the main phototransformation pathway. In surface water bodies where the direct photolysis has comparable kinetics as the reaction with OH, a decrease of the quantum yield would enhance the relative importance of the OH pathway, which yields considerably less toxic intermediates than the direct photolysis.     

Photochemical generation of reactive species upon irradiation of rainwater: Negligible photoactivity of dissolved organic matter

This paper focuses on the study of the photochemical activity of dissolved organic matter present in rainwater. Formation rates of the reactive species hydroxyl radical (OH^•), singlet oxygen (¹O₂) and dissolved organic matter triplet states (³DOM^?) were determined by irradiation (UV-A) of wet-only rainwater samples collected in Turin (Italy) in the presence of specific scavengers (benzene, furfuryl alcohol and phenol, respectively). Photo-formation rates of OH^• (≈ 3 · 10⁻¹¹ M s⁻¹) and ¹O₂ (≈ 10⁻¹⁴ M s⁻¹) were lower (1 or 2 orders of magnitude) or largely lower (4 to 10 orders of magnitude) than those determined for fog and cloud samples in previous studies. ³DOM^? formation rate values were either negligible or quite low (≈ 10⁻¹² M s⁻¹) by comparison with those evaluated for surface water samples. Deduced steady-state [OH^•] were in the same range as those reported for fog samples in the literature (8.7 · 10⁻¹⁶ to 1.5 · 10⁻¹⁵ M), while [¹O₂] was often several orders of magnitude lower and, therefore, could be considered as negligible. Nitrite (NO₂⁻) constituted the main source of OH^• (69 ± 21 to 138 ± 36%), and the deduced contribution of DOM was low or nil. All the results obtained in this study tend to demonstrate that DOM (including HUmic LIke Substances, HULIS) present in rainwater is poorly or not photoactive. Therefore, there could be considerable difference between rainwater DOM (HULIS included) and the organic matter present in surface waters, particularly the humic substances, as far as the photochemical activity is concerned.     

Photochemistry of excited-state species in natural waters: A role for particulate organic matter

Laser flash photolysis (LFP) was used to characterize a triplet excited state species isolated from Black River and San Joaquin wetlands particulate organic matter (POM). The solubilized organic matter, isolated from POM by pH-independent diffusion in distilled water, was named PdOM. UV–visible absorption spectroscopy, excitation–emission matrix spectroscopy (EEMs), and ¹H NMR were used to characterize the PdOM. While LFP of dissolved organic matter (DOM) is known to generate the solvated electron, LFP of the PdOM transient in argon-, air-, and nitrous oxide-saturated solutions indicated that this was a triplet excited state species (³PdOM*). The lifetime and the reactivity of ³PdOM* with sorbic acid, a triplet state quencher, were compared with that of the triplet excited state of benzophenone, a DOM proxy. A second excited state species (designated DOM*), with a longer lifetime, was reported in a number of previous studies but not characterized. The lifetime of DOM*, measured for seventeen organic matter isolates, lignin, tannic acid, and three wetlands plant extracts, was shown to differentiate allochthonous from autochthonous DOM. ³POM* and DOM* were also observed in lake water and a constructed wetlands' water. Aqueous extracts of fresh and aged plant material from the same wetland were shown to be one source of these excited state species. This study provides evidence of a role for POM in the photochemistry of natural and constructed wetland waters.     

Inhibition vs. enhancement of the nitrate-induced phototransformation of organic substrates by the OH scavengers bicarbonate and carbonate

Contrary to common expectations, the hydroxyl scavengers, carbonate and bicarbonate, are able to enhance the phototransformation by nitrate of a number of substituted phenols. Carbonate and bicarbonate, in addition to modifying the solution pH, are also able to induce a considerable formation of the carbonate radicals upon nitrate photolysis. The higher availability of less-reactive species than the hydroxyl radical would contribute to substantially enhance the photodegradation of the phenols/phenolates that are sufficiently reactive toward the carbonate radical. This phenomenon has a potentially important impact on the fate of the relevant compounds in surface waters. In contrast, the degradation of compounds that are not sufficiently reactive toward CO₃^−• is inhibited by carbonate and bicarbonate because of the scavenging of ^•OH.     

Development and application of functional assays for freshwater dissolved organic matter

A series of 11 standardised, reproducible, assays have been developed of physico-chemical functions of dissolved organic matter (DOM) in freshwaters. The assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo(a)pyrene binding, hydrophilicity and adsorption to alumina. To obtain DOM for the assays, a 45 L sample of filtered freshwater was rotary-evaporated to reduce the volume to ca. 500 cm3. The concentrate was then passed through a strong cation exchanger, in the Na+ form, to remove alkaline-earth cations, and then through 0.7 and 0.2 microm filters. Eight samples, two each from a lake and three streamwaters, were processed. The yields of dissolved organic carbon (DOC) ranged from 70% to 107% (average 91%). The samples of DOM, stored in the dark at 4 degrees C, retained their functional assay characteristics for up to 7 months. When assaying the concentrates, parallel assays were performed with Suwannee River fulvic acid (SRFA), as a quality control standard. For most of the assays, the results for eight freshwater DOM samples are similar to those obtained with SRFA, the chief exception being the greater hydrophilicity of the DOM samples. For eight of the assays, variability among the DOM samples is significantly (p < 0.01) greater than can be explained by analytical error, i.e. by comparison with results for the SRFA quality standard; the three exceptional assays are photochemical fading, copper binding and benzo(a)pyrene binding. The two lakewater samples studied gave the most extreme assay results, probably because of the influence of phytoplankton-derived DOM. Significant correlations of hydrophilicity and adsorption with optical absorbance may mean that some DOM functional properties can be predicted from comparatively simple measurements.     

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.     

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

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

Size distribution of methylmercury associated with particulate and dissolved organic matter in freshwaters

Water samples were collected from 20 wetland, river and lake sites across Eastern Ontario and Western Quebec to investigate the distribution of methylmercury (MeHg) associated with various size fractions of dissolved organic matter (DOM). Tangential Flow UltraFiltration (TUF) was used to fractionate DOM by nominal molecular size (<0.2 μm, <300 kDa, <30 kDa, <5 kDa and <1 kDa). DOM fluorescence (DOM FL) and absorbance (DOC Abs) were used to quantify DOM photoreactivity and aromaticity in each sample. Significant differences in the size-associated distribution of MeHg, Dissolved Organic Carbon (DOC), DOM FL, and DOM Abs were observed between wetlands, rivers, and lakes. The low molecular weight (LMW) fraction (<5 kDa) in wetlands contained the majority of MeHg (70.0 ± 13.8%), DOC (56.1 ± 9.4%), and DOM FL (77.4 ± 7.5%). DOM FL was also high in the LMW fraction for rivers (60.6 ± 25%) and lakes (75.2 ± 16.9%). Mean MeHg concentrations in the LMW fraction of lakes (41 ± 26 pg L^− 1) and rivers (32 ± 19 pg L^− 1) were substantial but much lower than wetlands. Rivers had the highest percentage of methylmercury (38.0 ± 23.5%) in the particulate (>0.2 µm) fraction. This research highlights the importance of low molecular weight dissolved organic matter in methylmercury fate. For example, a large proportion of MeHg was found in the LMW weight fractions (mean = 47.3 ± 25.4%) of the wetlands, rivers, and lakes in this study.     

Reduction of dissolved organic matter and trihalomethane formation potential during laboratory-scale soil-aquifer treatment

Dissolved organic matter (DOM) in recovered groundwater from soil-aquifer treatment (SAT) has the potential to generate harmful disinfection by-products. This study investigated the reduction of mass and trihalomethane formation potential (THMFP) of DOM fractions from secondary effluent during laboratory-scale SAT. Using XAD-8 and XAD-4 resins, DOM was fractionated into three fractions: hydrophobic acid (HPO-A), transphilic acid (TPI-A) and hydrophilic fraction (HPI). HPO-A was removed by 61.1%, TPI-A by 54.9% and HPI by 75.0% as dissolved organic carbon (DOC) during the laboratory-scale SAT, respectively. The reduction of THMFP from HPO-A, TPI-A and HPI was 27.24, 26.24 and 36.08%, respectively. Specific THMFP for each DOM fraction increased across the soil columns. HPO-A was found to be the major precursor of THMs. THMFP was strongly correlated to ultraviolet light at 254 nm (UV-254) for HPO-A and HPI, while the relationship between THMFP and UV-254 for TPI-A was significantly poor.     

Transformation and characterisation of dissolved organic matter during the thermophilic aerobic biodegradation of faeces

We conducted a comparison of the characteristics of dissolved organic matter (DOM) taken from the bio-toilet and other sources. A characterisation of DOM was carried out to assess the stability of the compost generated during the thermophilic and aerobic biodegradation of faeces. In addition, levels of soluble microbial products generated in the bio-toilet composting reactor were compared with those taken from other sources. The results showed that (i) the main component of DOM from the bio-toilet are solutes with molecular weight (MW)>30,000 Da (40%), whereas micromolecules (MW< 1000 Da) constituted more than 60% of the DOM from other solid samples, while liquid samples reached even more than 90%; (ii) the DOM stabilisation level in the composting reactor of the bio-toilet system was greater than that shown by DOM from other sources; (iii) stabilisation of DOM in the bio-toilet system was characterised by an increasing amount of macromolecules (MW>30,000 Da) after a decreasing trend was observed in the early stages of the biodegradation process; and (iv) net production of lipopolysaccharide (LPS) in wastewater treatment plants is greater than in the bio-toilet.     

Behavior and characteristics of dissolved organic matter during column studies of soil aquifer treatment

Soil column experiments were performed to investigate the behavior and characteristics of dissolved organic matter (DOM) during soil aquifer treatment (SAT), and to differentiate among the mechanisms responsible for the changes in the structural and functional properties of DOM during SAT. To determine the biological transformation of DOM, biodegradability tests using a biodegradation-column system were conducted. DOM was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). Dissolved organic carbon (DOC) was removed by 70% during SAT, and the sorption and anaerobic biodegradation in SAT led to a DOC reduction of 27.4%. The significant changes in fluorescence properties of DOM were observed during SAT. However, the sorption and anaerobic biodegradation in SAT seemed to have no significant effect on the chemical structure of fluorescing constituents in DOM. The DOM fractions exhibited different changes in Fourier-transform infrared (FT-IR) spectra characteristics during SAT. Biodegradation resulted in the enrichment of aromatic structures and the decreased content of the oxygen-containing functional groups, such as CO and C-O, in DOM. On the other hand, the production of C-O and amide-2 functional groups occurred as a result of the sorption combined with anaerobic biodegradation in SAT.     

Comparison of river and canal water dissolved organic matter fluorescence within an urbanised catchment

Recently, growing interest has been shown in the study of canal water quality, yet no research using continuous fluorescence monitoring to characterise dissolved organic matter (DOM) has been performed. This paper evaluated DOM characteristics at hourly resolution. A comparison was made between canal and nearby urban river fluorescence spectra, to emphasise the specific nature of canal water DOM. Results showed that canal water had a significant proportion of microbially derived DOM, while the urban river had a greater proportion of terrestrially derived fractions. The microbial character of canal water DOM originated from the low flow of water, the nutrients predominance and continuous DOM processing. Hence, DOM fluorescence is invariant over a timescale of days, and recreational navigation and precipitation events have no major influence on DOM characteristics. Our results are expected to be applicable to future research on highly regulated freshwater systems for DOM quantity estimation or for water quality models.     

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation-emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r(2)=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5 x 10(4) (T(1)) and approximately 7.6 x 10(3) (T(2)) and with varying relative abundance among samples. The T(1)-peak intensity correlated strongly with [UDON] (r(2)=0.516, p<0.001), while T(2)-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.     

The effects of dissolved natural organic matter on the adsorption of synthetic organic chemicals by activated carbons and carbon nanotubes

Understanding the influence of natural organic matter (NOM) on synthetic organic contaminant (SOC) adsorption by carbon nanotubes (CNTs) is important for assessing the environmental implications of accidental CNT release and spill to natural waters, and their potential use as adsorbents in engineered systems. In this study, adsorption of two SOCs by three single-walled carbon nanotubes (SWNTs), one multi-walled carbon nanotube (MWNT), a microporous activated carbon fiber (ACF) [i.e., ACF10] and a bimodal porous granular activated carbon (GAC) [i.e., HD4000] was compared in the presence and absence of NOM. The NOM effect was found to depend strongly on the pore size distribution of carbons. Minimal NOM effect occurred on the macroporous MWNT, whereas severe NOM effects were observed on the microporous HD4000 and ACF10. Although the single-solute adsorption capacities of the SWNTs were much lower than those of HD4000, in the presence of NOM the SWNTs exhibited adsorption capacities similar to those of HD4000. Therefore, if released into natural waters, SWNTs can behave like an activated carbon, and will be able to adsorb, carry, and transfer SOCs to other systems. However, from an engineering application perspective, CNTs did not exhibit a major advantage, in terms of adsorption capacities, over the GAC and ACF. The NOM effect was also found to depend on molecular properties of SOCs. NOM competition was more severe on the adsorption of 2-phenylphenol, a nonplanar and hydrophilic SOC, than phenanthrene, a planar and hydrophobic SOC, tested in this study. In terms of surface chemistry, both adsorption affinity to SOCs and NOM effect on SOC adsorption were enhanced with increasing hydrophobicity of the SWNTs.     

Characterization of dissolved extracellular organic matter (dEOM) and bound extracellular organic matter (bEOM) of Microcystis aeruginosa and their impacts on UF membrane fouling

Extracellular organic matter (EOM) of cyanobacteria was classified into the dissolved EOM (dEOM) which was released into culture solution and the bound EOM (bEOM) which surrounded the cells. The dEOM and bEOM extracted from Microcystis aeruginosa in stationary phase were used to study their characteristic differences and then their impacts on ultrafiltration (UF) membrane fouling. Component analyses showed that dEOM was comprised of proteins, polysaccharides and humic-like substances, while that bEOM contained only proteins and polysaccharides. Additionally, polysaccharides dominated in dEOM with a polysaccharide/DOC ratio of 1.11 mg mg⁻¹, while proteins were the primary components of bEOM with a protein/DOC ratio of 1.08 mg mg⁻¹. Results of size fractionation and XAD resin fractionation revealed that bEOM was mainly distributed in the high-MW and hydrophobic fractions, while that dEOM was more hydrophilic. Result of UF experiments indicated that dEOM which had a higher organic content and stronger hydrophilicity caused more severe flux decline and reversible fouling, and that bEOM led to slower flux decline but more irreversible fouling due to less electrostatic repulsive and more hydrophobic adhesion. The impacts of these two kinds of EOM on the UF fouling caused by cyanobacterial cells were also investigated. It was found that both flux decline and irreversible membrane fouling caused by the cells were aggravated when cells were together with EOM, especially for bEOM which might increase the surface hydrophobicity of the cells.     

Sorption of the pharmaceuticals carbamazepine and naproxen to dissolved organic matter: Role of structural fractions

Pharmaceutical compounds and dissolved organic matter (DOM) are co-introduced into the environment by irrigation with reclaimed wastewater and/or application of biosolids. In this study, we evaluate the role and mechanism of interaction of the pharmaceuticals naproxen and carbamazepine with structural fractions of biosolids-derived DOM. Sorption interactions were estimated from dialysis-bag experiments at different pHs.Sorption of naproxen and carbamazepine by the hydrophobic acid fraction exhibited strong pH-dependence. With both pharmaceuticals, the highest sorption coefficients (K_DOC) were at pH 4. With the hydrophobic neutral fraction, pH affected only naproxen sorption (decreasing with increasing pH). Among the hydrophilic DOM fractions, the hydrophilic acid fraction exhibited the highest K_DOC value for carbamazepine, probably due to their bipolar character. In the hydrophilic acid fraction-naproxen system, significant anionic repulsion was observed with increasing pH. The hydrophilic base fraction contains positively charged functional groups. Therefore with increasing ionization of naproxen (with increasing pH), K_DOC to this fraction increased. The hydrophilic neutral fraction exhibited the lowest K_DOC with both studied pharmaceuticals.The K_DOC value of carbamazepine with the bulk DOM sample was higher than the calculated K_DOC value based on sorption by the individual isolated fractions. The opposite trend was observed with naproxen at pH 8: the calculated K_DOC value was higher than the value obtained for the bulk DOM. These results demonstrate that DOM fractions interact with each other and do not act as separate sorption domains.     

Adsorption of Cu(II) to schwertmannite and goethite in presence of dissolved organic matter

Sorption processes involving secondary iron minerals may significantly contribute to immobilisation of metals in soils and surface waters. In the present work the effect of dissolved organic matter (DOM) from a concentrated bog-water on the adsorption of Cu(II) onto schwertmannite (Fe₈O₈(OH)₆SO₄) and goethite (α-FeOOH) has been studied. The acid/base behaviour of DOM up to pH 6 was explained by assuming a diprotic acid with a density of carboxylate groups of 6.90 μeq (mg C)⁻¹. The resulting acidity constants, recalculated to zero ionic strength were and .The uptake of DOM to schwertmannite and goethite was highest at low pH although adsorption was significant also under mildly alkaline conditions. Adsorption to the two minerals was similar although at high pH more DOM was adsorbed to schwertmannite than to goethite.DOM enhanced the adsorption of Cu(II) at moderately low pH in the goethite system but there was no effect of DOM in the case of schwertmannite. The presence of Cu(II) resulted in a decreased adsorption of DOM to goethite at weakly acidic pH and increased adsorption at high pH. In the case of schwertmannite, Cu(II) did not affect DOM uptake.     

Influence of dissolved organic matter on estrone removal by NF membranes and the role of their structures

The influence of different dissolved organic matter (DOM) on the removal of steroid hormone estrone during nanofiltration (NF) processes was investigated. Commercial dextran and humic acid (HA) as well as hydrophobic acid fraction (HpoA) derived from treated effluent were selected as DOM. To better understand the mechanism by which they affect estrone transport across NF membrane, the structural characteristics of DOM were also examined. The experimental results showed that DOM studied displayed obviously diverse impacts on estrone removal by NF membranes. These impacts were found to correlate with the structural characteristics of DOM. The presence of dextran without aromatic ring had little effects on the fate and transport of estrone during NF processes. The addition of HA without phenolic groups but great aromaticity improved estrone adsorption on membrane significantly while the “enhancement effect” on estrone rejection was limited. Moreover, estrone rejection by NF membranes was obviously increased by the presence of HpoA which possesses both phenolic groups and aromaticity. Some of the findings reported may be critically important for understanding the removal mechanism of estrone by NF membrane in real water matrix where various DOM co-present.     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

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.