Elsevier

Chemosphere

Volume 85, Issue 5, October 2011, Pages 717-723
Chemosphere

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil – An approach combining tracer substance, bioassay and target analysis

https://doi.org/10.1016/j.chemosphere.2011.05.060Get rights and content

Abstract

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.

Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC–MS–MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14–47 μg L−1). Following a flood event, concentrations of about 16–20 μg L−1 could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L−1 near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L−1 in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.

Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g−1 and up to 0.7 ng g−1, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.

Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.

Highlights

► First-time investigation of flood impact on groundwater/drinking water resources. ► Tracer substance analysis marked deep infiltration of flood water into groundwater. ► Detection of estrogenic activity supported this finding. ► High relevance for drinking water supply safety and groundwater protection. ► Indicates further focuses to reach aims of European Water Framework Directive.

Introduction

Bankside groundwater contamination is of increasing concern in many regions worldwide since bank filtrate is a common drinking water resource (Levin et al., 2002). Groundwater pollution is critical since there is usually a substantial time lag between introduction and detection of contaminants, and groundwater is difficult to monitor (Finch et al., 2007). Thus, due to slow groundwater flow, pollution may impact drinking water supply in the long term (Kühlers et al., 2009).

There are several impacts to groundwater as drinking water resource. However, pollution is usually attributed to anthropogenic waste disposal practices and industrial as well as agricultural activities (Boehlke, 2002, Naik et al., 2007). Furthermore, groundwater quality may be influenced by flood events. Those have the potential to remobilize huge amounts of sediments that act as sink but also as important secondary source of contaminants. Remobilized sediments contribute to suspended particulate matter (SPM) which is translocated in stream or deposited on floodplain soil (Kosmehl et al., 2004, Netzband, 2007, Schulze et al., 2007, Brils, 2008). Floods cause translocation of particle-bound and dissolved substances in relevant concentrations and freights (Hollert et al., 2007, Wölz et al., 2009). Consequently, bankside groundwater may be polluted from direct recharging via infiltration or via translocation from floodplain soil (Brouyere et al., 2004, Kazama et al., 2007).

Impacts to groundwater quality are in the focus of the Water Framework Directive (2006/118/EC) that provides a general set of subjects of protection and objectives to achieve a ‘good chemical and biological status’ for all waters by 2015. This includes the protection of groundwater resources (Groundwater Directive; 2006/118/EC) and, thus, Water Framework Directive demands measures to ensure the progressive reduction of groundwater pollution and to prevent further incidents (Borja et al., 2004).

In this study, the hypothesis was stated that contaminants remobilized in floods deeply infiltrate bankside aquifer and, thus, impact groundwater quality. For this end, groundwater was sampled over 2 years at a non-inundated site near Karlsruhe, Germany, close to the river Rhine. Samples were analyzed for the pharmaceutical carbamazepine (CBZ) as a typical river contaminant as well as for estrogenic activities with transgenic bakery yeast Saccharomyces cerevisiae in the Yeast Estrogen Screen (YES) assay. Furthermore, flood SPM and floodplain soil was sampled at the river Rhine barrage of Iffezheim, Germany, which is close to the groundwater sampling site. Automated fractionation was used to assess estrogenic activity of distinct HPLC-separated fractions of SPM extracts and for target analysis. Thus, the presented study aimed

  • to assess bankside groundwater for CBZ as tracer indicating river water infiltration as well as for estrogenic activity;

  • to fractionate flood SPM and floodplain soil and to assess estrogenic activity with fractions as well as to analyze fractions for target chemicals to determine and evaluate activities in comparison with groundwater, and finally;

  • to conclude on whether contaminants present in flood river water may impact groundwater and drinking water quality.

Section snippets

Materials and methods

In this chapter provider of chemicals will only be given if other than Sigma–Aldrich, Deisenhofen, Germany, since most chemicals were purchased from this company. Any chemicals were at least reagent grade.

Carbamazepine – tracer in aquifer groundwater

CBZ was measured in bankside groundwater sampled over 2 years at a transect starting at the river Rhine (Fig. 3). The concentration was elevated at well No. 1 which is closest to the river Rhine and ranged between 14 and 47 μg L−1 over the sampling period. At well No. 2 before August 2007 CBZ was not present or below detection limit with one exception giving 13 μg L−1 (August, 2006). However, in the weeks and months following the flood event in August 2007 CBZ was measured with concentrations

Conclusions

The hypothesis that elevated concentrations of contaminants may infiltrate bankside groundwater and impact quality as a consequence of flood events appears to be proved. Investigations showed that CBZ is an appropriate tracer substance to verify river expansion into groundwater. Derived from the present results it can be expected that river water easily infiltrates bankside groundwater over distances of some hundred meters away from the river. Consequently, contaminant composition and freight

Acknowledgements

The authors would like to express their thanks to Dr. Routledge and Prof. Sumpter (Brunel University, UK) for supplying the yeast cells for the YES assay. We are particularly grateful to Angela Sperreuter and Marion Heinrich for technical support. We further thank Katharina Graf for assistance with conducting biotests. We also thank the Federal Ministry of Education and Research (BMBF), Germany, for supporting the RIMAX-HoT project within the RIMAX Joint No. 02WH0691. This study was further

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