An integrative method to quantify contaminant fluxes in the groundwater of urban areas

Background, Aims, and Scope  Groundwater in urban areas is often contaminated and emission sources can be located close to groundwater wells. The delineation of contaminant plumes is difficult because of the various potential emission sources. Thus, detection, quantification and remediation of contaminated sites in a city need more integrative approaches. Methods  A method has been developed which allows quantification of mass fluxes of contaminants in groundwater between control planes. Budget zones along the flow path are defined to calculate a contaminant balance and to quantitatively reveal input areas. Concentrations and water budgets are used to calculate mass balances for each contaminant. The city of Darmstadt (Germany) was chosen to evaluate the method. Results  The groundwater monitoring wells (GMWs) upstream of the city showed anthropogenically superposed background values for all naturally occurring inorganic species. The contaminant concentrations increased in the city (probably influenced by road traffic, gas stations, leaking sewers, etc.). Downstream from the city, concentrations usually decreased. Organic compounds typical for urban environments, such as polycyclic aromatic hydrocarbons (PAH), locally exceeded drinking water regulations. In GMWs with high concentrations of organic contaminants in the city or downstream from industrial areas, a significant increase in Fe²⁺ and Mn²⁺ could be observed, in some cases coinciding with a decrease in NO₃, SO₄ and an increase in NH₄. Discussion  For typical urban contaminants, a positive budget was calculated in several zones, which shows that emissions from urban sources are reaching the groundwater. Negative budgets can be mainly explained with diving plumes and degradation. The input calculated from the individual budget zones is usually higher than the input estimated from urban emissions. Differences between the calculated and the estimated input can be explained with additional sources or (bio)degradation processes. Conclusions  It was confirmed that high concentrations of contaminants do not necessarily correlate with high fluxes. Integrative approaches can reveal areas of high contaminant mass input. The results obtained with the new method are plausible compared to the land use and the estimated urban input. The concentration pattern of Fe²⁺, Mn²⁺, SO₄ and NO₃ is partly due to natural processes, triggered by the degradation of organic matter and organic contaminants. Recommendations  Since this method includes mass balances and flux calculations, avoiding an overestimation of single point contaminant concentration, it is recommended to use this approach to quantify groundwater contamination in cities. Further research is focusing on the role of urban soils as natural reservoirs for the input of contaminants.