Total organic carbon analysis as a precursor to disinfection byproducts in potable water: oxidation technique considerations

In recent years, an increasing number of regulations and methodologies have begun to utilize total organic carbon (TOC) analysis for monitoring microbial contamination and/or disinfectant byproduct (DBP) precursors. This paper highlights some analytical differences and similarities between the two widely used TOC oxidation techniques: UV persulfate and high temperature combustion (HTC). Previous papers have come to different and sometimes contradictory conclusions on this subject. However, these studies either compared instruments with significantly different flow paths or TOC systems from different eras. Unlike previous studies, this paper compares two modern TOC analyzers with nearly identical flow paths for sample recovery, detection limits, and analysis of real world samples. On average, both persulfate and HTC oxidation yielded good recoveries for 10 hard to oxidize compounds and potable water samples from 5 different locations across the USA. In general, persulfate yielded more precise results because of its lower background response relative to sample response while HTC gave slightly higher results (roughly 2% to 3%) for surface water samples.     

Ascorbic acid treatment to reduce residual halogen-based oxidants prior to the determination of halogenated disinfection byproducts in potable water

Treatment of potable water samples with ascorbic acid has been investigated as a means for reducing residual halogen-based oxidants (disinfectants), i.e. HOCl, Cl2, Br2 and BrCl, prior to determination of EPA Method 551.1A and 551.1B analytes. These disinfection byproducts include certain haloalkanes, haloalkenes, haloethanenitriles, haloaldehydes, haloketones and trichloronitromethane. When used as a dehalogenating agent immediately before analysis, only one analyte, 2,2,2-trichloroethanediol (chloral hydrate), is significantly decomposed. Ascorbic acid is superior to thiosulfate and sulfite as it does not destroy trichloroethanenitrile (trichloroacetonitrile), trichloronitromethane (chloropicrin) or dibromoethanenitrile (dibromoacetonitrile). Unlike ammonia or amines, it is not nucleophilic and cannot form hemiaminals (carbinolamines) with carboxaldehydes and ketones. Ascorbic acid treatment can rapidly consume (reduce) large amounts of active (oxidizing) halogen compounds, producing only inorganic halides and dehydroascorbic acid and not additional halogenated organic molecules.     

The role of Raman spectroscopy in the analytical chemistry of potable water

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attractive for these applications for many reasons, including remote non-invasive sampling, minimal sample preparation and tolerance of water. To a lesser extent, Raman spectroscopy is beginning to play a significant role in environmental analysis for the same reasons. At present, the environmental applications typically apply only to the most contaminated situations due to the still relatively high limits of detection. However, some emerging sampling technologies hold out the promise that Raman may soon be more widely applicable to the analytical chemistry of potable water. Herein we discuss these recent advances, summarize some examples of environmental applications to aqueous systems and suggest avenues of future developments that we expect to be most useful for potable water analysis. Also, a simplified, but detailed, theory of normal Raman scattering is presented. While resonance-enhanced Raman spectroscopy, surface-enhanced Raman spectroscopy and non-linear Raman techniques are briefly discussed, their theories and instrumental configurations are not addressed. Also, this article deals primarily with the modern dispersive Raman experiment (as opposed to the Fourier transform Raman experiment), because it seems most suited for potable water analysis. The goal of this article is to give the environmental scientist with no specialized knowledge of the topic just enough theory and background to evaluate the utility of this rapidly developing analytical tool.     

Co-occurrence profiles of trace elements in potable water systems: a case study

Potable water samples (N?=?74) from 19 zip code locations in a region of Greece were profiled for 13 trace elements composition using inductively coupled plasma mass spectrometry. The primary objective was to monitor the drinking water quality, while the primary focus was to find novel associations in trace elements occurrence that may further shed light on common links in their occurrence and fate in the pipe scales and corrosion products observed in urban drinking water distribution systems. Except for arsenic at two locations and in six samples, rest of the analyzed elements was below maximum contaminant levels, for which regulatory values are available. Further, we attempted to hierarchically cluster trace elements based on their covariances resulting in two groups; one with arsenic, antimony, zinc, cadmium, and copper and the second with the rest of the elements. The grouping trends were partially explained by elements’ similar chemical activities in water, underscoring their potential for co-accumulation and co-mobilization phenomena from pipe scales into finished water. Profiling patterns of trace elements in finished water could be indicative of their load on pipe scales and corrosion products, with a corresponding risk of episodic contaminant release. Speculation was made on the role of disinfectants and disinfection byproducts in mobilizing chemically similar trace elements of human health interest from pipe scales to tap water. It is warranted that further studies may eventually prove useful to water regulators from incorporating the acquired knowledge in the drinking water safety plans.     

Lead (Pb) quantification in potable water samples: implications for regulatory compliance and assessment of human exposure

Assessing the health risk from lead (Pb) in potable water requires accurate quantification of the Pb concentration. Under worst-case scenarios of highly contaminated water samples, representative of public health concerns, up to 71–98 % of the total Pb was not quantified if water samples were not mixed thoroughly after standard preservation (i.e., addition of 0.15 % (v/v) HNO₃). Thorough mixing after standard preservation improved recovery in all samples, but 35–81 % of the total Pb was still un-quantified in some samples. Transfer of samples from one bottle to another also created high errors (40–100 % of the total Pb was un-quantified in transferred samples). Although the United States Environmental Protection Agency’s standard protocol avoids most of these errors, certain methods considered EPA-equivalent allow these errors for regulatory compliance sampling. Moreover, routine monitoring for assessment of human Pb exposure in the USA has no standardized protocols for water sample handling and pre-treatment. Overall, while there is no reason to believe that sample handling and pre-treatment dramatically skew regulatory compliance with the US Pb action level, slight variations from one approved protocol to another may cause Pb-in-water health risks to be significantly underestimated, especially for unusual situations of “worst case” individual exposure to highly contaminated water.     

The role of size exclusion chromatography-flame atomic absorption spectrometry in the treatment chemistry of potable water

The percentage composition of Al13, [AlO4Al12(OH)24(H2O)12]7+, in water treatment coagulants is an important criterion in the development and use of polymeric coagulants. Polymeric coagulants are generally used in cold climates or with highly turbid waters. Size exclusion chromatography flame atomic absorption spectrometry (SEC-FAAS) can separate Al13 and monomeric Al within 6 min. The percentage composition of Al13 and monomeric Al is determined by solving two simultaneous equations. Due to overlapping peaks, a 10% error is associated with this method of quantification. This method can be used on coagulants of varying "r values" (r=[OH-]/[Al3+]), or on mixtures of those coagulants and monomeric aluminium.     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

Degradation of chlortoluron in water disinfection processes: a kinetic study

The kinetics of the reaction between chlortoluron, a phenylurea herbicide [N'-(2-hydroxy-4-methyl-5-chlorophenyl)-N,N-dimethylurea], and hypochlorite, the active species in water disinfection processes involving chlorine, were investigated by HPLC-UV and HPLC-electrospray ionisation mass spectrometry (HPLC-ESI-MS). In particular, the concentrations of the main chlortoluron by-products were monitored as a function of time by HPLC-ESI-MS and a kinetic model was developed to fit the relevant curves. The results showed that chlortoluron degradation starts with two parallel pathways, namely, chlorination and hydroxylation of the aromatic ring, which are then followed by consecutive chlorination reactions, and after almost 2 weeks by ring opening and partial mineralisation, as confirmed by head-space solid-phase microextraction gas chromatography-MS (SPME-GC-MS) and total organic carbon (TOC) measurements. Kinetic constants for the first reactions of the overall process, under pseudo-first-order conditions (hypochlorite excess), were estimated by a fitting procedure.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.     

The development of cryoprobe nuclear magnetic resonance spectroscopy for the rapid detection of organic contaminants in potable water

The detection of trace levels of a range of organic contaminants (including pesticides, toxins and an explosive) in potable water, using cryoprobe NMR spectroscopy with limited sample preparation and rapid acquisition times, is described. Emphasis is placed on the applicability of NMR spectroscopy for use in emergency scenarios as the unbiased nature of the technique facilitates the detection and characterization of unknown compounds at levels as low as 50 microg L(-1).     

The first monoclonal antibody-based,matrix-resistant immunoassay for the carbamate herbicide asulam,in water

To date, no ligand binding assay has been described for the carbamate herbicide asulam, although a variety of physical methods, dependent on pre-concentration of water samples, have been documented for its assessment. However, asulam is increasingly used in sensitive agricultural areas, and statutory regulations concerning its monitoring will undoubtedly become more stringent. Antibodies are optimal partners in ligand binding assays, but it is commonly understood by immunological researchers that where no antibody reactive with a particular antigen has yet been described, the immunogenicity of the antigen may be particularly restricted. By the expedient of employing a specialised approach to final immunisation with an asulam-protein conjugate, prior to the immortalisation of a specific anti-asulam antibody-producing cell, we have succeeded in generating a monoclonal antibody reactive specifically with asulam that can be configured in a convenient immunoassay. This antibody may be used flexibly in a number of ways: small sample volumes of 10 microl can be assessed to sensitivities of 4.35 x 10(-7) M (10 microg L(-1)) while avoiding discrepancies contributed by the assay matrix; this antibody-based assay can also be formatted to deliver sensitivities at levels stipulated by regulatory authorities (e.g., 4.35 x 10(-9) M or 0.1 microg L(-1)) directly from a water sample, without prior pre-concentration.     

Assessing regulatory violations of disinfection by-products in water distribution networks using a non-compliance potential index

Inactivating pathogens is essential to eradicate waterborne diseases. However, disinfection forms undesirable disinfection by-products (DBPs) in the presence of natural organic matter. Many regulations and guidelines exist to limit DBP exposure for eliminating possible health impacts such as bladder cancer, reproductive effects, and child development effects. In this paper, an index named non-compliance potential (NCP) index is proposed to evaluate regulatory violations by DBPs. The index can serve to evaluate water quality in distribution networks using the Bayesian Belief Network (BBN). BBN is a graphical model to represent contributing variables and their probabilistic relationships. Total trihalomethanes (TTHM), haloacetic acids (HAA5), and free residual chlorine (FRC) are selected as the variables to predict the NCP index. A methodology has been proposed to implement the index using either monitored data, empirical model results (e.g., multiple linear regression), and disinfectant kinetics through EPANET simulations. The index’s usefulness is demonstrated through two case studies on municipal distribution systems using both full-scale monitoring and modeled data. The proposed approach can be implemented for data-sparse conditions, making it especially useful for smaller municipal drinking water systems.     

Remote sensing as a tool for monitoring water quality parameters for Mediterranean Lakes of European Union water framework directive (WFD) and as a system of surveillance of cyanobacterial harmful algae blooms (SCyanoHABs)

Remote sensing has been used from the 1980s to study inland water quality. However, it was not until the beginning of the twenty-first century that CHRIS (an experimental multi-angle sensor with good spectral and spatial resolutions) and MERIS (with good temporal and spectral resolutions) started to acquire imagery with very good resolutions, which allowed to develop a reliable imagery acquisition system so as to consider remote sensing as an inland water management tool. This paper presents the methodology developed, from the field data acquisition with which to build a freshwater spectral library and the study of different atmospheric correction systems for CHRIS mode 2 and MERIS images, to the development of algorithms to determine chlorophyll-a and phycocyanin concentrations and bloom sites. All these algorithms allow determining water eutrophic and ecological states, apart from generating surveillance maps of toxic cyanobacteria with the main objective of Assessment of the Water Quality as it was used for Monitoring Ecological Water Quality in smallest Mediterranean Reservoirs integrated in the Intercalibration Exercise of European Union Water Framework Directive (WFD). We keep on using it to monitor the Ecological Quality Ratio (EQR) in Spain inland water.     

Utility of cefixime as a complexing reagent for the determination of Ni(II) in synthetic mixture and water samples

A simple, sensitive, and accurate UV spectrophotometric method has been developed for the determination of nickel in synthetic mixture and water samples. The method is based on the complexation reaction of nickel ion with cefixime, thus leading to the formation of Ni–cefixime complex in ethanol-distilled water medium at room temperature. The complex showed the maximum absorption wavelength at 332 nm. Beer’s law is obeyed in the working concentration range of 0.447–4.019 μg?mL^?1 with apparent molar absorptivity of 7.314?×?10³?L?mol^?1?cm^?1 and Sandell’s sensitivity of 0.008 μg/cm²/0.001 absorbance unit. The limits of detection and quantitation for the proposed method are 0.016 and 0.054 μg?mL^?1, respectively. The factors such as cefixime concentration and solvent affecting the complexation reaction were carefully studied and optimized. The method is validated as per the International Conference on Harmonisation guideline. The method is successfully applied to the determination of Ni(II) in synthetic mixture and wadi water samples collected from Al Rustaq. The same water samples are also analyzed by atomic absorption spectrophotometry. Both methods determined the amount of Ni(II) in water sample and found to be approximately the same.     

Multi-level modelling of chlorination by-product presence in drinking water distribution systems for human exposure assessment purposes

During drinking water treatment and distribution, chlorine reacts with organic matter occurring in water to form various chlorination by-products (CBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). This paper presents the occurrence of THMs and HAAs in different water distribution systems (DS) of the same region and their modelling for exposure assessment purposes. This study was conducted in eight DS supplying chlorinated water to the population of Québec City, Canada. These systems differ in type of water source (i.e. surface, ground or mixed water), in treatment applied at the plant, and in size and structure of the DS. Two spatio-temporal databases for THMs and HAAs were implemented, one for model development and the other for model validation. The analysis of the data demonstrates significant seasonal and spatial variations of these compounds. A multi-level statistical modelling approach was applied to estimate the ranges for occurrence of THMs and HAAs in the eight DS (i.e. a single model for the study region for each CBP species). The modelling approach integrates available or easily measurable parameters. For both THMs and HAAs, a two-level model considering a sampling-site random effect was selected among various models initially developed. The model capacity for estimating the presence of THMs and HAAs in drinking water and its usefulness for exposure assessment purposes in the studied region was demonstrated.     

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.