Comparing three Australian natural organic matter isolates to the Suwannee river standard: Reactivity, disinfection by-product yield, and removal by drinking water treatments.

Water treatments that provide efficient removal of organic and inorganic disinfection by-product (DBP) precursors across variable natural organic matter (NOM) sources are desirable. Treatments that effectively remove inorganic DBP precursors such as bromide, which significantly shift the speciation of DBP formation towards more toxic DBPs, are of particular interest and have been less investigated. This study characterised NOM isolated from three major drinking water sources in Southeast Queensland (SEQ), Australia, and compared it to the International Humic Substances Society (IHSS) Suwannee River NOM isolate (SR) in terms of DBP precursor removal treatments and DBP formation. Each NOM isolate was used to make synthetic water samples with otherwise identical water quality parameters, that were treated with enhanced coagulation (EC) or EC followed by; anion exchange (MIEX® resin), powdered activated carbon (PAC), granular activated carbon (GAC) or silver impregnated activated carbon (SIAC), to investigate the removal of DBP precursors (bromide and DOC), minimisation of DBPs, as well as the change in specific chlorine demand. EC/SIAC treatment was the most effective method of DBP control studied, due to the efficient simultaneous NOM and bromide adsorption of the SIAC (99 ±â€¯1% bromide removal regardless of NOM source). This treatment also resulted in >92% removal of each of the measured DBPs across all NOM sources, with the exception of DBAN and 1,1-DCP, which achieved >80% removal across all NOM sources. Increases in tribromomethane (TBM) and dibromoacetonitrile (DBAN) formation were observed after all other treatment/NOM-isolate combinations, due to increased Br:DOC ratio after treatment, whereas chlorinated DBPs were generally well-controlled by all treatment/NOM-isolate combinations. Differences in reactivity of the individual NOM isolates were found to be related to both the origin of the isolate and the treatment employed, however, bromide removal capacity for each treatment was independent of NOM source.

Using fluorescence-parallel factor analysis for assessing disinfection by-product formation and natural organic matter removal efficiency in secondary treated synthetic drinking waters.

Parallel factor (PARAFAC) analysis of fluorescence excitation-emission matrices (EEMs) was used to investigate the organic matter and DBP formation characteristics of untreated, primary treated (enhanced coagulation; EC) and secondary treated synthetic waters prepared using a Suwannee River natural organic matter (SR-NOM) isolate. The organic matter was characterised by four different fluorescence components; two humic acid-like (C1 and C2) and two protein-like (C3 and C4). Secondary treatment methods tested, following EC treatment, were; powdered activated carbon (PAC), granular activated carbon (GAC), 0.1% silver-impregnated activated carbon (SIAC), and MIEX® resin. Secondary treatments were more effective at removing natural organic matter (NOM) and fluorescent DBP-precursor components than EC alone. The formation of a suite of 17 DBPs including chlorinated, brominated and iodinated trihalomethanes (THMs), dihaloacetonitriles (DHANs), chloropropanones (CPs), chloral hydrate (CH) and trichloronitromethane (TCNM) was determined after chlorinating water sampled before and after each treatment step. Regression analysis was used to investigate the relationship between peak component fluorescence intensity (FMAX), DBP concentration and speciation, and more commonly used aggregate parameters such as DOC, UV254 and SUVA254. PARAFAC component 1 (C1) was in general a better predictor of DBP formation than other aggregate parameters, and was well correlated (R ≥ 0.80) with all detected DBPs except dibromochloromethane (DBCM) and dibromoacetonitrile (DBAN). These results indicate that the fluorescence-PARAFAC approach could provide a robust analytical tool for predicting DBP formation, and for evaluating the removal of NOM fractions relevant to DBP formation during water treatment.

Sample Enrichment for Bioanalytical Assessment of Disinfected Drinking Water: Concentrating the Polar, the Volatiles, and the Unknowns.

Enrichment methods used in sample preparation for the bioanalytical assessment of disinfected drinking water result in the loss of volatile and hydrophilic disinfection byproducts (DBPs) and hence likely tend to underestimate biological effects. We developed and evaluated methods that are compatible with bioassays, for extracting nonvolatile and volatile DBPs from chlorinated and chloraminated drinking water to minimize the loss of analytes. For nonvolatile DBPs, solid-phase extraction (SPE) with TELOS ENV as solid phase performed superior compared to ten other sorbents. SPE yielded >70% recovery of nonpurgeable adsorbable organic halogens (AOX). For volatile DBPs, cryogenic vacuum distillation performed unsatisfactorily. Purge and cold-trap with crushed ice serving as condensation nuclei achieved recoveries of 50-100% for trihalomethanes and haloacetonitriles and approximately 60-90% for purged AOX from tap water. We compared the purgeable versus the nonpurgeable fraction by combining purge-and-trap extraction with SPE. The purgeable DBP fraction enriched with the purge-and-trap method exerted a lower oxidative stress response in mammalian cells than the nonpurgeable DBPs enriched with SPE after purging, while contributions of both fractions to bacterial cytotoxicity was more variable. 37 quantified DBPs explained almost the entire AOX in the purge-and-trap extracts, but <16% in the SPE extracts demonstrating that the nonpurgeable fraction is dominated by unknown DBPs.

Comparing a silver-impregnated activated carbon with an unmodified activated carbon for disinfection by-product minimisation and precursor removal.

During disinfection, bromide, iodide and natural organic matter (NOM) in source waters can lead to the formation of brominated and/or iodinated disinfection by-products (DBPs), which are often more toxic than their chlorinated analogues. The objective of this study was to compare the efficiency of a silver-impregnated activated carbon (SIAC) with the equivalent unimpregnated granular activated carbon (GAC) for the removal of bromide, iodide and NOM from a matrix of synthetic waters with variable NOM, halide, and alkalinity concentrations, and to investigate the impact on DBP formation. An enhanced coagulation (EC) pre-treatment was employed prior to sample exposure to either carbon adsorbent. Excellent halide removals were observed by the SIAC treatment across the sample matrix, with iodide concentrations consistently reduced to below the method reporting limit (<2 µg/L) from as high as 25 µg/L, and 95±4% removal of bromide achieved. Bromide removal by unimpregnated GAC was poor, however iodide removal was comparable to that achieved by SIAC. The combination of EC with SIAC treatment removed 77±8% of the dissolved organic carbon (DOC) present, across the sample matrix, which was similar to removals by EC/GAC (67±14%). Combined EC/SIAC treatment reduced both total trihalomethanes (tTHMs) and total dihaloacetonitriles (tDHANs) formation by 97±3%, while also achieving a greater than 74% removal of two chloropropanones and a 92±8% decrease in chloral hydrate (CH), compared to untreated samples, regardless of the sample's starting water quality (bromide, alkalinity and NOM concentration). Combined EC/GAC treatment led to similar DBP removals to EC/SIAC for the fully chlorinated DBPs, however, brominated DBPs were less efficiently removed, or experienced concentration increases.

Enhanced coagulation with powdered activated carbon or MIEX secondary treatment: a comparison of disinfection by-product formation and precursor removal.

The removal of both organic and inorganic disinfection by-product (DBP) precursors prior to disinfection is important in mitigating DBP formation, with halide removal being particularly important in salinity-impacted water sources. A matrix of waters of variable alkalinity, halide concentration and dissolved organic carbon (DOC) concentration were treated with enhanced coagulation (EC) followed by anion exchange (MIEX resin) or powdered activated carbon (PAC) and the subsequent disinfection by-product formation potentials (DBP-FPs) assessed and compared to DBP-FPs for untreated samples. Halide and DOC removal were also monitored for both treatment processes. Bromide and iodide adsorption by MIEX treatment ranged from 0 to 53% and 4-78%, respectively. As expected, EC and PAC treatments did not remove halides. DOC removal by EC/PAC was 70 ± 10%, while EC/MIEX enabled a DOC removal of 66 ± 12%. Despite the halide removals achieved by MIEX, increases in brominated disinfection by-product (Br-DBP) formation were observed relative to untreated samples, when favourable Br:DOC ratios were created by the treatment. However, the increases in formation were less than what was observed for the EC/PAC treated waters, which caused large increases in Br-DBP formation when high Br-DBP-forming water quality conditions occurred. The formation potential of fully chlorinated DBPs decreased after treatment in all cases.

Predictive models for water sources with high susceptibility for bromine-containing disinfection by-product formation: implications for water treatment.

This study examines a matrix of synthetic water samples designed to include conditions that favour brominated disinfection by-product (Br-DBP) formation, in order to provide predictive models suitable for high Br-DBP forming waters such as salinity-impacted waters. Br-DBPs are known to be more toxic than their chlorinated analogues, in general, and their formation may be favoured by routine water treatment practices such as coagulation/flocculation under specific conditions; therefore, circumstances surrounding their formation must be understood. The chosen factors were bromide concentration, mineral alkalinity, bromide to dissolved organic carbon (Br/DOC) ratio and Suwannee River natural organic matter concentration. The relationships between these parameters and DBP formation were evaluated by response surface modelling of data generated using a face-centred central composite experimental design. Predictive models for ten brominated and/or chlorinated DBPs are presented, as well as models for total trihalomethanes (tTHMs) and total dihaloacetonitriles (tDHANs), and bromide substitution factors for the THMs and DHANs classes. The relationships described revealed that increasing alkalinity and increasing Br/DOC ratio were associated with increasing bromination of THMs and DHANs, suggesting that DOC lowering treatment methods that do not also remove bromide such as enhanced coagulation may create optimal conditions for Br-DBP formation in waters in which bromide is present.

N-nitrosodimethylamine and trihalomethane formation and minimisation in Southeast Queensland drinking water.

This study assesses the prevalence of disinfection by-product (DBP) precursors in some Southeast Queensland drinking water sources by conducting formation potential experiments for the four regulated trihalomethanes (THMs), and the potent carcinogen, N-nitrosodimethylamine (NDMA). NDMA formation potentials were consistently low (<5-21 ng/L), and total THM (tTHM) formation potentials were consistently below the Australian Drinking Water Guideline (250 µg/L). NDMA concentration of finished drinking waters was also monitored and found to be <5 ng/L in all cases. The effect of coagulation and advanced oxidation on the formation of NDMA and THMs is also reported. UV/H(2)O(2) pre-treatment was effective in producing water with very low THMs concentrations, and UV irradiation was an effective method for NDMA degradation. H(2)O(2) was not required for the observed NDMA degradation to occur. Coagulation using alum, ferric chloride or poly(diallyldimethylammonium chloride) (polyDADMAC) was ineffective in removing DBPs precursors from the source water studied, irrespective of the low dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) attained. Rather, coagulation with polyDADMAC caused an increase in NDMA formation potential upon chloramination, and all coagulants led to an increased tTHM formation potential upon chlorination due to the high bromide concentration of the source water studied.