Determination of human and veterinary antibiotics in indirect potable reuse systems

This paper reports the optimization and validation of an analytical method for the determination of the residual concentration of the prescription antibiotics metronidazole, trimethoprim, sulfamethoxazole, azithromycin, clindamicyn, clarithromycin, erythromycin-H2O, roxithromycin and tylosin in wastewater and advanced treated wastewater. The method applied was used in a study of removal efficiency of these compounds at a full scale operational water reclamation plant using microfiltration-reverse osmosis (MF-RO) (Kwinana, Western Australia). The analytical procedure involves off-line solid-phase extraction (SPE) followed by liquid chromatography - tandem mass spectrometry (LC-MS/MS) operated in multiple reaction monitoring mode. Method validation included determination of linearity, accuracy, precision, method limits of quantitation (MLQs), reproducibility and matrix effect. SPE recoveries were generally higher than 89% for both pre- and post- RO water, except for erythromycin which yielded approximately 50% recovery. The overall precision of the method was better than 16% RSD (relative standard deviation), for all compounds and matrices. MLQ ranged between 23-53 ng/L and 2.5-31 ng/L for pre- and post- RO water, respectively. In-house reproducibility expressed as RSD was generally better than 10%. Inter-laboratory tests revealed a generally good agreement between concentrations of antibiotics reported by all participants. Results demonstrate that MF/RO treatment is capable of removing antibiotics present at relevant environmental concentration in secondary effluent (from the low to-mid ng/L range) to below MLQs (2.5-31 ng/L), and more importantly, three to six orders of magnitude below the health guideline values developed for this project. Estimated RO rejections ranged between > 91 and 99%

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

Disinfection by-products from halogenation of aqueous solutions of terpenoids

We report the formation of trihalomethanes and other disinfection by-products from four polyfunctional terpenoids during simulated chlorination of natural waters. Complex suites of products were identified by closed loop stripping analysis (CLSA)/gas chromatography-mass spectrometry (GC-MS) from halogenation of b-carotene and retinol. b-Ionone appeared to be a key intermediate in the halogenation of b-carotene and retinol, reacting further under the reaction conditions to produce trans-b-ionone-5,6-epoxide and b-cyclocitral. Halogenation of the four terpenoids also produced trihalomethanes (THMs), most likely through haloform reaction on methyl ketone groups within many of the intermediates. Since halogenation of retinol produced a significant quantity of THMs at a slow reaction rate, retinol-based structures may possibly contribute to the slow reacting phase of THM formation in natural waters. Two polyhydroxyphenol model compounds were halogenated for comparison. The only products identified by CLSA/GC-MS from halogenation of 40,5,7- trihydroxyflavanone and ellagic acid were THMs. 40,5,7-Trihydroxyflavanone rapidly produced THMs, with an extremely high molar yield (94%) at pH 7. Terpenoids of the b-ionone and retinol type should be considered to be significant THM precursors, while 40,5,7-trihydroxyflavanone has been shown to be an extremely significant THM precursor, potentially present within natural organic matter in water treatment processes and distribution system

Simultaneous analysis of 10 trihalomethanes at nanogram per liter levels in water using solid-phase microextraction and gas chromatography mass-spectrometry

Trihalomethanes are predominantly formed during disinfection of water via reactions of the oxidant with natural organic matter. Even though chlorinated and brominated trihalomethanes are the most widespread organic contaminants in drinking water, when iodide is present in raw water iodinated trihalomethanes can also be formed. The formation of iodinated trihalomethanes can lead to taste and odor problems and is a potential health concern since they have been reported to be more toxic than their brominated or chlorinated analogs. Currently, there is no published standard analytical method for I-THMs in water. The analysis of 10 trihalomethanes in water samples in a single run is challenging because the iodinated trihalomethanes are found at very low concentrations (ng/L range), while the regulated chlorinated and brominated trihalomethanes are present at much higher concentrations (above μg/L). An automated headspace solid-phase microextraction technique, with a programmed temperature vaporizer inlet coupled with gas chromatography-mass spectrometry, was developed for routine analysis of 10 trihalomethanes i.e. bromo-, chloro- and iodo-trihalomethanes in water samples. The carboxen/polydimethylsiloxane/divinylbenzene fiber was found to be the most suitable. The optimization, linearity range, accuracy and precision of the method are discussed. The limits of detection range from 1 ng/L to 20 ng/L for iodoform and chloroform, respectively. Matrix effects in treated groundwater, surfacewater, seawater, and secondary wastewater were investigated and it was shown that the method is suitable for the analysis of trace levels of iodinated trihalomethanes in a wide range of waters.The method developed in the present study has the advantage of being rapid, simple and sensitive. A survey conducted throughout various process stages in an advanced water recycling plant showed the presence of iodinated trihalomethanes at ng/L levels

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

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

Use of vibratory shear enhanced processing to treat magnetic ion exchange concentrate: A techno-economic analysis

Disposal of waste generated by inland water treatment technologies is highly expensive. The introduction of vibratory shear enhanced processing (VSEP) to treat waste produced from magnetic ion exchange (MIEX) shows benefits in terms of performance and economics. A small VSEP unit fitted with a nanofiltration (NF) membrane is capable of treating up to 15. kL of MIEX waste per day, is able remove more than 97% of dissolved organic compounds as well as recover over 80% of waste in the form of permeate. The reuse of permeate to makeup brine has seen significant reductions in salt consumption and waste disposal at Wanneroo Groundwater Treatment Plant (GWTP). During the first year of VSEP operation, salt consumption reduced by 42% and waste disposal was projected to reduce by 23.9%. Further improvements in both cost categories were observed in the second year of operation and considering the same trend is followed, the payback period of the project will occur between the 6th and 7th year of operation for discounted analysis and has a positive net present value

Determination of sixteen polycyclic aromatic hydrocarbons in aqueous and solid samples from an Italian wastewater treatment plant

This study addresses the issue of whether it is possible to accurately predict the removalefficiencies of metals of environmental concern (i.e., Al, Ag, As, B, Ba, Cd, Cr, Fe, Mn, Hg, Ni,Pb, Cu, V, and Zn) in a wastewater treatment plant. The plant in question (at Fusina, Venice,Italy) is fed by mixed wastes from municipal and industrial sources (300 000 equivalentinhabitants) and discharges the treated effluent into the Venice lagoon. The year-long samplingcampaign (2001-2002) yielded a substantial amount of analytical data and relatively wide rangesof concentrations of metals in the influent samples, which made it possible to study the removalefficiencies by plotting the terms (inlet concentration - outlet concentration) vs (inlet concentration)for each metal investigated. The data in the plots were fitted using the linear regressionmodel Y ) BX. The slope rates (terms B), which were estimated by the least-squares method,have been adopted as the removal efficiencies, and they can be considered as constants in theconcentration ranges recorded in this work. The relative abundance of metals in the rawwastewaters feeding Fusina WWTP followed the order Al > Fe > B > Zn > Ba > Mn > Cu >Pb > Hg ) Ni > Cr ) As > V > Ag > Cd, while in the effluent the order was Fe > Al > Zn >Mn > Ba > Ni > Cu > Pb > Cr > Ag > As > Hg ) V > Cd. The removal percentages (%) of themetals were Al ) 92 ( 1; Ag ) 94 ( 1; As ) 76 ( 3; B ) n.d.; Ba ) 85 ( 2; Cd ) 85 ( 2; Cr )87 ( 1; Fe ) 90 ( 1; Mn ) 61 ( 2; Hg ) 93 ( 1; Ni ) 50 ( 3; Pb ) 92 ( 1; Cu ) 93 ( 1; V )74 ( 2; and Zn ) 75 ( 3

Impact of NOM character on copper adsorption by trace ferric hydroxide from iron corrosion in water supply system

The fate of trace concentrations of cupric sulfate (<0.4 mg/L) dosed into chloraminated distribution systems to inhibit nitrification has been shown in this study to be controlled by at least two crucial factors: the character of natural organic matter (NOM) and iron hydroxide corrosion products present at low concentrations (<2 mg/L). This research quantified the removal of Cu(II) ions added into waters containing trace Fe(OH)3 flocs and the effect of NOM of different character on this removal. The dominant dissolved copper species in NOM-containing waters were found to be Cu(II)–NOM complexes. Both intramolecular chelation and intermolecular complexation can occur, with the latter occurring preferentially and resulting in the aggregation of smaller organic molecules to form larger molecules. The presence of ferric hydroxide flocs when Cu(II) ions were added into NOM-containing waters was shown to result in removal of Cu(II) ions, presumably as Cu(II)–NOM complexes. This removal was through adsorption processes obeying Freundlich isotherms, although the presence of larger NOM molecules and heterogeneous copper species (e.g. Cu(OH)2(s) and CuO(s)) appeared to shield smaller Cu(II)–NOM complexes from adsorption to some extent. For the strategy of inhibition of nitrification in distribution systems by the addition of Cu(II) ions, complexation of Cu(II) ions by NOM and adsorption of Cu(II)–NOM complexes by ferric hydroxide flocs released from pipe walls pose significant operational challenges to maintaining the concentration of Cu(II) ions through the distribution system

Laboratory Scale Investigations of Potential Odour Reduction Strategies in Biosolids

This study investigated sources of odours from biosolids produced from a Western Australian wastewater treatment plant and examined potential odour reduction strategies on a laboratory scale. Odour reduction methods that were trialled included chemical additions and reduction of centrifuge speed. Chemical addition trials were conducted by adding alum, polyaluminium chloride or ferric chloride to digested sludge that had been sampled prior to the dewatering stage. Trials of chemical addition (alum) to plant dewatered cake were also undertaken. The impact of reducing centrifuge speed on biosolids odour was also investigated using a laboratory scale centrifuge calibrated to operate such that the shear forces on the sample would, as closely as possible, represent those on the plant. To identify the odorous compounds present in biosolids and to assess the effectiveness of the odour reduction measures, headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS SPME-GC-MS) methods were developed. Target odour compounds included volatile sulphur compounds (e.g. DMS, DMDS, DMTS) and other volatile organic compounds (toluene, thylbenzene, styrene, p-cresol, indole, skatole and geosmin). In our laboratory trials, aluminium sulphate added to digested sludge prior to dewatering offered the best odour reduction strategy among the options that were investigated, resulting in approximately 40% reduction in peak concentration of the total volatile organic sulphur compounds (TVOSC), relative to a control sample