Development of multi-residue gas chromatography coupled with mass spectrometry methodologies for the measurement of 15 chemically different disinfection by-products (DBPs) of emerging concern in drinking water from two different Portuguese water treatment plants.

In water treatment plants (WTPs), chemical agents, such as chlorine and ozone, might react with organic matter and anthropogenic contaminants, forming a high diversity of disinfection by-products (DBPs). Due to the potential toxicological effects, the identification of unregulated DBPs (UR-DBPs) is critical to help water managers in the selection of effective water treatment processes, contributing to improving water safety plans. Given the limited validated analytical methods to detect UR-DBPs, here we developed new multi-residue gas chromatography coupled with mass spectrometry methodologies for the detection and quantification of 15 UR-DBPs, including aldehydes, haloketones (HKs), nitrosamines and alcohols, in drinking water matrices. Solid-phase extraction (SPE), for the nitrosamine group, and solid-phase micro extraction (SPME), for the remaining DBPs, were used as sample preparation methods. The developed methodologies allowed the quantification of target UR-DBPs at trace concentration levels (ng L-1), with method quantification limits (MQLs) ranging from 14.4 ng L-1 to 26.0 ng L-1 (SPE-GC-MS) and 2.3 ng L-1 and 1596 ng L-1 (SPME-GC-MS). The methods were applied to different drinking water matrices, considering distinct delivery points of EPAL - Empresa Portuguesa das Águas Livres WTPs. Overall, the aldehyde group, represented by decanal, nonanal and 2-ethylheaxanal, showed the highest occurrence, followed by HKs and nitrosamines. The results of this study suggested that the formation of these UR-DBPs should be further monitored in WTPs.

Assessment of Water Quality Parameters and their Seasonal Behaviour in a Portuguese Water Supply System: a 6-year Monitoring Study.

Water quality monitoring is a fundamental tool in the management of freshwater resources. The purpose of monitoring is to provide meaningful quality data for local action planning and catchment-wide decision making. The assessment of water quality is crucial to guarantee the efficient operation of the Water Treatment Plants (WTPs), promoting health conditions and contributing for a more sustainable urban water cycle. In accordance, the objective of this study was to evaluate key target chemical and microbiological water quality parameters, some of them already monitored within Portuguese/EU legal framework and others still not regulated, but with environmental and human heath relevance. A local monitoring database model, using a 6-year period (from 2014 to 2019) of water quality data, regarding water samples collected on representative sampling locations covering the freshwater abstraction sites, conventional WTPs and distribution network was assessed. This work provides new knowledge regarding occurrence and seasonal behaviour for both microbiological and chemical water quality parameters, essential to understand/manage the water supply system. Additionally, relationships between the target variables were also assessed. Particularly, strong correlations were identified between TOC and THMs formation at distribution network (r = 0.69; p ≤ 0.001); nitrates were the water quality parameter that revealed the best correlation between surface water source and treated water (r = 0.81; p ≤ 0.001), suggesting that treatment yield/performance is dependent on surface water load. The local and continuous monitoring of water systems are crucial to implement new approaches to guarantee the best quality of drinking water throughout the supply system.

Responses of benthic diatoms to waters affected by post-fire contamination.

Wildfire effects go beyond direct impact in terrestrial ecosystems. Specifically, the periphytic communities of aquatic ecosystems standing within and downstream the burnt areas are relevant ecological receptors of post-fire runoff contamination. Nevertheless, the off-site impacts of wildfires in these communities are limitedly studied so far. The present study aimed to assess the effects of river water contaminated with ash-loaded runoff in the growth benthic diatom Navicula libonensis (Schoeman 1970). Four surface water samples were collected approximately one year after the wildfire for laboratory testing with the diatom: one was collected from a site upstream the burnt area, within the Unhais river (UU); three were collected from sites standing within the burnt area, one in the Unhais river (UB) and two in the Zêzere river (Z1 and Z2), reflecting different hydrological regimes. N. libonensis was proven able to discriminate among river sites affected and unaffected by wildfire runoff, reflecting, in general, the expected trends considering the physico-chemical characterization of the water samples. The water samples from the sites standing within the burnt area inhibited the biomass yield and growth rate of the tested diatom, ranking the samples regarding toxicity as follows: Z1 > UB > Z2 > UU. However, UB rather than Z1 presented the highest contaminant burden, namely metal elements, and some were found above widely accepted safety benchmarks (polycyclic aromatic hydrocarbons were not detected). This inconsistency can be linked to unknown interactions among metals within each water sample, to differential nutrient enrichment of samples, as well as hydrological factors. Overall, our results suggest that monospecific laboratory assays with sensitive diatoms can be valuable as cost-effective screening tools to prioritize sites affected by wildfires runoff requiring in-depth monitoring of negative effects in benthic producer communities.

Toxicological assessment of seven unregulated drinking water Disinfection By-products (DBPs) using the zebrafish embryo bioassay.

Disinfection By-products (DBPs) are formed during the chemical treatment of water for human consumption, by the reaction of raw water with chemical agents used in the different steps of the process. Disinfection is one of the most important steps, inactivating pathogens and preventing their regrowth during water distribution. However, it is also involved in DBPs formation due to the use of disinfectant agents, such as chlorine, which reacts with dissolved precursors, such as pharmaceuticals, toxins, pesticides, among others. Given their widespread occurrence, potential human health and (eco) toxicological impacts are of particular interest due to their potential carcinogenicity and various non-carcinogenic effects, such as endocrine disruption. In this study, the developmental toxicity of chemically- different unregulated DBPs was evaluated using zebrafish embryo bioassay. Embryos were exposed to different concentrations of the target DBPs and multiple endpoints, including, mortality, morphological abnormalities and locomotor behavior were assessed at specific developmental stages (24, 48, 72 and 96 hpf). The different families of DBPs tested included nitrosamines, aldehydes, alcohols and ketones. The results show that the effects were compound dependent, with EC10 values varying between 0.04 mg/L (2-ethyl-1-hexanal) to 9.2 mg/L (hexachloroacetone). Globally, several of the tested unregulated DBPs displayed higher toxicity when compared with the available data for some already regulated, such as trihalomethanes (THMs), which highlights the importance of screening the toxicity of still untested and poorly characterized DBPs.

Hazard and mode of action of disinfection by-products (DBPs) in water for human consumption: Evidences and research priorities.

Disinfection of water system is an essential strategy to protect human health from pathogens and prevent their regrowth during water distribution, but the reaction of disinfectant agents with organic matter can lead to the formation of disinfection by-products (DBPs). Given their widespread occurrence, potential human health impacts and (eco)toxicity associated with exposure to DBPs are of particular interest due to their potential carcinogenicity and vary non-carcinogenic effects, such as endocrine disruption. Understanding the public health implications of this emerging issue is crucial for societies and decision-makers, supporting more effective water safety plans. Here, we review the recent literature on the effects of DBPs presented in drinking water and treated swimming pools water, focusing particularly in unregulated compounds and the putative underlying mode of action, linking the available data with adverse health outcomes. Overall, the majority of studies highlight the limited knowledge in the understanding of the underlying mode of action of DBPs. Yet, available evidences indicate that different signaling pathways seem to be involved in the adverse outcomes associated with distinct DBPs classes. The main knowledge gaps in this field are also identified, and future research priorities discussed.

Bioaugmentation of membrane bioreactor with Achromobacter denitrificans strain PR1 for enhanced sulfamethoxazole removal in wastewater.

Achromobacter denitrificans strain PR1, previously found to harbour specific degradation pathways with high sulfamethoxazole (SMX) degradation rates, was bioaugmented into laboratory-scale membrane bioreactors (MBRs) operated under aerobic conditions to treat SMX-containing real domestic wastewater. Different hydraulic retention times (HRTs), which is related to reaction time and loading rates, were considered and found to affect the SMX removal efficiency. The availability of primary substrates was important in both bioaugmented and non-bioaugmented activated sludge (AS) for cometabolism of SMX. High HRT (24 h) resulted in low food to microorganism ratio (F/M) and low SMX removal, due to substrate limitation. Decrease in HRT from 24 h to 12 h, 6 h and finally 4 h led to gradual increases in primary substrates availability, e.g. organic compounds and ammonia, resulted in increased SMX removal efficiency and degradation rate, and is more favorable for high-rate wastewater treatment processes. After inoculation into the MBRs, the bioaugmentation strain was sustained in the reactor for a maximum of 31 days even though a significant decrease in abundance was observed. The bioaugmented MBRs showed enhanced SMX removal, especially under SMX shock loads compared to the control MBRs. The results of this study indicate that re-inoculation is required regularly after a period of time to maintain the removal efficiency of the target compound.

Comparison of UV photolysis, nanofiltration, and their combination to remove hormones from a drinking water source and reduce endocrine disrupting activity.

A sequential water treatment combining low pressure ultraviolet direct photolysis with nanofiltration was evaluated to remove hormones from water, reduce endocrine disrupting activity, and overcome the drawbacks associated with the individual processes (production of a nanofiltration-concentrated retentate and formation of toxic by-products). 17ß-Estradiol, 17α-ethinylestradiol, estrone, estriol, and progesterone were spiked into a real water sample collected after the sedimentation process of a drinking water treatment plant. Even though the nanofiltration process alone showed similar results to the combined treatment in terms of the water quality produced, the combined treatment offered advantage in terms of the load of the retentate and decrease in the endocrine-disrupting activity of the samples. Moreover, the photolysis by-products produced, with higher endocrine disrupting activity than the parent compounds, were effectively retained by the membrane. The combination of direct LP/UV photolysis with nanofiltration is promising for a drinking water utility that needs to cope with sudden punctual discharges or deterioration of the water quality and wants to decrease the levels of chemicals in the nanofiltration retentate.