Elsevier

Chemosphere

Volume 261, December 2020, 127706
Chemosphere

Seasonal performance assessment of four riverbank filtration sites by combined non-target and effect-directed analysis

https://doi.org/10.1016/j.chemosphere.2020.127706Get rights and content

Highlights

  • Combined non-target and effect-directed analysis valuable for process assessment.

  • Low component numbers in river lead to reduced effects in production wells.

  • First application of effect-directed analysis on riverbank filtration.

Abstract

Targeting the most relevant organic micropollutants (OMP) in routine analysis appears difficult due to formation of transformation products of unknown concentration or toxicity. Performance assessment of water purification processes is still based upon limited target data. Therefore, we broadened the assessment of the removal efficiencies with combined non-target and effect-directed analysis at four riverbank filtration (RBF) sites in Germany. To assess micropollutant elimination, constancy and formation during different seasons, considering local redox conditions, travel distances and total component number in the river, non-target analysis features were grouped into categories. Furthermore, RBF sites were investigated with four endpoints (baseline toxicity, acetylcholinesterase inhibition, antibiotic effects and estrogenic effects) for thin-layer chromatography - effect-directed analysis for the first time. Results showed elimination or reduction of many features and effects, but also constancy and formation of varying proportions. Fall river samples showed precipitation-caused dilution in both tests. Spring samples showed increased effects only in acetylcholinesterase inhibition and estrogenic effects, probably due to phytoestrogens or algae bloom during vegetation period. Sites were ranked considering the total number of features, group proportions, seasonal variations and intensity and number of effects in abstraction wells. Oxic conditions and low initial component numbers in the river (Ruhr sites) resulted in less effects and fewer formations. Longer travel distances were important for a more efficient reduction of effects and features. Combination of non-target and effect-directed analysis proved to be valuable for a more comprehensive assessment of process performance beyond target analysis as also unknown OMP are observed with both methods.

Introduction

A broad variety of chemically different organic micropollutants (OMP) is constantly emitted into the environment, both from point sources (e.g. wastewater treatment plants, WWTP) or from diffuse sources (e.g. agriculture) (Schwarzenbach et al., 2006; Stamm et al., 2016). Due to formation of transformation products (TP) during water and wastewater treatment and in the environment, the amount of substances with biological activity increases (Bertelkamp et al., 2014; Hollender et al., 2014; Krauss and Hollender, 2008). Environmental impact as well as human health effects have not yet been fully understood. However, endocrine disrupting compounds in the environment are linked to decreased sperm quality and quantity in men over the past 50 years (Carlsen et al., 1995; Rodprasert et al., 2019; Sifakis et al., 2017; Snyder et al., 2003). Furthermore, complex mixtures of OMP and their TP can lead to additive or synergistic effects (Petrie et al., 2015; Schwarzenbach et al., 2006). Since decades, riverbank filtration (RBF) has been used as a first water purification step representing a natural and cost-effective method for a sustainable improvement of surface water quality (Thakur et al., 2012). River water is purified by abstracting filtered groundwater near a riverbed (Ahmed and Marhaba, 2017). The purification process is amongst others dependent on river water quality (Hunt et al., 2003), travel time and distance (Ray et al., 2008), soil characteristics at the hyporheic zone (Tyagi et al., 2013; Wu et al., 2007), temperature of river water (Sharma et al., 2012) and redox conditions (Tufenkji et al., 2002). These parameters were derived from known OMP (targets), which, however, only provide an incomplete picture of emerging contaminants (Bader et al., 2016; Petrovic et al., 2010). Non-target analysis (NTA) by liquid chromatography - high resolution mass spectrometry (LC-HRMS) represents a suitable method for monitoring complex water samples as it enables discovering new compounds by using all analytical information gained from the applied method for further data evaluation (Müller et al., 2011). Whereas most studies aim at identification of unknown substances with NTA (Ibáñez et al., 2008; Letzel et al., 2015; Ruff et al., 2015; Samanipour et al., 2018), information can also be gained by comparing and prioritizing different samples without further identification (Müller et al., 2011). Thereby, differences between WWTP influents and effluents were identified and the removal efficiency during wastewater treatment steps was assessed (Bader et al., 2016; Nürenberg et al., 2015; Schollée et al., 2015; Verkh et al., 2018). In drinking water production, it was used to prioritize features from a landfill leachate in raw water at waterworks (Müller et al., 2011). Only few RBF sites have been studied so far with NTA: Albergamo et al. (2019) assessed time trends over the last 60 years at a transect at the Lek river (with sample enrichment) and Schlüsener et al. (2015) identified phosphinic acids and phosphine oxides in groundwater from infiltrated river water. At Ergolz river (Switzerland) removal capacity at one site was studied which showed reduced cumulative intensity from river to groundwater wells and finally to the abstraction well (Hollender et al., 2018). Results indicated transformation of many components and formation of new substances caused by longer mean travel times.

Another approach towards the complete understanding of OMP behavior in the environment is effect-directed analysis (EDA), which is a combination of fractionation, bio-testing and subsequent chemical analysis (Brack, 2003; Hecker and Hollert, 2009). Fractionation of the sample, e.g. by high-performance thin-layer chromatography (HPTLC) provides information on structure or molecular weight and offers the advantage of combining a multitude of bioassays with different modes of action without changing the separation conditions (Aranda and Morlock, 2006; Brack, 2003; Hecker and Hollert, 2009). EDA is routinely used in environmental risk assessment (Biselli et al., 2005; Brack, 2005; Phillips et al., 2009; von der Ohe et al., 2009) and identification is not always necessary depending on the aim of the study (Weiss et al., 2017). WWTP have been investigated e.g. for removal or transformation of estrogenic (Buchinger et al., 2013) or neurotoxic substances (Weiss et al., 2017). Common endpoints are bioluminescence inhibition, cytotoxic effects, acetylcholinesterase (AchE) inhibition or estrogenic effects (yeast estrogen screen (YES)) (Choma and Grzelak, 2011; Choma and Jesionek, 2015). Bioluminescence inhibition tests with the bacteria Aliivibrio fischeri have been applied to surface water (Weber et al., 2005), wastewater (Reemtsma et al., 1999), landfill leachates (Schulz et al., 2008) or monitoring of metabolites in groundwater (Müller et al., 2010). A typical estrogenic substance is 17β-estradiol which is degraded to estrone, estriol and nonestrogenic metabolites in soil or WWTP (Casey et al., 2005; Yu et al., 2007). Although estrogens show a high affinity to soil and short half-lives (Casey et al., 2005), they are frequently detected in aquatic systems (Adeel et al., 2017; Kolpin et al., 2002, 2010). Increased concentrations of phytoestrogens are found during growing season and in run-offs after accumulation in soil during winter season (Kolpin et al., 2010; Procházková et al., 2017). Effects on algae and daphnia from veterinary antibiotics in the environment were found at concentrations of 5–100 μg/L (Holten Lützhoft et al., 1999; Wollenberger et al., 2000). AChE inhibitors are used to treat Alzheimer’s disease and therefore are likely to be found in water samples alongside other pharmaceuticals (Weiss et al., 2017) and pesticides with neurotoxic effects (Costa et al., 2008).

To the authors’ knowledge, EDA has not yet been applied to the assessment of RBF removal efficiency. Hitherto it is common practice to divide risk assessment into exposure and effect assessment, although both are closely connected (Schwarzenbach et al., 2006). Therefore, in this study, we combine comprehensive chemical analysis with effect-directed analysis for process assessment at four RBF sites at two rivers with different travel distances, geological/hydrogeochemical settings and catchment characteristics. The aim is to gain more information on the occurrence and behavior of OMP in RBF systems and to assess RBF sites not only based on target data, but also on elimination or formation of possibly toxic and yet unknown OMP and TP.

Section snippets

Sample material and study sites

Water samples were taken from four RBF sites, two sites at the Ems river and two at the Ruhr river (Suppl. Inform. Fig. S1) which were characterized and chemically analyzed by target analysis in our former study (Oberleitner et al., 2020). Thereby also seasonal variations were discussed.

Similar to our former study, here, transects comprising river water (R), a groundwater well near the river (B1) and the abstraction well (W) were investigated at each RBF site (Fig. S1) at three different

Performance assessment based on categorization, seasonality and travel distance by non-target analysis

Results of NTA of defined groups (transect of first section or total distance and sampling time/season) are presented in summarizing figures by absolute (Fig. 1, Fig. 2) and relative feature numbers (Suppl. Inform. Fig. S3) for each site. Total number of features is varying throughout the seasons (Fig. 1, Fig. 2, numbers at top) but generally a larger number of features was detected for Ems river sites (Ea 4,000–8,000, Eb 5,000–11,000) compared to Ruhr river sites (Ra 2,000–3,000, Rb

Conclusions

Four examined sites show significant differences concerning their removal performance for OMP in NTA and EDA. Ranking of the sites was possible considering total feature numbers, proportion of eliminations in seasonal variations and occurrence of effective zones in EDA. In conclusion, oxic conditions at the Ruhr river sites proved to be preferable for reduction of effects and high conductivity aquifers proved to be well suited. In NTA reduced feature numbers and therefore OMP numbers in the

CRediT authorship contribution statement

Daniela Oberleitner: Methodology, Software, Validation, Formal analysis, Investigation, Writing - original draft, Visualization. Lena Stütz: Methodology, Validation, Formal analysis, Investigation, Writing - original draft, Visualization. Wolfgang Schulz: Conceptualization, Methodology, Resources, Writing - review & editing, Visualization, Supervision. Axel Bergmann: Conceptualization, Resources, Writing - review & editing, Supervision. Christine Achten: Conceptualization, Methodology,

Declaration of competing interest

The authors declare that they have no conflict of interest.

Acknowledgements

The authors would like to thank Tobias Bader, Thomas Lucke and Robin Schmid for assistance in data evaluation.

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