Ina Kristiana

The formation of halogen-specific TOX from chlorination and chloramination of natural organic matter isolates

The formation of disinfection by-products (DBPs) is a public health concern. An important way to evaluate the presence of DBPs is in terms of the total organic halogen (TOX), which can be further specified into total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI). The formation and distribution of halogen-specific TOX during chlorination and chloramination of natural organic matter (NOM) isolates in the presence of bromide and iodide ions were studied. As expected, chloramination produced significantly less TOX than chlorination. TOCl was the dominant species formed in both chlorination and chloramination. TOI was always produced in chloramination, but not in chlorination when high chlorine dose was used, due to the limited presence of HOI in chlorination as a result of the oxidation of iodide to iodate in the presence of excess chlorine. The formation of TOI during chloramination increased as the initial iodide ion concentration increased, with a maximum of approximately 60% of the initial iodide ion becoming incorporated into NOM. Iodine incorporation in NOM was consistently higher than bromine incorporation, demonstrating that the competitive reactions between bromine and iodine species in chloramination favoured the formation of HOI and thus TOI, rather than TOBr. Correlations between the aromatic character of the NOM isolates (SUVA(254) and % aromatic C) and the concentrations of overall TOX and halogen-specific TOX in chloramination were observed. This indicates that the aromatic moieties in NOM, as indicated by SUVA(254) and % aromatic C, play an important role in the formation of overall TOX and halogen-specific TOX in chloramination. THMs comprised only a fraction of TOX, up to 7% in chloramination and up to 47% in chlorination. Although chloramine produces less TOX than chlorine, it formed proportionally more non-THM DBPs than chlorine. These non-THM DBPs are mostly unknown, corresponding to unknown health risks. Considering the higher potential for formation of iodinated DBPs and unknown DBPs associated with the use of chloramine, water utilities need to carefully balance the risks and benefits of using chloramine as an alternative disinfectant to chlorine in order to satisfy guideline values for THMs.

Bioanalytical assessment of the formation of disinfection byproducts in a drinking water treatment plant

Disinfection of drinking water is the most successful measure to reduce water-borne diseases and protect health. However, disinfection byproducts (DBPs) formed from the reaction of disinfectants such as chlorine and monochloramine with organic matter may cause bladder cancer and other adverse health effects. In this study the formation of DBPs through a full-scale water treatment plant serving a metropolitan area in Australia was assessed using in vitro bioanalytical tools, as well as through quantification of halogen-specific adsorbable organic halogens (AOXs), characterization of organic matter, and analytical quantification of selected regulated and emerging DBPs. The water treatment train consisted of coagulation, sand filtration, chlorination, addition of lime and fluoride, storage, and chloramination. Nonspecific toxicity peaked midway through the treatment train after the chlorination and storage steps. The dissolved organic matter concentration decreased after the coagulation step and then essentially remained constant during the treatment train. Concentrations of AOXs increased upon initial chlorination and continued to increase through the plant, probably due to increased chlorine contact time. Most of the quantified DBPs followed a trend similar to that of AOXs, with maximum concentrations observed in the final treated water after chloramination. The mostly chlorinated and brominated DBPs formed during treatment also caused reactive toxicity to increase after chlorination. Both genotoxicity with and without metabolic activation and the induction of the oxidative stress response pathway showed the same pattern as the nonspecific toxicity, with a maximum activity midway through the treatment train. Although measured effects cannot be directly translated to adverse health outcomes, this study demonstrates the applicability of bioanalytical tools to investigate DBP formation in a drinking water treatment plant, despite bioassays and sample preparation not yet being optimized for volatile DBPs. As such, the bioassays are useful as monitoring tools as they provide sensitive responses even at low DBP levels.

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: Application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.

Formation of N-nitrosamines from chlorination and chloramination of molecular weight fractions of natural organic matter.

N-Nitrosamines are a class of disinfection by-products (DBPs) that have been reported to be more toxic than the most commonly detected and regulated DBPs. Only a few studies investigating the formation of N-nitrosamines from disinfection of natural waters have been reported, and little is known about the role of natural organic matter (NOM) and the effects of its nature and reactivity on the formation of N-nitrosamines. This study investigated the influence of the molecular weight (MW) characteristics of NOM on the formation of eight species of N-nitrosamines from chlorination and chloramination, and is the first to report on the formation of eight N-nitrosamines from chlorination and chloramination of MW fractions of NOM. Isolated NOM from three different source waters in Western Australia was fractionated into several apparent MW (AMW) fractions using preparative-scale high performance size exclusion chromatography. These AMW fractions of NOM were then treated with chlorine or chloramine, and analysed for eight species of N-nitrosamines. Among these N-nitrosamines, N-nitrosodimethylamine (NDMA) was the most frequently detected. All AMW fractions of NOM produced N-nitrosamines upon chlorination and chloramination. Regardless of AMW characteristics, chloramination demonstrated a higher potential to form N-nitrosamines than chlorination, and a higher frequency of detection of the N-nitrosamines species was also observed in chloramination. The results showed that inorganic nitrogen may play an important role in the formation of N-nitrosamines, while organic nitrogen is not necessarily a good indicator for their formation. Since chlorination has less potential to form N-nitrosamines, chloramination in pre-chlorination mode was recommended to minimise the formation of N-nitrosamines. There was no clear trend in the formation of N-nitrosamines from chlorination of AMW fractions of NOM. However, during chloramination, NOM fractions with AMW <2.5 kDa were found to produce higher concentrations of NDMA and total N-nitrosamines. The precursor materials of N-nitrosamines appeared to be more abundant in the low to medium MW fractions of NOM, which correspond to the fractions that are most difficult to remove using conventional drinking water treatment processes. Alternative or advanced treatment processes that target the removal of low to medium MW NOM including activated carbon adsorption, biofiltration, reverse osmosis, and nanofiltration, can be employed to minimise the formation of N-nitrosamines.

Analysis of polysulfides in drinking water distribution systems using headspace solid-phase microextraction and gas chromatography-mass spectrometry

Sulfide and polysulfides are strong nucleophiles and reducing agents that participate in many environmentally significant processes such as the formation of sulfide minerals and volatile organic sulfur compounds. Their presence in drinking water distribution systems are of particular concern and need to be assessed, since these species consume disinfectants and dissolved oxygen, react with metal ions to produce insoluble metal sulfides, and cause taste and odour problems. The analysis of sulfide and polysulfides in drinking water distribution systems is challenging due to their low concentrations, thermal instability and their susceptibility to undergo oxidation and disproportionation reactions. This paper reports on the development and optimisation of a rapid, simple, and sensitive method for the determination of sulfide and polysulfides in drinking water distribution systems. The method uses methyl iodide to derivatize sulfide and polysulfides into their corresponding dimethyl(poly)sulfides, which are then extracted using solid-phase microextraction in the headspace mode and analysed by gas chromatography-mass spectrometry. Good sensitivity was achieved for the analysis of dimethyl(poly)sulfides, with detection limits ranging from 50 to 240 ng L(-1). The method also demonstrated good precision (repeatability: 3-7%) and good linearity over two orders of magnitude. Matrix effects from raw drinking water containing organic carbon (3.8 mg L(-1)) and from sediment material from a drinking water distribution system were shown to have no interferences in the analysis of dimethyl(poly)sulfides. The method provides a rapid, robust, and reliable mean to analyse trace levels of sulfides and polysulfides in aqueous systems. The new method described here is more accessible and user-friendly than methods based on closed-loop stripping analysis, which have been traditionally used for the analysis of these compounds. The optimised method was used to analyse samples collected from various locations in a drinking water distribution system. Some of the samples were shown to contain inorganic polysulfides, and their presence was associated with high sediment density in the system and the absence of disinfectant residual in the bulk water.

Analysis of halonitriles in drinking water using solid-phase microextraction and gas chromatography–mass spectrometry

Halonitriles are a class of nitrogen-containing disinfection by-products (DBPs) that have been reported to be more toxic and carcinogenic than the regulated DBPs. While haloacetonitriles (HANs) are often measured in drinking waters, there is little information on the formation, characteristics, and occurrence of other, higher molecular weight halonitriles. Halopropionitriles and halobutyronitriles have been predicted to be highly toxic and carcinogenic, and may have sufficient potency and selectivity to account for epidemiological associations of chlorinated and chloraminated water with adverse health effects. This paper reports on the development, optimisation, and validation of a simple, robust, and sensitive analytical method for the determination of halonitriles in waters, as well as the application of the method to study the formation and characteristics of halonitriles. This is the first reported method development for analysis halopropionitriles and halobutyronitriles, and the first study on their formation and occurrence as DBPs in drinking waters. The new method uses headspace solid-phase microextraction to extract the halonitriles from water, which are then analysed using gas chromatography-mass spectrometry (HS SPME/GC-S). The method demonstrated good sensitivity (detection limits: 0.9-80 ng L⁻¹) and good precision (repeatability: 3.8-12%), and is linear over three orders of magnitude. Matrix effects from raw drinking water containing organic carbon (4.1 mg L⁻¹) were shown to be negligible in the analysis of halonitriles. The optimised method was used to study the stability and persistence of halonitriles in aqueous samples, and the formation and occurrence of halonitriles in waters. Results from laboratory-scale disinfection experiments showed that haloacetonitriles were formed in chlorinated and chloraminated samples, but 2,2-dichloropropionitrile was only measured in chloraminated samples. Results from surveys of several drinking water distribution systems confirmed the laboratory findings.

Analysis of free amino acids in natural waters by liquid chromatography-tandem mass spectrometry.

This paper reports a new analytical method for the analysis of 18 amino acids in natural waters using solid-phase extraction (SPE) followed by liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS) operated in multiple reaction monitoring mode. Two different preconcentration methods, solid-phase extraction and concentration under reduced pressure, were tested in development of this method. Although concentration under reduced pressure provided better recoveries and method limits of detection for amino acids in ultrapure water, SPE was a more suitable extraction method for real samples due to the lower matrix effects for this method. Even though the strong cation exchange resin used in SPE method introduced exogenous matrix interferences into the sample extracts (inorganic salt originating from the acid-base reaction during the elution step), the SPE method still incorporates a broad sample clean-up and minimised endogenous matrix effects by reducing interferences originating from real water samples. The method limits of quantification (MLQ) for the SPE LC-MS/MS method in ultrapure water ranged from 0.1 to 100 μg L(-1) as N for the different amino acids. The MLQs of the early eluting amino acids were limited by the presence of matrix interfering species, such as inorganic salts in natural water samples. The SPE LC-MS/MS method was successfully applied to the analysis of amino acids in 3 different drinking water source waters: the average total free amino acid content in these waters was found to be 19 μg L(-1) as N, while among the 18 amino acids analysed, the most abundant amino acids were found to be tyrosine, leucine and isoleucine.

Analysis of halogen-specific TOX revisited: Method improvement and application.

A method was optimised and evaluated for the analysis of total organic halogen (TOX) in drinking water samples. It involved adsorption of organic halogen onto activated carbon, followed by combustion of the activated carbon and adsorbed material, absorption of the resulting hydrogen halide gases in an absorbing solution, and analysis of halide ions in the solution using an on-line ion chromatograph. Careful optimisation and validation of the method resulted in significant improvements compared to previously reported methods. Method detection limits were 5µgL(-1) for TOCl (as Cl(-)), 2µgL(-1) for TOBr (as Br(-)), and 2µgL(-1) for TOI (as I(-)). Interferences with TOI measurement occurred when iodide or iodate was present in the sample at concentrations at or above 100µgL(-1) and 500µgL(-1), respectively. In general, excellent method recoveries were determined for a wide range of model compounds. The method was used to investigate the formation of halogen-specific TOX through a water treatment plant and in laboratory-scale disinfection experiments. Up to 70% of bromide in the water was converted to TOBr following disinfection at the plant. In the disinfection experiments, TOI was preferentially formed in chloraminated samples, and trihalomethanes only constituted a small fraction (≤20%) of TOX, highlighting the significant proportion of halogenated organic DBPs that are not measured regularly. This is the first report of a comprehensive assessment of the key parameters influencing the efficiency and reliability of the analysis of halogen-specific TOX in drinking water with demonstration of its applications.

Electrochemical treatment of reverse osmosis concentrate on boron-doped electrodes in undivided and divided cell configurations

An undivided electrolytic cell may offer lower electrochlorination through reduction of chlorine/hypochlorite at the cathode. This study investigated the performance of electrooxidation of reverse osmosis concentrate using boron-doped diamond electrodes in membrane-divided and undivided cells. In both cell configurations, similar extents of chemical oxygen demand and dissolved organic carbon removal were obtained. Continuous formation of chlorinated organic compounds was observed regardless of the membrane presence. However, halogenation of the organic matter did not result in a corresponding increase in toxicity (Vibrio fischeri bioassay performed on extracted samples), with toxicity decreasing slightly until 10AhL(-1), and generally remaining near the initial baseline-toxicity equivalent concentration (TEQ) of the raw concentrate (i.e., ∼2mgL(-1)). The exception was a high range toxicity measure in the undivided cell (i.e., TEQ=11mgL(-1) at 2.4AhL(-1)), which rapidly decreased to 4mgL(-1). The discrepancy between the halogenated organic matter and toxicity patterns may be a consequence of volatile and/or polar halogenated by-products formed in oxidation by OH electrogenerated at the anode. The undivided cell exhibited lower energy compared to the divided cell, 0.25kWhgCOD(-1) and 0.34kWhgCOD(-1), respectively, yet it did not demonstrate any improvement regarding by-products formation.

Organic chloramines in chlorine-based disinfected water systems: A critical review

This paper is a critical review of current knowledge of organic chloramines in water systems, including their formation, stability, toxicity, analytical methods for detection, and their impact on drinking water treatment and quality. The term organic chloramines may refer to any halogenated organic compounds measured as part of combined chlorine (the difference between the measured free and total chlorine concentrations), and may include N-chloramines, N-chloramino acids, N-chloraldimines and N-chloramides. Organic chloramines can form when dissolved organic nitrogen or dissolved organic carbon react with either free chlorine or inorganic chloramines. They are potentially harmful to humans and may exist as an intermediate for other disinfection by-products. However, little information is available on the formation or occurrence of organic chloramines in water due to a number of challenges. One of the biggest challenges for the identification and quantification of organic chloramines in water systems is the lack of appropriate analytical methods. In addition, many of the organic chloramines that form during disinfection are unstable, which results in difficulties in sampling and detection. To date research has focussed on the study of organic monochloramines. However, given that breakpoint chlorination is commonly undertaken in water treatment systems, the formation of organic dichloramines should also be considered. Organic chloramines can be formed from many different precursors and pathways. Therefore, studying the occurrence of their precursors in water systems would enable better prediction and management of their formation.