Nitrosamines in pilot-scale and full-scale wastewater treatment plants with ozonation.

Ozone-based treatment trains offer a sustainable option for potable reuse applications, but nitrosamine formation during ozonation poses a challenge for municipalities seeking to avoid reverse osmosis and high-dose ultraviolet (UV) irradiation. Six nitrosamines were monitored in full-scale and pilot-scale wastewater treatment trains. The primary focus was on eight treatment trains employing ozonation of secondary or tertiary wastewater effluents, but two treatment trains with chlorination or UV disinfection of tertiary wastewater effluent and another with full advanced treatment (i.e., reverse osmosis and advanced oxidation) were also included for comparison. N-nitrosodimethylamine (NDMA) and N-nitrosomorpholine (NMOR) were the most prevalent nitrosamines in untreated (up to 89 ng/L and 67 ng/L, respectively) and treated wastewater. N-nitrosomethylethylamine (NMEA) and N-nitrosodiethylamine (NDEA) were detected at one facility each, while N-nitrosodipropylamine (NDPrA) and N-nitrosodibutylamine (NDBA) were less than their method reporting limits (MRLs) in all samples. Ozone-induced NDMA formation ranging from <10 to 143 ng/L was observed at all but one site, but the reasons for the variation in formation remain unclear. Activated sludge, biological activated carbon (BAC), and UV photolysis were effective for NDMA mitigation. NMOR was also removed with activated sludge but did not form during ozonation.

Fate of N-nitrosodimethylamine, trihalomethane and haloacetic acid precursors in tertiary treatment including biofiltration.

The presence of disinfection by-products (DBPs) such as trihalomethanes (THMs), haloacetic acids (HAAs) and N-nitrosamines in water is of great concern due to their adverse effects on human health. In this work, the removal of N-nitrosodimethylamine (NDMA), total THM and five HAA precursors from secondary effluent by biological activated carbon (BAC) is investigated at full and pilot scale. In the pilot plant two filter media, sand and granular activated carbon, are tested. In addition, we evaluate the influence of ozonation prior to BAC filtration on its performance. Among the bulk of NDMA precursors, the fate of four pharmaceuticals containing a dimethylamino moiety in the chemical structure are individually investigated. Both NDMA formation potential and each of the studied pharmaceuticals are dramatically reduced by the BAC even in the absence of main ozonation prior to the filtration. The low removal of NDMA precursors at the sand filtration in comparison to the removal of NDMA precursors at the BAC suggests that adsorption may play an important role on the removal of NDMA precursors by BAC. Contrary, the precursors for THM and HAA formation are reduced in both sand filtration and BAC indicating that the precursors for the formation of these DBPs are to some extent biodegradable.

Removal of PFOS, PFOA and other perfluoroalkyl acids at water reclamation plants in South East Queensland Australia.

This paper examines the fate of perfluorinated sulfonates (PFSAs) and carboxylic acids (PFCAs) in two water reclamation plants in Australia. Both facilities take treated water directly from WWTPs and treat it further to produce high quality recycled water. The first plant utilizes adsorption and filtration methods alongside ozonation, whilst the second uses membrane processes and advanced oxidation to produce purified recycled water. At both facilities perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) were the most frequently detected PFCs. Concentrations of PFOS and PFOA in influent (WWTP effluent) ranged up to 3.7 and 16 ng L⁻¹ respectively, and were reduced to 0.7 and 12 ng L⁻¹ in the finished water of the ozonation plant. Throughout this facility, concentrations of most of the detected perfluoroalkyl compounds (PFCs) remained relatively unchanged with each successive treatment step. PFOS was an exception to this, with some removal following coagulation and dissolved air flotation/sand filtration (DAFF). At the second plant, influent concentrations of PFOS and PFOA ranged up to 39 and 29 ng L⁻¹. All PFCs present were removed from the finished water by reverse osmosis (RO) to concentrations below detection and reporting limits (0.4-1.5 ng L⁻¹). At both plants the observed concentrations were in the low parts per trillion range, well below provisional health based drinking water guidelines suggested for PFOS and PFOA.

Sampling for PPCPs in wastewater systems: comparison of different sampling modes and optimization strategies.

The aim of this study was to assess uncertainties associated with different sampling modes when evaluating loads of pharmaceuticals and personal care products (PPCPs) in sewers and influents to sewage treatment plants (STPs). The study demonstrates that sampling uncertainty can range from "not significant" to "far greater than the uncertainty due to chemical analysis", which is site- and compound-specific and depends on the (in)accuracy of the analytical method. Conventional sampling devices operated in common time- or flow-proportional sampling modes, and applying traditional sampling intervals of 30 min or longer can result in the collection of nonrepresentative samples. At the influent of a STP, wastewater may appear as a continuous stream, but it is actually composed of a number of intermittently discharged, individual wastewater packets from household appliances, industries, or subcatchments in pressurized sewer systems. The resulting heterogeneity can cause significant short-term variations of pollutant loads. We present different experimental results and a modeling approach showing that the magnitude of sampling uncertainty depends mainly on the number of pollutant peaks and the sampling frequency; sampling intervals of 5 min or shorter may be required to properly account for temporal PPCP variations in influents of STPs. A representative sample is a prerequisite for providing meaningful analytical results and cannot be compensated with a large number of samples, accurate chemical analysis, or sophisticated statistical evaluation. This study highlights that generalizing from one case to another is difficult and hence a careful systems analysis of the catchment under investigation, or precautionary choice for a sophisticated sampling mode, is necessary to prove reproducibility.

Determining the fraction of pharmaceutical residues in wastewater originating from a hospital.

Pharmaceutical residues in water are frequently analysed and discussed in connection with sewage treatment, ecotoxicity and, natural and drinking water quality. Among different localities hospitals are suspected, or implied, to be a major and highly variable source of pharmaceuticals that substantially contribute to the total wastewater load. In this study, the contribution of pharmaceuticals from a hospital to a sewage treatment plant (STP) serving around 45,000 inhabitants was evaluated. Approximately 200 hospital beds result in a hospital bed density of 4.4 beds per 1000 inhabitants, which is a typical value for developed world countries. Prior to sampling, a sound systems analysis was performed, and a sophisticated continuous flow-proportional sampling regime was applied. Hence, overall experimental uncertainty was reduced to a minimum, and measurements provide clear evidence that, for 28 of 59 investigated substances, over 85% of the pharmaceutical residue loads do not originate from the hospital when applying a conservative error estimation. Only for 2 substances, trimethoprim (18%) and roxithromycin (56%), was the maximum observed contribution of the hospital >15%. On average, the contribution of the hospital for the compounds detected in both, hospital effluent and sewage treatment plant influent was small and fairly constant. Five compounds were only detected in hospital wastewater, and 24 neither in the hospital wastewater nor in the total wastewater at the influent of the STP. For these compounds no experimental contribution could be calculated. For the compounds where audit data for both the national consumption and the specific hospital under investigation were available, a prediction of the fraction of pharmaceuticals originating from the hospital was performed. Three quarters of the compounds, classified with the existing audit data, were in the same "hospital contribution category" as determined by measurements. For most of the other compounds, plausible reasons could be identified to explain the observed deviations.