Absorbance spectroscopy-based examination of effects of coagulation on the reactivity of fractions of natural organic matter with varying apparent molecular weights

Absorbance spectra of fractions of natural organic matter (NOM) with varying apparent molecular weights (AMWs) were examined in this study. Size exclusion chromatography (SEC) was employed to obtain AMW distributions for three Australian water sources which represented low- and high-dissolved organic carbon (DOC) surface waters and a source with highly degraded NOM. These waters were coagulated with alum and other coagulants. Effects of coagulation on AMW distributions were quantified based on an absorbance slope index (ASI) calculated using NOM absorbance measured at 220, 230, 254 and 272 nm. This index can be calculated for any AMW fraction of NOM. Similarly to SUVA₂₅₄, ASI values decrease consistently in coagulated waters and are correlated with trihalomethane yields. Comparison of ASI indexes in different water sources indicates the presence of both common trends and differences indicative of NOM site-specificity.     

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

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

Assimilable organic carbon in molecular weight fractions of natural organic matter

Assimilable organic carbon (AOC) in natural organic matter (NOM) has been measured in three Norwegian waters. The AOC measurement has been done on unfiltered and membrane-filtered (molecular weight (MW) cut-off of 1000 and 10,000) samples. While the colour in the waters is mainly related to the NOM with MW > 10,000, the AOC was mainly related to the NOM with MW < 1000. The fraction of the NOM with MW < 1000 corresponds to 16-38% of the total organic carbon (TOC), and 4-9% of the colour. This shows that a water treatment process removing the colour and a large part of the TOC in the water will not necessarily result in a reduction in the biofilm formation potential.     

Disinfection byproduct formation in reverse-osmosis concentrated and lyophilized natural organic matter from a drinking water source

Drinking water treatment and disinfection byproduct (DBP) research can be complicated by natural organic matter (NOM) temporal variability. NOM preservation by lyophilization (freeze-drying) has been long practiced to address this issue; however, its applicability for drinking water research has been limited because the selected NOM sources are atypical of most drinking water sources. The purpose of this research was to demonstrate that reconstituted NOM from a lyophilized reverse-osmosis (RO) concentrate of a typical drinking water source closely represents DBP formation in the original NOM. A preliminary experiment assessed DBP formation kinetics and yields in concentrated NOM, which demonstrated that chlorine decays faster in concentrate, in some cases leading to altered DBP speciation. Potential changes in NOM reactivity caused by lyophilization were evaluated by chlorination of lyophilized and reconstituted NOM, its parent RO concentrate, and the source water. Bromide lost during RO concentration was replaced by adding potassium bromide prior to chlorination. Although total measured DBP formation tended to decrease slightly and unidentified halogenated organic formation tended to increase slightly as a result of RO concentration, the changes associated with lyophilization were minor. In lyophilized NOM reconstituted back to source water TOC levels and then chlorinated, the concentrations of 19 of 21 measured DBPs, constituting 96% of the total identified DBP mass, were statistically indistinguishable from those in the chlorinated source water. Furthermore, the concentrations of 16 of 21 DBPs in lyophilized NOM reconstituted back to the RO concentrate TOC levels, constituting 86% DBP mass, were statistically indistinguishable from those in the RO concentrate. This study suggests that lyophilization can be used to preserve concentrated NOM without substantially altering the precursors to DBP formation.     

Effect of membrane character and solution chemistry on microfiltration performance

To help understand and predict the role of natural organic matter (NOM) in the fouling of low-pressure membranes, experiments were carried out with an apparatus that incorporates automatic backwashing and long filtration runs. Three hollow fibre membranes of varying character were included in the study, and the filtration of two different surface waters was compared. The hydrophilic membrane had greater flux recovery after backwashing than the hydrophobic membranes, but the efficiency of backwashing decreased at extended filtration times. NOM concentration of these waters (7.9 and 9.1mg/L) had little effect on the flux of the membranes at extended filtration times, as backwashing of the membrane restored the flux to similar values regardless of the NOM concentration. The solution pH also had little effect at extended filtration times. The backwashing efficiency of the hydrophilic membrane was dramatically different for the two waters, and the presence of colloid NOM alone could not explain these differences. It is proposed that colloidal NOM forms a filter cake on the surface of the membranes and that small molecular weight organics that have an adsorption peak at 220nm but not 254nm were responsible for "gluing" the colloids to the membrane surface. Alum coagulation improved membrane performance in all instances, and this was suggested to be because coagulation reduced the concentration of "glue" that holds the organic colloids to the membrane surface.     

Influence of the character of NOM on the ozonation of MIB and geosmin

Tastes and odours (T&Os) are a major concern in drinking water as they are not efficiently removed by conventional water treatment. Ozonation has been effective for their destruction in some studies. However, the natural organic matter (NOM) in waters can affect the ozonation process and subsequently affect the destruction of T&Os. Five NOM fractions were isolated and ozonated in synthetic waters. The fraction containing the more highly coloured, higher molecular weight compounds exhibited the highest ozone (O3) demand, whereas the low aromatic fraction exhibited the lowest O3 demand. The character of the NOM fractions influenced the ozonation of MIB and geosmin. The destruction of MIB and geosmin was significantly higher in the fraction with the highest colour and UV/visible absorbance at all O3 doses. The destruction of the compounds in the other fractions showed the same trends, increasing MIB and geosmin destruction with increasing UV/visible absorbing character of the NOM. MIB was also ozonated in two real waters. with results showing a competing effect between NOM concentration and NOM character. The O3 reaction time was shown to be important for the destruction of both compounds.     

Formation of organic chloramines during water disinfection - chlorination versus chloramination

Many of the available studies on formation of organic chloramines during chlorination or chloramination have involved model organic nitrogen compounds (e.g., amino acids), but not naturally occurring organic nitrogen in water. This study assessed organic chloramine formation during chlorination and chloramination of 16 natural organic matter (NOM) solutions and 16 surface waters which contained dissolved organic nitrogen (DON). Chlorination rapidly formed organic chloramines within 10 min, whereas chloramination formed organic chloramination much more slowly, reaching the maximum concentration between 2 and 120 h after the addition of monochloramine into the solutions containing DON. The average organic chloramine formation upon addition of free chlorine and monochloramine into the NOM solutions were 0.78 mg-Cl₂/mg-DON at 10 min and 0.16 mg-Cl₂/mg-DON at 24 h, respectively. Organic chloramine formation upon chlorination and chloramination increased as the dissolved organic carbon/dissolved organic nitrogen (DOC/DON) ratio decreased (i.e., DON contents increased). Chlorination of molecular weight (10,000 Da) fractionated water showed that molecular weight of DON would not impact the amount of organic chloramines produced. Comparison of three different disinfection schemes at water treatment plants (free chlorine, preformed monochloramine, and chlorine/ammonia additions) indicated organic chloramine formation could lead to a possible overestimation of disinfection capacity in many chloraminated water systems that add chlorine followed by an ammonia addition to form monochloramine.     

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

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

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

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

The impact of rainstorm events on coagulation and clarifier performance in potable water treatment

This paper examines turbidity removal at a water treatment works in England that receives raw water which is difficult to treat during certain rainstorm events. Rainstorm events lead to elevated levels of turbidity and organic matter found in river waters. A robustness index based on settled turbidity was used to identify periods and events that adversely affected the treatment process. This coupled with raw water sampling data indicated that a change in nature and an increase in natural organic matter (NOM) concentrations occurred following rainstorm events. Experimental work investigated the effect of temperature and NOM on the coagulation process and the results show how increasing levels of NOM significantly impaired the coagulation of particulate material, leading to an increase in settled turbidity.     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

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.     

Natural organic matter and DBP formation potential in Alaskan water supplies

Disinfection by-products (DBP) are formed when natural organic matter (NOM) in water reacts with a disinfectant, usually chlorine. DBPs are a health risk element and regulated under the Safe Drinking Water Act. A study was conducted to evaluate the characteristics of NOM that contribute to DBPs in 17 different drinking water systems in Alaska. In order to determine the nature of the organic matter contributing to DBPs, DBP formation potential was compared with standard water quality parameters such as UV-254, color and dissolved organic carbon (DOC), as well as pyrolysis-gas chromatography/mass spectrometry (GC/MS). Results showed strong correlations between UV-254 and DBP formation potential for all waters studied. DOC, on the other hand, was less strongly correlated to DBP formation potential. Unlike previous studies, the total trihalomethane and haloacetic acid formation potentials were equal on a mass concentration basis for the waters studied. Pyrolysis-GC/MS indicated that NOM contributing to DBPs were primarily phenolic compounds. This finding was consistent with previous studies; however, unlike other studies, no correlation was found between aliphatic compounds in the raw waters and DBP formation potential.     

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.     

A pilot plant evaluation of the Magnetic Ion EXchange® process for the removal of dissolved organic carbon at Draycote water treatment works

Natural organic matter (NOM) in water sources is undesirable for customers because it reacts with chlorine to form trihalomethanes (THMs), which can be harmful to health, and other organochlorine compounds that can cause taste complaints. A new Magnetic Ion EXchange process (MIEX^® DOC) has been reported as being successful in removing NOM from raw water. The aim of this research was (a) to evaluate the performance of the MIEX^® process in removing NOM from hard, lowland water on a pilot plant scale and (b) to compare the performance of the MIEX^® process with low pH coagulation DAF, in particular, with respect to reducing THM levels. A 45 and 40% reduction in the amount of NOM and in the levels of THMs, respectively, in chlorine‐dosed water was achieved when the MIEX^® process was used with dissolved air flotation (DAF).     

Impact of UV/H(2)O(2) advanced oxidation treatment on molecular weight distribution of NOM and biostability of water

The presence of natural organic matter (NOM) poses several challenges to the commercial practice of UV/H₂O₂ process for micropollutant removal. During the commercial application of UV/H₂O₂ advanced oxidation treatment, NOM is broken down into smaller species potentially affecting biostability by increasing Assimilable Organic Carbon (AOC) and Biodegradable Organic Carbon (BDOC) of water. This work investigated the potential impact of UV/H₂O₂ treatment on the molecular weight distribution of NOM and biostability of different water sources. A recently developed flow cytometric method for enumeration of bacteria was utilized to assess biological stability of the treated water at various stages through measurement of AOC. BDOC was also assessed for comparison and to better study the biostability of water. Both AOC and BDOC increased by about 3-4 times over the course of treatment, indicating the reduction of biological stability. Initial TOC and the source of NOM were found to be influencing the biostability profile of the treated water. Using high performance size exclusion chromatography, a wide range of organic molecule weights were found responsible for AOC increase; however, low molecular weight organics seemed to contribute more. Positive and meaningful correlations were observed between BDOC and AOC of different waters that underwent different treatments.     

Reactivity of natural organic matter with aqueous chlorine and bromine

While both aqueous bromine (HOBr/OBr(-)) and chlorine (HOCl/OCl(-)) react with natural organic matter (NOM) during water treatment, limited direct parallel comparison of bromine versus chlorine has been conducted. Experiments with model compounds and natural waters indicated more efficient substitution reactions with bromine than chlorine. Kinetic experiments with NOM isolates with and without pre-ozonation were conducted to obtain second-order rate constants (k) with bromine and chlorine. Two-stage reaction kinetics (rapid initial and slower consumption stages) were observed. Bromine reacted about 10 times faster than chlorine with NOM isolates during both stages. The rapid initial stage reactions were too fast to quantify k values, but qualitative estimates ranged between 500 and 5000 M(-1)s(-1). For the slower second stage k values for bromine were 15 to 167 M(-1)s(-1) over the pH range of 5-11, and lower for chlorine (k = 0.7-5M(-1)s(-1)). Values of k correlated with initial SUVA values of NOM (UVA measured at 254 nm divided by DOC). Based upon UV/VIS and solid-state (13)C-NMR spectroscopy, chlorine addition to a NOM isolate resulted in significant oxidation of aromatic and ketone groups while bromine had significantly less change in spectra. Overall, the improved knowledge that bromine reacts faster and substitutes more efficiently than chlorine will be useful in developing strategies to control disinfection by-product formation during water treatment.     

Influence of the characteristics of natural organic matter on the fouling of microfiltration membranes

Natural organic matter (NOM) plays a significant role in fouling microfiltration membranes in drinking water treatment processes even though the NOM is retained only to a small extent. The aim of this study was to obtain a better understanding of the interactions between the fractional components of NOM and microfiltration membranes. Filtration experiments were performed using 0.22 μm hydrophobic and hydrophilic polyvinylidene fluoride (PVDF) membranes in a stirred-cell system on the NOM isolated from three Australian surface waters. As expected, the fouling rate for the hydrophobic membrane was considerably greater than for the hydrophilic membrane. Focusing on the hydrophobic membrane, it was shown that the high molecular weight fraction of NOM (>30 kDa) was responsible for the major flux decline. Filtration tests on the four fractions of NOM isolated on the basis of hydrophobicity and charge using non-functionalised and anionic resins revealed that the fouling potential for the three waters was hydrophilic neutral>hydrophobic acids>transphilic acids>hydrophilic charged. The low-aromatic hydrophilic neutral compounds were the main determinant of the rate and extent of flux decline. This was linked to the colloidal size fraction (>30 kDa) and to the selective concentration of calcium in the fraction leading to organics-Ca²⁺ bridging. It was also shown that the higher the aromaticity of the NOM the greater the flux decline, and the aromatics mainly resided in the hydrophobic acids fraction. Overall, the fouling mechanism controlling the flux decline involved the combined effects of adsorptive and colloidal fouling by the hydrophilic neutral fraction in the internal pore structure of the membrane.     

Seasonal variations in natural organic matter and its impact on coagulation in water treatment

In the past decade, a number of UK and US water utilities have been experiencing operational difficulties connected with the increased dissolved organic carbon (DOC) levels during the autumn and winter periods. This has been observed as an increase in the production of disinfection-by-products (DBP), and a greater coagulant demand. Resin adsorption techniques were used to fractionate raw water and investigate the variation in surface charge and coagulant-humic interactions over a 36-month period. A change in the natural organic matter (NOM) composition throughout the year was observed, with the fulvic acid fraction (FAF) increasing from 36% in September to 61% in November. However, a reduction in treatment performance is not simply due to an increase in DOC concentrations (from 4.3 to 14.5 mg L-1), but also a change in the charge density of the NOM. It was found that hydrophilic NOM fractions possess negligible charge density (<0.06 meq g-1DOC), and it is the hydrophobic NOM fractions, FAF in particular, that exert the greater dominance on coagulation control. The hydrophilic NOM fractions are less amenable to removal through conventional coagulation with metal salts, and are therefore likely to indicate the DOC residual remaining after treatment. Understanding the seasonal changes in NOM composition and character and their reactivity with coagulants should lead to a better optimisation of the coagulation process and a more consistent water quality.     

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.