Drinking Water

Groundwater is a major drinking water resource but its quality with regard to organic micropollutants (MPs) is insufficiently assessed. Therefore, we aimed to investigate Swiss groundwater more comprehensively using liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS). First, samples from 60 sites were classified as having high or low urban or agricultural influence based on 498 target compounds associated with either urban or agricultural sources. Second, all LC-HRMS signals were related to their potential origin (urban, urban and agricultural, agricultural, or not classifiable) based on their occurrence and intensity in the classified samples. A considerable fraction of estimated concentrations associated with urban and/or agricultural sources could not be explained by the 139 detected targets. The most intense nontarget signals were automatically annotated with structure proposals using MetFrag and SIRIUS4/CSI:FingerID with a list of >988,000 compounds. Additionally, suspect screening was performed for 1162 compounds with predicted high groundwater mobility from primarily urban sources. Finally, 12 nontargets and 11 suspects were identified unequivocally (Level 1), while 17 further compounds were tentatively identified (Level 2a/3). amongst these were 13 pollutants thus far not reported in groundwater, such as: the industrial chemicals 2,5-dichlorobenzenesulfonic acid (19 detections, up to 100 ng L^-1), phenylphosponic acid (10 detections, up to 50 ng L^-1), triisopropanolamine borate (2 detections, up to 40 ng L^-1), O-des[2-aminoethyl]-O-carboxymethyl dehydroamlodipine, a transformation product (TP) of the blood pressure regulator amlodipine (17 detections), and the TP SYN542490 of the herbicide metolachlor (Level 3, 33 detections, estimated concentrations up to 100–500 ng L^-1). One monitoring site was far more contaminated than other sites based on estimated total concentrations of potential MPs, which was supported by the elucidation of site-specific nontarget signals such as the carcinogen chlorendic acid, and various naphthalenedisulfonic acids. Many compounds remained unknown, but overall, source related prioritisation proved an effective approach to support identification of compounds in groundwater.

Organic micropollutants (MPs) are increasingly detected in water resources, which can be a concern for human health and the aquatic environment. Ultraviolet (UV) radiation based advanced oxidation processes (AOP) such as low-pressure mercury vapor arc lamp UV/H₂O₂ can be applied to abate these MPs. During UV/H₂O₂ treatment, MPs are abated primarily by photolysis and reactions with hydroxyl radicals (^•OH), which are produced in situ from H₂O₂ photolysis. Here, a model is presented that calculates the applied UV fluence (H_calc) and the ^•OH exposure (CT_•OH,calc ) from the abatement of two selected MPs, which act as internal probe compounds. Quantification of the UV fluence and hydroxyl radical exposure was generally accurate when a UV susceptible and a UV resistant probe compound were selected, and both were abated at least by 50 %, e.g., iopamidol and 5-methyl-1H-benzotriazole. Based on these key parameters a model was developed to predict the abatement of other MPs. The prediction of abatement was verified in various waters (sand filtrates of rivers Rhine and Wiese, and a tertiary wastewater effluent) and at different scales (laboratory experiments, pilot plant). The accuracy to predict the abatement of other MPs was typically within ±20 % of the respective measured abatement. The model was further assessed for its ability to estimate unknown rate constants for direct photolysis (k_UV,_MP) and reactions with ^•OH (k•_OH,_MP). In most cases, the estimated rate constants agreed well with published values, considering the uncertainty of kinetic data determined in laboratory experiments. A sensitivity analysis revealed that in typical water treatment applications, the precision of kinetic parameters (k_UV,_MP for UV susceptible and for UV resistant probe compounds) have the strongest impact on the model's accuracy.

Chemical disinfectants employed in water and wastewater treatment can produce a variety of transformation products, including carbonyl compounds (e.g., saturated and unsaturated aldehydes and ketones). Experiments conducted under conditions relevant to chlorination at drinking water treatment plants and residual chlorine application in distribution systems indicate that α,β-unsaturated carbonyl compounds readily react with free chlorine and free bromine over a wide pH range but react slowly with combined chlorine (i.e., NH₂Cl). For nearly all of the 11 α,β-unsaturated carbonyl compounds studied, the apparent second-order rate constants for the reaction with free chlorine increased in a linear manner with hypochlorite (OCl^–) concentrations, yielding species-specific second-order rate constants for the reaction with OCl^– ranging from 0.21 to 12 M^–1 s^–1. Predictions based on the second-order rate constants indicate that a substantial fraction (i.e., >60%) of several of the more prominent α,β-unsaturated carbonyls (e.g., acrolein, crotonaldehyde) will be transformed to an appreciable extent in distribution systems by free chlorine. Products from the reaction of chlorine with acrolein, crotonaldehyde, and methyl vinyl ketone were tentatively identified using nuclear magnetic resonance (NMR) and gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC–HRT-MS). These products lacked unsaturated carbons and, in some cases, contained multiple halogens.

Copper (Cu) is a promising antimicrobial for premise plumbing, where ions can be dosed directly via copper silver ionization or released naturally via corrosion of Cu pipes, but Cu sometimes inhibits and other times stimulates Legionella growth. Our overarching hypothesis was that water chemistry and growth phase control the net effect of Cu on Legionella. The combined effects of pH, phosphate concentration, and natural organic matter (NOM) were comprehensively examined over a range of conditions relevant to drinking water in bench-scale pure culture experiments, illuminating the effects of Cu speciation and precipitation. It was found that cupric ions (Cu²⁺) were drastically reduced at pH > 7.0 or in the presence of ligand-forming phosphates or NOM. Further, exponential phase L. pneumophila were 2.5× more susceptible to Cu toxicity relative to early stationary phase cultures. While Cu²⁺ ion was the most effective biocidal form of Cu, other inorganic ligands also had some biocidal impacts. A comparison of 33 large drinking water utilities' field-data from 1990 and 2018 showed that Cu²⁺ levels likely decreased more dramatically (>10×) than did the total or soluble Cu (2×) over recent decades. The overall findings aid in improving the efficacy of Cu as an actively dosed or passively released antimicrobial against L. pneumophila.

As a low-maintenance and cost-effective process, gravity-driven membrane (GDM) filtration is a promising alternative for decentralized drinking water supply, while the low flux impedes its extensive application. In order to address such issue, an integrated process consisting of granular activated carbon (GAC) layer and GDM was developed. The performance of virgin (fresh GAC) or preloaded GAC (saturated GAC) was compared. Flux stabilization was observed both in the fresh and saturated GAC/GDM process during long-term filtration and their stable fluxes were both improved by approximately 50% relative to the GDM control. Moreover, integrating GAC with GDM contributed to efficient removals for dissolved organic compounds (DOC), assimilable organic carbon (AOC) and low molecular weight substances both in fresh and saturated GAC/GDM filtration. Compared to GDM control, coupling GAC to GDM could significantly reduce the concentrations of extracellular polymeric substances (EPS) and total cell counts (TCC) within the biofouling layer, and engineer highly heterogeneous structures of biofouling layer on the membrane surface. In the fresh GAC/GDM process, the improved flux obtained was mainly related to less coverage of biofouling layer and lower EPS concentrations due to efficient removals of membrane foulants by GAC adsorption. The achieved higher stable flux can be maintained during long-term filtration (after GAC saturation) owing to the combined effects of EPS reduction and formation of highly heterogeneous structures of biofouling layer in the saturated GAC/GDM system. Overall, the integrated GAC/GDM process can hopefully facilitate improvements both in the stabilized flux and permeate quality, with practical relevance for GDM applications in decentralized drinking water supply.