Toxic Groundwater Contaminants: An Overlooked Contributor to Urban Stream Syndrome?

Screening for common groundwater contaminants was performed along eight urban stream reaches (100s–1000s of m) at approximately 25–75 cm below the streambeds. Four sites had known or suspected chlorinated-solvent plumes; otherwise no groundwater contamination was known previously. At each site, between 5 and 22 contaminants were detected at levels above guideline concentrations for the preservation of aquatic life, while several others were detected at lower levels, but which may still indicate some risk. Contaminants of greatest concern include numerous metals (Cd, Zn, Al, Cu, Cr, U), arsenic, various organics (chlorinated and petroleum), nitrate and ammonium, and chloride (road salt likely), with multiple types occurring at each site and often at the same sampling location. Substantial portions of the stream reaches (from 40 to 88% of locations sampled) possessed one or more contaminants above guidelines. These findings suggest that this diffuse and variable-composition urban groundwater contamination is a toxicity concern for all sites and over a large portion of each study reach. Synergistic toxicity, both for similar and disparate compounds, may also be important. We conclude that groundwater contaminants should be considered a genuine risk to urban stream aquatic ecosystems, specifically benthic organisms, and may contribute to urban stream syndrome

Elevated Dissolved Phosphorus in Riparian Groundwater along Gaining Urban Streams

Findings of low concentrations of dissolved phosphorus in groundwater in large surveys [e.g., United States Geological Survey’s National Water-Quality Assessment (NAWQA) Program (Dubrovsky, N. M.; et al. The Quality of Our Nation’s Water: Nutrients in the Nation’s Streams and Groundwater, 1992–2004. U.S. Geological Survey Circular 1350; USGS: Reston, VA, 2010.); >5000 wells] support the common perception that groundwater is generally of little importance for transporting phosphorus. Here, we address whether this applies to urban riparian settings, where discharging groundwater may potentially contribute to urban stream syndrome and downstream eutrophication problems. This survey study includes 665 samples of groundwater collected along gaining stream reaches at six urban sites. Considering the combined sample set, 27% had soluble reactive phosphorus (SRP) concentrations >0.1 mg L^–1, which is more than double that determined in the NAWQA Program (12%), while for individual sites the range was 12–52%, excluding one site with consistently low SRP (0%). None of the sites showed significant correlation between SRP and the artificial sweetener acesulfame, a promising wastewater indicator, including two with known wastewater contamination (but the lowest SRP). Rather, high SRP concentrations were associated with geochemically reducing conditions. This could mean that natural aquifer or stream sediment materials were a primary contributor of the elevated SRP observed in this study

Profiling Oil Sands Mixtures from Industrial Developments and Natural Groundwaters for Source Identification

The objective of this study was to identify chemical components that could distinguish chemical mixtures in oil sands process-affected water (OSPW) that had potentially migrated to groundwater in the oil sands development area of northern Alberta, Canada. In the first part of the study, OSPW samples from two different tailings ponds and a broad range of natural groundwater samples were assessed with historically employed techniques as Level-1 analyses, including geochemistry, total concentrations of naphthenic acids (NAs) and synchronous fluorescence spectroscopy (SFS). While these analyses did not allow for reliable source differentiation, they did identify samples containing significant concentrations of oil sands acid-extractable organics (AEOs). In applying Level-2 profiling analyses using electrospray ionization high resolution mass spectrometry (ESI-HRMS) and comprehensive multidimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF/MS) to samples containing appreciable AEO concentrations, differentiation of natural from OSPW sources was apparent through measurements of O₂:O₄ ion class ratios (ESI-HRMS) and diagnostic ions for two families of suspected monoaromatic acids (GC × GC-TOF/MS). The resemblance between the AEO profiles from OSPW and from 6 groundwater samples adjacent to two tailings ponds implies a common source, supporting the use of these complimentary analyses for source identification. These samples included two of upward flowing groundwater collected <1 m beneath the Athabasca River, suggesting OSPW-affected groundwater is reaching the river system