Natural Organic Matter Surrogates Research Articles

Adsorption of Natural Organic Matter Surrogates from Aqueous Solution by Multiwalled Carbon Nanotubes

Adsorption of two natural organic matter (NOM) surrogates (tannic acid and gallic acid) by powdered activated carbon (PAC) and four kinds of multiwalled carbon nanotubes (MWCNTs) with different diameters was investigated in aqueous solution. The tannic acid (TA) adsorption isotherm fit the Langmuir model best, while adsorption of gallic acid (GA) fit the Freundlich model. PAC has a higher adsorption capacity for GA due to the pore-filling effect, while TA adsorption on PAC was lower than that on MWCNTs because of the molecule sieving effect. Adsorption of GA and TA on MWCNTs decreased with increasing MWCNT diameter, but neither surface area nor total pore volume alone can fully explain adsorption of the two NOM surrogates on MWCNTs. Adsorption mechanisms including electrostatic interaction, hydrophobic interaction, hydrogen bond, and π–π interaction play roles in the adsorption process. This study implies that NOM properties have a great effect on their adsorption on MWCNTs, and these properties should be further considered when evaluating the risks of NOM-coated nanomaterials.

A critical review of trihalomethane and haloacetic acid formation from natural organic matter surrogates

Disinfection by-products (DBPs) in drinking water, including trihalomethanes (THMs) and haloacetic acids (HAAs), arise from reactions of natural organic matter (NOM) with chlorine and other disinfectants. The objective of this review was to investigate relationships between the molecular properties of NOM surrogates and DBP formation using data collated for 185 compounds. While formation of THMs correlated strongly with chlorine substitution, no meaningful relationships existed between compound physicochemical properties and DBP formation. Thus non-empirical predictors of DBP formation are unlikely in natural waters. Activated aromatic compounds are well known to be reactive precursors; in addition DBP formation from β-dicarbonyl, amino acid and carbohydrate precursors can be significant. Therefore effective DBP control strategies need to encompass both hydrophobic and hydrophilic NOM components, as well as consider data from NOM surrogates in the context of knowledge from representative treatment scenarios. In future experiments, employing surrogates of NOM is likely to remain a powerful tool in the search for unknown precursors and in understanding their response to various disinfection conditions.

Photocatalytic oxidation of natural organic matter surrogates and the impact on trihalomethane formation potential

Natural organic matter (NOM) consists of a complex mixture of organics and acts as precursors for a range of disinfection by-products (DBPs) including trihalomethanes (THMs). The characteristics of these precursors are still not well identified and here we have used a range of NOM surrogates that allows us to investigate how the characteristics of NOM relate to treatability with photocatalytical oxidation. Nine surrogates of NOM (five amino acids, two carbohydrates, two phenolic compounds) were evaluated and the impact of retention time on dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP) measured. Adsorption of the compounds onto TiO 2 was evaluated and electrostatic forces played a significant role in their removal although photocatalytic oxidation was found to be unselective. DOC and THMFP decreased significantly with retention time except for l-leucine where the by-products formed during photocatalytic oxidation were significantly more reactive with chlorine than the parent compound.

Disinfection by-product formation of natural organic matter surrogates and treatment by coagulation, MIEX ® and nanofiltration

Potentially the most effective means of controlling disinfection by-products (DBPs) is to remove precursors before disinfection. To understand relationships between physical properties, treatability and DBP formation, nine natural organic matter (NOM) surrogates were studied. Their DBP formation and removal by coagulation, MIEX ® anion exchange resin and two nanofiltration membranes was measured. Whereas treatability of NOM surrogates was explained in terms of their physicochemical properties, the same was not true of DBP formation. Hence it was not possible to selectively remove compounds which generate high amounts of DBPs. Instead, precursor removal strategies based upon empirical DBP formation potential testing are more apt. Under conditions simulating full-scale performance, MIEX ® did not offer improved performance over coagulation. A hydrophobic nanofiltration membrane proved successful for removing neutral, hydrophilic surrogates, and hence is also suitable for DBP precursors of this character.

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.

Disinfection Byproduct Formation and Fractionation Behavior of Natural Organic Matter Surrogates

While natural organic matter (NOM) surrogates are established in disinfection byproduct (DBP) research, their use in fractionation studies is rare. To understand how surrogates relate to drinking waters, a range of NOM surrogates were fractionated with XAD resins. Their trihalomethane (THM), haloacetic acid (HAA), haloacetaldehyde, haloacetonitrile, and haloketone formations after chlorination were recorded. While compounds with higher log K(ow) values behaved as hydrophobic acids, fractionation of the more hydrophilic compounds did not clearly correlate to the log K(ow). High HAA formation from ferulic and aspartic acids and 1,1,1-trichloropropanone (1,1,1-TCP) formation from 3-oxopropanoic acid were notable. Three amino acids, asparagine, aspartic acid, and tryptophan, formed significant levels of dichloroacetonitrile (DCAN) and trichloroacetaldehyde (TCA). Formation of DBPs did not correlate to any compound physical property; however, there were several correlations between DBP groups. The most significant were between dichloroacetic acid (DCAA) and dichloroacetonitrile (DCAN), DCAN and TCA, and dichloroacetaldehyde (DCA) and trichloroacetaldehyde, indicating the possibility of similar relationships in natural waters.

Chemical and biological oxidation of NOM surrogates and effect on HAA formation

Formation of disinfection by-products (DBPs) can be controlled by removal of disinfection by-product precursors before disinfection. Variable success has been reported, depending on the treatment used and water tested. Chemical and biological oxidations are candidate technologies to control DBP formation. Given the uncertainty over the identity of DBP precursors, the use of surrogates of natural organic matter (NOM) allows fundamental probing of the links between compound character, removal and DBP formation. Nine compounds were chosen to represent NOM and their removal by two advanced oxidation processes (AOPs), UV-C irradiation and biological treatment compared while haloacetic acid (HAA) formation before and after treatment was measured. Although AOPs were able to fully remove all compounds, incomplete mineralisation led to increased HAA levels, dramatically in the case of two amino acids. Biological treatment was effective in removing amino acids but also moderately increased the HAA formation potential (HAAFP) of hydrophilic compounds. These findings indicate waters with high amino acid concentrations will be susceptible to raised HAA levels following AOP treatment and careful process selection for HAA control is required in such cases.

Phenanthrene release from natural organic matter surrogates under simulated human gastrointestinal conditions

The aliphatic region of natural organic matter (NOM) can retain polycyclic aromatic hydrocarbons (PAH) due to the presence of non-polar binding sites. Thus NOM may act as a vehicle for entry of PAH into the gastrointestinal system in man and animals. In this study, the release of phenanthrene from the aliphatic NOM surrogates cutin and cutan was measured under simulated human gastrointestinal formulations using three treatments designed to simulate the biological and chemical conditions of the gastrointestinal environment. The three experimental treatments were composed of fecal microorganisms, chyme, and chyme+fecal microorganisms. Water was used as a control treatment. Phenanthrene laden biopolymer and a C18 membrane were immersed in each treatment. Phenanthrene was extracted from each membrane and measured with HPLC. Membrane-associated phenanthrene was taken to represent the fraction that had desorbed from the biopolymer. Cutin was found to yield an average phenanthrene release 55% higher than cutan (94% vs. 39%). A significant decrease ( p < 0.05 ) in phenanthrene release was observed in both the chyme and chyme+fecal microorganism treatments as compared to the water treatment (control). The presence of enteric microorganisms did not significantly influence phenanthrene release and did not reduce phenanthrene bioaccessibility in gastrointestinal chyme. Over 80% of the phenanthrene in cutin was recovered in the C18 matrix and its relative amount was uninfluenced by the treatments. For cutan, only 25–50% of the phenanthrene was recovered, suggesting that cutin-associated phenanthrene was more loosely bound. These data demonstrate that the fractions of NOM retained phenanthrene to a varying extent and thus the predictions of phenanthrene bioavailability should also be assessed on the basis of the constituents of the NOM matrix.

ATR-FTIR investigation of the role of phenolic groups in the interaction of some NOM model compounds with aluminum hydroxide

The role of phenolic groups in the interaction of natural organic matter (NOM) with metal hydroxides was investigated with ATR-FTIR spectroscopy and adsorption tests by employing a series of dihydroxybenzoic acids (DHBAs) as the NOM surrogates and aluminum hydroxide as the adsorbent. All DHBAs examined in this study were found to be adsorbed on aluminum hydroxide by forming inner-sphere complexes. Carboxylic groups governed the complexation of DHBAs with aluminum hydroxide at low pH or in cases when the two hydroxyl groups were not adjacent to each other and neither of them was ortho to the carboxylic group. The involvement of the phenolic groups, ortho to another phenolic group or ortho to the carboxylic groups, in the complexation increased with increasing pH as the deprotonation of phenolic groups was easier at higher pH. The presence of phenolic groups increased the electron density of the carboxylic groups and facilitated the inner-sphere complexation of the carboxylic groups with metal hydroxide. The correlation between the p K a values and the amount of organic acid adsorbed on the aluminum hydroxide revealed that the adsorption of DHBAs at acidic pH was largely dependent on the surface chelate formation rather than on the electronic effect.

The ionic strength effect on microcystin and natural organic matter surrogate adsorption onto PAC

This work aims to contribute to a better understanding of the ionic strength effect on microcystin and natural organic matter (NOM) surrogate adsorption by analyzing the importance of adsorbate molecular size, and surface concentration. Adsorption kinetics and/or isotherms were performed on PAC Norit SA-UF for four microcystin variants (MC-LR, MC-LY, MC-LW, MC-LF), and three NOM surrogates (salicylic acid (SA), tannic acid (TA), Aldrich humic acid (AHA)) at different solution ionic strengths. Results showed that the ionic strength effect depends upon the adsorbate surface concentration, cation charge (mono or divalent), and adsorbate molecular size. Potassium seemed not to affect the MC-LR adsorption, while calcium enhanced MC-LR kinetics and adsorption capacity. K + and, particularly, Ca 2+ improved the adsorption kinetics of the other microcystin variants. For identical surface concentration and ionic strength, the impact of K + and Ca 2+ on NOM surrogates depended on the adsorbate molecular size: K + effect was only observed for AHA, whereas Ca 2+ caused no effect on SA adsorption, slightly enhanced TA adsorption, and greatly enhanced AHA adsorption. MC-LR isotherms with two salt concentrations (KCl or CaCl 2) indicated that, for the studied range of equilibrium surface concentration (5.3–18.7 mg/g), an enhanced adsorption regime prevails, and no transition regime was observed.

Spatial and temporal evolution of trihalomethanes in three water distribution systems

Spatial and seasonal changes in trihalomethane (THM) concentrations were investigated in three distribution systems of Quebec (Canada) which are supplied by different surface waters and which use a variety of physicochemical treatment strategies. The investigation was based on an intensive 25-week sampling programme, undertaken at a time of year when the temperature of southern Quebec surface waters exceeds 4°C (April–November). THMs and other water quality and operational parameters were monitored at points along the distribution system — between the treatment plant and the system extremities — which represented variable residence times of water. Results showed that THM concentrations vary significantly (from 1.5 to 2 times, depending on the utility) between finished waters as they leave the plant and water at the system extremities. When water temperature exceeds 15°C, spatial THM variations are particularly high (from 2 to 4 times, depending on the utility). The development of multivariate regression models showed that water temperature was a better predictor of THM seasonal variability than chlorine dose, surrogates of natural organic matter and pH. Also, initial THM formation (in finished waters leaving the plant) was a good predictor of THM levels at distribution system extremities.