A robust procedure for the determination of 16 US EPA PAHs in both aqueous (e.g. wastewaters, industrial discharges, treated effluents) and solid samples (e.g. suspended solids and sludge) from a wastewater treatment plant (WWTP) is presented. Recovery experiments using different percentages of organic modifier, sorbents and eluting solvent mixtures were carried out in Milli-Q water (1000 mL) spiked with a mixture of the PAH analytes (100 ng/L of each analyte). The solid phase extraction (SPE) procedures applied to spiked waste water samples (1000 mL; 100 ng/L spiking level) permitted simultaneous recovery of all the 16PAHs with yields >70% (6-13% RSD). SPE clean up procedures applied to sewage and stabilized sludge extracts, showed percent recoveries in the range 73-92% (7-13% RSD) and 71-89% (7-12% RSD), respectively. The methods were used for the determination of PAHs in aqueous and solid samples from the WWTP of Fusina (Venice, Italy). Mean concentrations, as the sum of the 16PAHs in aqueous and suspended solid samples, were found to be approx. in the 1.12-4.62 microg/L range. Sewage and stabilized sludge samples contained mean PAH concentrations, as sum of 16 compounds, in the concentration range of 1.44-1.26 mg/kg, respectively. Extraction and clean up procedures for sludge samples were validated using EPA certified reference material IRM-104 (CRM No. 912). Instrumental analyses were performed by coupling HPLC with UV-diode array detection (UV-DAD) and fluorescence detection (FLD).

A full-scale (110 ML/d) potable water treatment plant (WTP) based on the MIEX process, an innovative new process based on a strong base anion-exchange resin with magnetic properties, has been operating in Perth Western Australia since 2001. This plant has been configured so that a combined MIEX-coagulation (MIEX-C) process can be operated in parallel with a conventional enhanced coagulation (EC) process, allowing comparison of the performance of the two processes. Here, we report the use of size exclusion chromatography (SEC) to compare the removal of different apparent molecular weight (AMW) fractions of DOC by the two processes. Water was sampled from five key locations within the WTP, and SEC was carried out using three different on-line detector systems, DOC-specific detection, UV absorbance detection at lambda = 254 nm, and fluorescence detection (lambda(ex) = 282 nm; lambda(em) = 353 nm). This approach provided information on the chemical nature of the DOC comprising the various AMW fractions. The study showed that the MIEX-C process outperformed the EC process with greater removal of DOC in each of the eight separate AMW fractions identified. While EC preferentially removed the fractions of highest AMW, and those exhibiting the greatest aromatic (humic) character, MIEX-C removed DOC across all AMW fractions and did not appear to discriminate as strongly on the basis of differences in aromatic character or AMW. The results demonstrate the benefits of combining these complementary treatment processes. The study also demonstrates the utility of SEC coupled with multiple detection systems in determining the characteristics of various AMW components of DOC.

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.

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 μg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 μg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.

The oxidation of dissolved manganese(II) (Mn(II)) during chlorination is a relatively slow process which may lead to residual Mn(II) in treated drinking waters. Chemical Mn(II) oxidation is autocatalytic and consists of a homogeneous and a heterogeneous process; the oxidation of Mn(II) is mainly driven by the latter process. This study demonstrates that Mn(II) oxidation during chlorination is enhanced in bromide-containing waters by the formation of reactive bromine species (e.g., HOBr, BrCl, Br2O) from the oxidation of bromide by chlorine. During oxidation of Mn(II) by chlorine in bromide-containing waters, bromide is recycled and acts as a catalyst. For a chlorine dose of 1 mg/L and a bromide level as low as 10 μg/L, the oxidation of Mn(II) by reactive bromine species becomes the main pathway. It was demonstrated that the kinetics of the reaction are dominated by the adsorbed Mn(OH)2 species for both chlorine and bromine at circumneutral pH. Reactive bromine species such as Br2O and BrCl significantly influence the rate of manganese oxidation and may even outweigh the reactivity of HOBr. Reaction orders in [HOBr]tot were found to be 1.33 (±0.15) at pH 7.8 and increased to 1.97 (±0.17) at pH 8.2 consistent with an important contribution of Br2O which is second order in [HOBr]tot. These findings highlight the need to take bromide, and the subsequent reactive bromine species formed upon chlorination, into account to assess Mn(II) removal during water treatment with chlorine.

No abstract

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.

The iodinated X-ray contrast media 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.