Rapid analysis of iodinated X-ray contrast media in secondary and tertiary treated wastewater by direct injection liquid chromatography-tandem mass spectrometry

The iodinated x-ray contrast media (ICM) are the most widely administered intravascular pharmaceuticals and are known to persist in the aquatic environment. A rapid method using direct injection liquid chromatography-tandem mass spectrometry (DI-LC-MS/MS) has been developed to measure eight ICM. These include iopamidol, iothalamic acid, diatrizoic acid, iohexol, iomeprol, iopromide, plus both ioxaglic acid and iodipamide, which have not previously reported in the literature. The LC-MS/MS fragmentation patterns obtained for each of the compounds are discussed and the fragments lost for each transition are identified. Matrix effects in post-RO water, MQ water, tap water and secondary effluent have also been investigated. The DI-LC-MS/MS method was validated on both secondary and tertiary treated wastewater, and applied to samples from an advanced activated sludge wastewater treatment plant (WWTP) and a water recycling facility using microfiltration (MF) and reverse osmosis (RO) in Perth, Western Australia. As well as providing information of the efficacy for RO to remove specific ICM, these results also represent the first values of ICM published in the literature for Australia

Occurrence of iodinated X-ray contrast media in indirect potable reuse systems

A lack of knowledge of the health and environmental risks associated with chemicals of concern (COCs) and also of their removal by advanced treatment processes, such as micro-filtration (MF) and reverse osmosis (RO), have been major barriers preventing establishment of large water recycling schemes. As part of a larger project monitoring over 300 COCs, iodinated x-ray contrast media compounds (ICM) were analysed in treated secondary wastewater intended for drinking purposes. ICM are the most widely administered intravascular pharmaceuticals and are known to persist in the aquatic environment. A direct injection liquid chromatography tandem mass spectrometry (DI-LC-MS/MS) method was used to monitor secondary treated wastewater from three major wastewater treatment plants in Perth, Western Australia. In addition, tertiary water treated with MF and RO was analysed from a pilot plant that has been built as a first step in trialling the aquifer recharge. Results collected during 2007 demonstrate that MF/RO treatment is capable of removing ICM to below the analytical limits of detection, with average RO rejection calculated to be greater than 92%. A screening health risk assessment indicated negligible human risk at the concentrations observed in wastewater

Chlorination of Amino Acids: Reaction Pathways and Reaction Rates

Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected by-products. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modelling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4x104 M-1 s-1) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9x102 M-1 s-1), although some N-monochlorovaline degraded into isobutyraldehyde (1.0x10-4 s-1). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3x10-4 s-1) and N-chloroisobutyraldimine (1.2x10-4 s-1). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odour threshold concentration, resulting in aesthetic challenges and an unknown health risk

Organic haloamines 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

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

Behaviour and fate of nine recycled water trace organics during managed aquifer recharge in an aerobic aquifer

The fate of nine trace organic compounds was evaluated during a 12 month large-scale laboratory column experiment. The columns were packed with aquifer sediment and evaluated under natural aerobic and artificial anaerobic geochemical conditions, to assess the potential for natural attenuation of these compounds during aquifer passage associated with managed aquifer recharge (MAR). The nine trace organic compounds were bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR), carbamazepine, oxazepam, iohexol and iodipamide. In the loworganic carbon content Spearwood sediment, all trace organicswere non-retardedwith retardation coefficients between 1.0 and 1.2, indicating that these compounds would travel at near groundwater velocities within the aquifer. The natural aerobic geochemical conditions provided a suitable environment for the rapid degradation for BPA, E2, iohexol (half life b1 day). Lag-times for the start of degradation of these compounds ranged from b15 to 30 days. While iodipamide was persistent under aerobic conditions, artificial reductive geochemical conditions promoted via the addition of ethanol, resulted in rapid degradation (half life b1 days). Pharmaceuticals (carbamazepine and oxazepam) and disinfection by-products (NDMA and NMOR) did not degrade under either aerobic or anaerobic aquifer geochemical conditions (half life N50 days). Field-based validation experiments with carbamazepine and oxazepam also showed no degradation. If persistent trace organics are present in recycled waters at concentrations in excess of their intended use, natural attenuation during aquifer passage alonemay not result in extracted watermeeting regulatory requirements. Additional pre treatment of the recycled water would therefore be required

Bioavailability of nanoscale metal oxides TiO(2), CeO(2), and ZnO to fish

addresses: The Hatherly Laboratories, University of Exeter, Prince of Wales Road, Exeter EX4 4PS, UK.types: Journal Article; Research Support, Non-U.S. Gov'tCopyright © 2010 American Chemical Society. Post print version of article deposited. The final published version is available from: http://dx.doi.org/10.1021/es901971aNanoparticles (NPs) are reported to be a potential environmental health hazard. For organisms living in the aquatic environment, there is uncertainty on exposure because of a lack of understanding and data regarding the fate, behavior, and bioavailability of the nanomaterials in the water column. This paper reports on a series of integrative biological and physicochemical studies on the uptake of unmodified commercial nanoscale metal oxides, zinc oxide (ZnO), cerium dioxide (CeO(2)), and titanium dioxide (TiO(2)), from the water and diet to determine their potential ecotoxicological impacts on fish as a function of concentration. Particle characterizations were performed and tissue concentrations were measured by a wide range of analytical methods. Definitive uptake from the water column and localization of TiO(2) NPs in gills was demonstrated for the first time by use of coherent anti-Stokes Raman scattering (CARS) microscopy. Significant uptake of nanomaterials was found only for cerium in the liver of zebrafish exposed via the water and ionic titanium in the gut of trout exposed via the diet. For the aqueous exposures undertaken, formation of large NP aggregates (up to 3 mum) occurred and it is likely that this resulted in limited bioavailability of the unmodified metal oxide NPs in fish

Validation of Dual Membrane Treatment for Indirect Potable Reuse

The Western Australia's Premier's Collaborative Research Program (PCRP) project 'Characterising Treated Wastewater for Drinking Purposes Following Reverse Osmosis Treatment' commenced in October 2005, to determine the potential risks of replenishing drinking water aquifers with MF/RO treated secondary wastewater from Perth?s wastewater treatment plants. A brief report on the project won the Michael Flynn Award for the best poster paper at Ozwater 10. The results included those published in Water, February 2010, by Rodriguez et al, entitled Efficiency of RO for removal of Chemical Contaminants. Consequently, this version has been drafted to cover the other aspects of the study, principally the identification of suitable indicators which could be used to validate treatment performance

Organic chloramines in drinking water: An assessment of formation, stability, reactivity and risk

© 2016 Elsevier Ltd. Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N-chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N-chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable