Kalinda Watson

Strategies for the removal of halides from drinking water sources, and their applicability in disinfection by-product minimisation: A critical review

The presence of bromide (Br(-)) and iodide (I(-)) in source waters leads to the formation of brominated and iodinated disinfection by-products (DBPs), which are often more toxic than their chlorinated analogues. The increasing scarcity of water resources in Australia is leading to use of impaired and alternative water supplies with high bromide and iodide levels, which may result in the production of more brominated and iodinated DBPs. This review aims to provide a summary of research into bromide and iodide removal from drinking water sources. Bromide and iodide removal techniques have been broadly classified into three categories, namely; membrane, electrochemical and adsorptive techniques. Reverse osmosis, nanofiltration and electrodialysis membrane techniques are reviewed. The electrochemical techniques discussed are electrolysis, capacitive deionization and membrane capacitive deionization. Studies on bromide and iodide removal using adsorptive techniques including; layered double hydroxides, impregnated activated carbons, carbon aerogels, ion exchange resins, aluminium coagulation and soils are also assessed. Halide removal techniques have been compared, and areas for future research have been identified.

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.

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.

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 samples 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.

Temporal and Spatial Variation of Trihalomethanes and Haloacetic Acids Concentration in Drinking Water: A Case Study of Queensland, Australia

A broad survey of regulated trihalomethanes (THM) and haloacetic acids (HAA) concentrations in Queensland drinking water was undertaken and the data were evaluated to assess the overall compliance of the region to Australian Drinking Water Guidelines (ADWG). The results presented here indicate that drinking water total trihalomethane (tTHM) concentrations were predominantly compliant with ADWG, with regions using chlorination being the only regions that exceeded the ADWG for THM. tTHM levels were highest in chlorinated water, whereas levels in combined chlorinated/chloraminated water were much lower. Chloraminated water produced the lowest tTHM levels in the regions examined. tTHM levels generally increased during summer and decreased in winter regardless of disinfection method. Surface waters formed a higher proportion of more highly chlorinated THM species relative to more highly brominated THM species, whereas bore water had a higher proportion of more highly brominated THM species due to the frequently higher bromide concentration and lower natural organic matter (NOM) concentration of these waters. The majority of regions were continuously compliant with ADWG for HAA concentrations, with primarily the trichloroacetic acid guideline value being exceeded, in chlorinated waters only.

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.