A novel concept for estimating the contaminant mass discharge of chlorinated ethenes emanating from clay till sites.

Interest in using contaminant mass discharge (CMD) for risk assessment of contaminated sites has increased over the years, as it accounts for the contaminant mass that is moving and posing a risk to water resources and receptors. The most common investigation of CMD involves a transect of multilevel wells; however, this is an expensive undertaking, and it is difficult to place it in the right position in a plume. Additionally, infrastructure at the site needs to be considered. To derive an initial CMD estimate at a contaminated site and to allow for the prioritization of further investigations and remedial actions, the ProfileFlux method has been developed. It is targeted at former industrial sites with a source zone in a low conductivity layer with primarily vertical flow overlying an aquifer with primarily horizontal groundwater flow. The ProfileFlux method was developed for mature chlorinated solvent plumes, typically originating from more than 30 to 50-year-old spills, as the usage of chlorinated solvents is primarily historical. Thus, it is assumed that the contaminant had time to distribute in the low conductivity layer by mainly diffusive processes. Today the contamination is continuously released to the underlying aquifer, where advection and dispersive (other than diffusive) processes are of higher importance. The approach combines high-resolution, depth-discrete vertical concentration profiles and a simple 2D flow and transport model to estimate CMD by comparing measured and simulated concentration profiles. The study presented herein includes a global sensitivity analysis, in order to identify crucial field parameters, and of particular importance in this regard are source length, groundwater flux and infiltration. The ProfileFlux method was tested at a well-examined industrial site primarily contaminated with trichloroethylene, thereby allowing a comparison between CMD from the ProfileFlux method and the traditional transect method. CMD was estimated at 117-170 g/year, when using the ProfileFlux method, against 143 g/year with the transect method, thus validating ProfileFlux method's ability to estimate CMD. In addition, applying the method identified weak points in the conceptual site model. The method will be incorporated into a user-friendly online tool directed at environmental consultants and decision-makers working on the risk assessment and prioritization of contaminated sites with the specific hydrogeological conditions of an aquifer with an overlying low permeability layer.

Natural attenuation of a chlorinated ethene plume discharging to a stream: Integrated assessment of hydrogeological, chemical and microbial interactions.

Attenuation processes of chlorinated ethenes in complex near-stream systems result in site-specific outcomes of great importance for risk assessment of contaminated sites. Additional interdisciplinary and comprehensive field research is required to enhance process understanding in these systems. In this study, several methods were combined in a multi-scale interdisciplinary in-situ approach to assess and quantify the near-stream attenuation of a chlorinated ethene plume, mainly consisting of cis-dichloroethene (cis-DCE) and vinyl chloride (VC), discharging to a lowland stream (Grindsted stream, Denmark) over a monitoring period of seven years. The approach included: hydrogeological characterisation, reach scale contaminant mass balance analysis, quantification of contaminant mass discharge, streambed fluxes of chlorinated ethenes quantified using Sediment Bed Passive Flux Meters (SBPFMs), assessment of redox conditions, temporal assessment of contaminant concentrations, microbial analysis, and compound-specific isotope analysis (CSIA). This study site exhibits a special attenuation behaviour not commonly encountered in field studies: the conversion from an initially limited degradation case (2012-16), despite seemingly optimal conditions, to one presenting notable levels of degradation (2019). Hence, this study site provides a new piece to the puzzle, as sites with different attenuation behaviours are required in order to acquire the full picture of the role groundwater-surface water interfaces have in risk mitigation. In spite of the increased degradation in the near-stream plume core, the contaminant attenuation was still incomplete in the discharging plume. A conceptualization of flow, transport and processes clarified that hydrogeology was the main control on the natural attenuation, as short residence times of 0.5-37 days restricted the time in which dechlorination could occur. This study reveals the importance of: taking an integrated approach to understand the influence of all attenuation processes in groundwater - surface water interactions; considering the scale and domain of interest when determining the main processes; and monitoring sufficiently both spatially and temporally to cover the transient conditions.

Assessing the Transport of Pharmaceutical Compounds in a Layered Aquifer Discharging to a Stream.

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive.

Assessing the chemical contamination dynamics in a mixed land use stream system.

Traditionally, the monitoring of streams for chemical and ecological status has been limited to surface water concentrations, where the dominant focus has been on general water quality and the risk for eutrophication. Mixed land use stream systems, comprising urban areas and agricultural production, are challenging to assess with multiple chemical stressors impacting stream corridors. New approaches are urgently needed for identifying relevant sources, pathways and potential impacts for implementation of suitable source management and remedial measures. We developed a method for risk assessing chemical stressors in these systems and applied the approach to a 16-km groundwater-fed stream corridor (Grindsted, Denmark). Three methods were combined: (i) in-stream contaminant mass discharge for source quantification, (ii) Toxic Units and (iii) environmental standards. An evaluation of the chemical quality of all three stream compartments - stream water, hyporheic zone, streambed sediment - made it possible to link chemical stressors to their respective sources and obtain new knowledge about source composition and origin. Moreover, toxic unit estimation and comparison to environmental standards revealed the stream water quality was substantially impaired by both geogenic and diffuse anthropogenic sources of metals along the entire corridor, while the streambed was less impacted. Quantification of the contaminant mass discharge originating from a former pharmaceutical factory revealed that several 100 kgs of chlorinated ethenes and pharmaceutical compounds discharge into the stream every year. The strongly reduced redox conditions in the plume result in high concentrations of dissolved iron and additionally release arsenic, generating the complex contaminant mixture found in the narrow discharge zone. The fingerprint of the plume was observed in the stream several km downgradient, while nutrients, inorganics and pesticides played a minor role for the stream health. The results emphasize that future investigations should include multiple compounds and stream compartments, and highlight the need for holistic approaches when risk assessing these dynamic systems.