A multi-pathway exposure assessment for polycyclic aromatic hydrocarbons among residents in the Athabasca oil sands region, Canada.

Due to increasing emissions from ongoing development of the oil sands in Northern Alberta, Canada, there is concern that local residents and organisms are experiencing elevated exposures to hazardous contaminants. We modified an existing human bioaccumulation model (ACC-Human) to represent the local food chain in the Athabasca oil sands region (AOSR), the focus of oil sands development in Alberta. We used the model to assess the potential exposure to three polycyclic aromatic hydrocarbons (PAHs) among local residents that have a high intake of locally sourced traditional foods. To place these estimates into context, we complemented them with estimated PAH intake through market foods and smoking. Our approach was able to produce realistic body burdens of the PAHs in aquatic and terrestrial wildlife and in humans, both in magnitude and with respect to the relative difference between smokers and non-smokers. Over the model simulation period (1967-2009), market food was the dominant dietary exposure route for phenanthrene and pyrene, while local food, and in particular local fish, dominated the intake of benzo[a]pyrene. Exposure to benzo[a]pyrene therefore was also predicted to increase over time in concert with expanding oil sands operations. Those smoking at the average rate of Northern Albertans take in an additional amount of all three PAHs that is at least as large as dietary intake. Estimated daily intake rates are below toxicological reference thresholds for all three PAHs. However, daily intake of BaP in adults is only ∼20 fold below those thresholds and is predicted to increase. Key uncertainties in the assessment included the effect of food preparation on the PAH content in food (e.g., smoking of fish), the limited availability of market food contamination data specific to Canada, and the PAH content of the vapor phase of first-hand cigarette smoke. Considering the satisfactory model evaluation, ACC-Human AOSR should be suited to making predictions of future contaminant exposure based on development scenarios in the AOSR or in response to potential emission reduction efforts. It should also be applicable to other organic contaminants of concern released by oil sands operations.

Phase partitioning, transport and sources of Benzotriazole Ultraviolet Stabilizers during a runoff event.

Benzotriazole Ultraviolet Stabilizers (BT-UVs) are ubiquitous in the environment, given their wide use as additives in consumer products. Their bio-accumulative and toxic properties are increasingly being scrutinised, evinced by the recent proposition to add UV328 to the Stockholm Convention on Persistent Organic Pollutants. Here, we measured concentrations of six BT-UVs in the dissolved and particulate phases of stream water collected from an urban and rural stream during a runoff event. Under baseflow conditions, the less hydrophobic BT-UVs were present at low concentrations in the dissolved phase, while much higher loads of particulate BT-UVs occurred during stormflow, especially in the urban creek. Time-weighted average BT-UV concentrations were up to 4 times higher in the urban than in the rural creek. BT-UVs were found to be prevalent in water obtained from laundering textiles, which plausibly constitutes a major portion of domestic wastewater, and can serve as a BT-UV source to aquatic waterways. However, the observed dilution of a sewage tracer during the run-off event suggests that unregulated wastewater seepage is not responsible for the high BT-UV loads in storm water. High levels of UV328 and UV234 were detected in a select few plastic debris items collected from the urban watershed and in artificial turf grass, respectively. Whereas this may allow for the leaching of those BT-UVs into the creek, most plastic debris is more likely a sink than a source of BT-UVs. The observed input of particle-bound BT-UVs at the onset of the rain event indicates that most of the BT-UVs reach the creek with contaminated particles that had built up on surfaces during the antecedent dry period. UV328 was the dominant BT-UV in those particles. If such particle build-up occurs on road surfaces, it may suggest that the use of UV328 in automotive applications contributes to their presence in urban storm water.

Comparing winter-time herbicide behavior and exports in urban, rural, and mixed-use watersheds.

The presence of pesticides in streams in winter, five to six years following bans on their municipal use suggests that complicated transport behaviour, such as subsurface retention and/or accumulation of pesticides and its release during storms, could be important for understanding recovery time frames following bans or legislation that aim to reduce chemical inputs. We investigated late fall and winter dynamics of four herbicides in paired urban and rural watersheds in Toronto, Canada during rainfall and snowmelt. The range of average concentrations and loads of the sum of atrazine, metolachlor, 2,4-D and mecoprop overlapped in the two types of watersheds, with slightly higher average concentrations in the rural watershed. Relatively consistent herbicide concentration-discharge patterns (i.e. dilution) were observed in the urban sub-watersheds during rainfall, while concentration-discharge patterns were much more variable in the rural watershed. This suggests relatively uniform transport pathways across the urban sub-watersheds, compared to the rural watershed. Concentration-discharge patterns of the neutral herbicides atrazine and metolachlor were similar in both watersheds during snowmelt, though varying discharge patterns resulted in divergent timings of peak concentrations. In contrast, the acidic pesticides 2,4-D and mecoprop, which are primarily associated with urban uses, showed much more variable behavior across both watersheds and merit further investigation. Overall, this work highlights the need to consider pesticide dynamics throughout the year in order to more thoroughly assess the long-term efficacy of legislation governing their use.

Investigating the Sources and Transport of Benzotriazole UV Stabilizers during Rainfall and Snowmelt across an Urbanization Gradient.

Benzotriazole UV stabilizers (BT-UVs) have attracted increasing attention due to their bioaccumulative nature and ubiquitous presence in surface waters. We apply high-frequency sampling in paired watersheds to describe, for the first time, the behavior of BT-UVs in stream channels during snowmelt and rainfall. Relative to a largely agricultural watershed, concentrations of BT-UVs in an urban watershed were 4-90 times greater during rainfall and 3-21 times greater during snowmelt. During rainfall, a decrease in BT-UV concentrations on particles with increasing suspended sediments and streamflow occurred at all urban sites due to input of relatively clean sediments, while both decreases and increases were observed at rural sites. Where increases occurred in the rural watershed, road sediments were consistently suggested as the source. Contrasts between the urban and rural sites were also observed during snowmelt. While BT-UV concentrations on particles peaked with peak suspended sediment levels at urban stream sites, the opposite was true at rural stream sites. This appeared to be driven partially by different snowpack melt rates in the two watersheds, with earlier melt and presumably higher streamflow facilitating suspension or erosion of more contaminated sediment in the urban stream. In general, it appears that relatively high, consistent emissions in the form of informal (plastic) debris disposal by consumers or industrial releases have likely led to more homogeneous BT-UV profiles and temporal behavior in the urban watershed. In the rural watershed, low emissions instead entail that emissions variability is more likely to translate to variability in chemical profiles and temporal behavior.

The transport of polycyclic aromatic hydrocarbons during rainfall and snowmelt in contrasting landscapes.

Though it has been established that stream concentrations of polycyclic aromatic hydrocarbons (PAHs) in urban watersheds can be much greater than those in less developed watersheds, knowledge of transport mechanisms is lacking, particularly in temperate, Northern climates with seasonal snow packs. We combine high-resolution stream water sampling with air, suspended solid and stream flow monitoring to investigate the source to stream transport of PAHs during rainfall and snowmelt in paired watersheds with contrasting land use. Despite similar particle loads, contamination of particles that is 8-48 times higher in the urban watersheds leads to area-normalized loads of PAHs that are 6-82 times greater than in the agricultural watersheds. In the urban watershed, average volumetric storm flow concentrations increase with longer antecedent dry period that allows build-up of PAHs on watershed surfaces. Cluster analysis suggests road dust is a minor source of suspended solid-bound PAHs in more agricultural watersheds during rainfall. During snowmelt, earlier peaks in concentration in the urban watershed are likely due to melt from snow packs and snow banks travelling quickly to the stream network via impervious surfaces and sewer drains. While road-derived inputs also appear to be important during snowmelt in the agricultural watershed, relatively delayed peak concentrations result from delayed inputs from snow packs in more pervious areas of the watershed.

Assessing the Source-to-Stream Transport of Benzotriazoles during Rainfall and Snowmelt in Urban and Agricultural Watersheds.

While benzotriazoles (BTs) are ubiquitous in urban waters, their sources and transport remain poorly characterized. We aimed to elucidate the origin and hydrological pathways of BTs in Toronto, Canada, by quantifying three BTs, electrical conductivity, and δ18O in high-frequency streamwater samples taken during two rainfall and one snowmelt event in two watersheds with contrasting levels of urbanization. Average concentrations of total BTs (∑BT) were 1.3 to 110 times higher in the more urbanized Mimico Creek watershed relative to the primarily agricultural and suburban Little Rouge Creek. Strong correlations between upstream density of major roads and total BT concentrations or BT composition within all events implicate vehicle fluids as the key source of BTs in both watersheds. Sustained historical releases of BTs within the Mimico Creek watershed have likely led to elevated ∑BT in groundwater, with elevated concentrations observed during baseflow that are diluted by rainfall and surface runoff. In contrast, relatively constant concentrations, caused by mixing of equally contaminated baseflow and rainfall/surface runoff, are observed in the Little Rouge Creek throughout storm hydrographs, with an occasional first flush occurring at a subsite draining suburban land. During snowmelt, buildup of BTs in roadside snowpiles and preferential partitioning of BTs to the liquid phase of a melting snowpack leads to early peaks in ∑BT in both streams, except the sites in the Little Rouge Creek with low levels of vehicle traffic. Overall, a history of BT release and land use associated with urbanization have led to higher levels of BTs in urban areas and provide a glimpse into future BT dynamics in mixed use, (sub)urbanizing areas.

Evaluating officially reported polycyclic aromatic hydrocarbon emissions in the Athabasca oil sands region with a multimedia fate model.

Emissions of organic substances with potential toxicity to humans and the environment are a major concern surrounding the rapid industrial development in the Athabasca oil sands region (AOSR). Although concentrations of polycyclic aromatic hydrocarbons (PAHs) in some environmental samples have been reported, a comprehensive picture of organic contaminant sources, pathways, and sinks within the AOSR has yet to be elucidated. We sought to use a dynamic multimedia environmental fate model to reconcile the emissions and residue levels reported for three representative PAHs in the AOSR. Data describing emissions to air compiled from two official sources result in simulated concentrations in air, soil, water, and foliage that tend to fall close to or below the minimum measured concentrations of phenanthrene, pyrene, and benzo(a)pyrene in the environment. Accounting for evaporative emissions (e.g., from tailings pond disposal) provides a more realistic representation of PAH distribution in the AOSR. Such indirect emissions to air were found to be a greater contributor of PAHs to the AOSR atmosphere relative to reported direct emissions to air. The indirect pathway transporting uncontrolled releases of PAHs to aquatic systems via the atmosphere may be as significant a contributor of PAHs to aquatic systems as other supply pathways. Emission density estimates for the three PAHs that account for tailings pond disposal are much closer to estimated global averages than estimates based on the available emissions datasets, which fall close to the global minima. Our results highlight the need for improved accounting of PAH emissions from oil sands operations, especially in light of continued expansion of these operations.