Dissolved polycyclic aromatic compounds in Canada's Athabasca River in relation to Oil Sands from 2013 through 2019.

The Canada-Alberta Oil Sands Monitoring (OSM) Program began long-term surface water quality monitoring on the lower Athabasca River in 2012. Sampling of low level, bio-accumulative polycyclic aromatic compounds (PACs) targeted a suite of parent and alkylated compounds in the Athabasca River (AR) mainstem using semi-permeable membrane devices (SPMDs). Samples were collected along a gradient from upstream reference near Athabasca, Alberta, through exposure to the Athabasca oil sands deposit (AOSD), various tributary inflows, and mining activities within the OSMA, to downstream recovery near Wood Buffalo National Park (WBNP) and reference on the Slave River. The program adapted over the years, shifting in response to program review and environmental events. The AOSD chemical fingerprint was present in samples collected within the AOSD, through the oil sands mineable area (OSMA), downstream to recovery from 2013 to 2019. PACs were dominated by alkylated phenanthrenes/anthracenes (PAs) and dibenzothiophenes (Ds), with elevated levels of alkylated fluorenes (Fs), naphthalenes (Ns), fluoranthenes/pyrenes (FlPys) and benzo[a]anthracenes/chrysenes (BaACs), increasing in concentration from C1 < C2 < C3 < C4. Concentrations of these petrogenic PACs were at their highest within the OSMA and downstream of tributaries. The AOSD fingerprint was absent from sites located outside of the influence of the AOSD and downstream of the Peace-Athabasca Delta on the Slave River. PAC concentrations in the AR increased with mainstem discharge and loadings from tributaries, were moderated by the PAD, and diluted by the Peace River. This work bolsters the baseline PAC information previously reported for the Athabasca River and waters downstream, reporting 7 years of data, from all sites within the mainstem monitoring program, and exploring potential regional and hydrological drivers of these between sites and over time.

Polycyclic Aromatic Compounds in Rivers Dominated by Petrogenic Sources after a Boreal Megafire.

Polycyclic aromatic compounds (PACs) threaten the health of aquatic ecosystems. In northeastern Alberta, Canada, decades of oil sands mining and upgrading activities have increased PAC delivery into freshwaters. This PAC pollution adds to natural inputs from river erosion of bitumen-bearing McMurray Formation outcrops and wildfire inputs. Quantifying these petrogenic and pyrogenic PAC inputs, which is key for understanding industrial impacts, remains a challenge. To distinguish petrogenic from pyrogenic inputs, we characterized river water PACs before and after the 2016 Fort McMurray wildfire, one of the largest natural disasters in Canadian history. Samples of wildfire ash and outcropping bitumen allow us to distinguish between these important PAC sources. River PAC concentrations ranged over multiple orders of magnitude (10s-10 000s ng/L). Petrogenic PACs dominated most of the postfire period with only short-term episodes of pyrogenic signatures in burned watersheds due to the wash-in of ash from the watershed. Wildfire PAC inputs during these events resulted in exceptional increases in concentrations that met or exceeded high (petrogenic) background concentrations, driven by the natural erosion of outcropping bitumen. Our dataset offers the first quantification of these two important PAC sources in this industrialized region and provides new insight into the impacts of increasing wildfire frequency and severity across the Boreal Forest.

Effects of glyphosate and two herbicide mixtures on microbial communities in prairie wetland ecosystems: a mesocosm approach.

A multitrophic outdoor mesocosm system was used to mimic a wetland ecosystem and to investigate the effects of glyphosate and two herbicide mixtures on wetland microbial communities. The glyphosate concentration used was 1000 times the environmentally relevant concentration (ERC). One herbicide mixture consisted of six auxin-type herbicides (2,4-D, MCPA, clopyralid, dicamba, dichlorprop, mecoprop), each at 1000 times the ERC. The second mixture was comprised of eight herbicides, including the six auxin-type herbicides as well as bromoxynil and glyphosate. For this mixture, a dose-response approach was used to treat mesocosms with the ERCs of each herbicide as the base concentration. Algal biomass and production and bacterial production and numbers for pelagic and attached communities were measured at different times over a 22-d period. The experimental results indicate that the eight-herbicide mixture, even at low concentrations, produced negative effects on microbial communities. Glyphosate on its own suppressed algal biomass and production for the duration of the study in pelagic and biofilm communities. Algal biomass and production, although initially depressed in the auxin-type herbicide treatment, were stimulated from Day 9 until experiment end. Due to their similar modes of action, the effects of this herbicide mixture appear to be a result of concentration addition. Such negative effects, however, were brief, and microbial communities recovered from herbicide exposure. Based on evidence presented in this study, it appears that glyphosate has a higher potential to inhibit primary production and chlorophyll content in pelagic and attached wetland algal communities than the auxin-type herbicide mixture.

Ecological causal assessment of benthic condition in the oil sands region, Athabasca River, Canada.

Contaminant loads to rivers of the Canadian oil sands region are linked to industrial and natural sources. To date, biomonitoring studies have been unable to unequivocally assess potential environmental impacts associated with this development. As part of the Joint Alberta-Canada Oil Sands Monitoring initiative, we aimed to assess cumulative effects of anthropogenic activities and exposure to natural bitumen geology on benthic macroinvertebrate assemblages in the lower Athabasca River. We examined associations among macroinvertebrates and environmental correlates, such as nutrients, ions, metals, polycyclic aromatic compounds, and total suspended solids. The study design included sites within and outside the mineable bitumen deposits, within and outside of the active mining and extraction area, and above and below municipal sewage effluents. We predicted observing a negative association between ecological condition of the river and exposure to natural bitumen and oil sands activity. However, contaminant concentrations in water and sediment were far below known toxicity thresholds, and benthic macroinvertebrate assemblages in sites exposed to oil sands mining activities appeared more affected by nutrient enrichment from the MSE than contaminants from mining or natural bitumen. Although sites within the area of intense oil sands activity showed signs of mild environmental stress, assemblage pattern was more strongly associated with MSE nutrient enrichment than to diffuse contamination from either natural bitumen or oil sands mining. Enrichment likely increases food resources available to consumers, thereby potentially masking toxic responses of consumers to contaminants. Current regulations prohibit the direct release of oil sands contaminants to waterways, with diffuse atmospheric deposition of aerial emissions and fugitive dust the main contaminant pathways to freshwaters. As the storage capacity of tailings ponds is reached, this nutrient-contaminant pattern could change if the river receives the proposed direct release of treated oil sands process water. Focused investigation-of-cause studies are required to better assess the consequences of cumulative interactions and ecological effects of nutrients and contaminant exposure in this system.

Pesticides in surface drinking-water supplies of the northern Great Plains.

BACKGROUND: Human health anomalies have been associated with pesticide exposure for people living in rural landscapes in the northern Great Plains of North America. OBJECTIVE: The objective of this study was to investigate the occurrence of 45 pesticides in drinking water from reservoirs in this area that received water primarily from snowmelt and rainfall runoff from agricultural crop lands. METHODS: Water from 15 reservoirs was sampled frequently during the spring pesticide application period (early May to mid-August) and less frequently for the remainder of the year. Drinking water was sampled in early July. Sample extracts were analyzed for pesticide content using mass spectrometric detection. RESULTS: We detected two insecticides and 27 herbicides in reservoir water. Consistent detection of a subset of 7 herbicides suggested that atmospheric deposition, either directly or in rain, was the principal pathway from fields to the reservoirs. However, the highest concentrations and number of herbicides in drinking water were associated with runoff from a localized 133-mm rainfall over 15 days toward the end of spring herbicide application. Water treatment removed from 14 to 86% of individual herbicides. Drinking water contained 3-15 herbicides (average, 6.4). CONCLUSIONS: We estimated the mean annual calculated concentration of herbicides in drinking water to be 75 ng/L (2,4-dichlorophenoxy)acetic acid, 31 ng/L (2-chloro-4-methylphenoxy)acetic acid, 24 ng/L clopyralid, 11 ng/L dichlorprop, 4 ng/L dicamba, 3 ng/L mecoprop, and 1 ng/L bromoxynil. The maximum total concentration of herbicides in drinking water was 2,423 ng/L. For the seven herbicides with established drinking water guidelines, all concentrations of the individual chemicals were well below their respective guideline. However, guidelines have not been established for the majority of the herbicides found in drinking water or for mixtures of pesticides.

Assessing the responses of creek chub (Semotilus atromaculatus) and pearl dace (Semotilus margarita) to metal mine effluents using in situ artificial streams in Sudbury, Ontario, Canada.

Mining of the world's second-largest nickel deposits in the area of Sudbury, Ontario, Canada, has caused acidification and metal saturation of some catchments. We conducted artificial stream studies in the years 2001 and 2002 to assess the effects of treated metal mine effluents (MMEs) from three different mining operations discharging to Junction Creek, Sudbury, on two fish species, creek chub (Semotilus atromaculatus) and pearl dace (Semotilus margarita). Treatments tested for 35 to 41 d included reference water, Garson MME (30%), Nolin MME (20%), and Copper Cliff MME (45%). In 2001, effects on chub included reduced survival and depressed testosterone levels (fivefold reduction) after exposure to all MMEs. In 2002, chub and dace survival were reduced to less than 60% in the Copper Cliff and Garson treatments. In addition, the total body weights of male and female dace were reduced after exposure to the Garson and Copper Cliff treatments. In 2001 and 2002, responses were most common to the 45% Copper Cliff and 30% Garson effluents, with consistent increases in nickel, rubidium, strontium, iron, lithium, thallium, and selenium observed across treatment waters and body tissues. More work is required to link observed effects to field effects and to identify multitrophic level responses of the ecosystem to the MMEs. The artificial stream studies provided a mechanism to identify changes in the endpoints of relevant fish species exposed to present-day metal mine discharges independent of historical depositions of metals in the Sudbury area.

Reduction of predation risk under the cover of darkness: Avoidance responses of mayfly larvae to a benthic fish.

Mayfly larvae of Paraleptophlebia heteronea (McDunnough) had two antipredator responses to a nocturnal fish predator (Rhinichthys cataractae (Valenciennes)): flight into the drift and retreat into interstitial crevices. Drift rates of Paraleptophlebia abruptly increased by 30 fold when fish were actively foraging in the laboratory streams but, even before fish were removed, drift began returning to control levels because larvae settled to the substrate and moved to areas of low risk beneath stones. This drifting response was used as an immediate escape behavior which likely decreases risk of capture from predators which forage actively at night. Surprisingly, drift most often occurred before contact between predator and prey, and we suggest that in darkness this mayfly may use hydrodynamic pressure waves for predator detection, rather than chemical cues, since fish forage in an upstream direction. Although drifting may represent a cost to mayfly larvae in terms of relocation to a new foraging area with unknown food resources, the immediate mortality risk probably out-weighs the importance of staying within a profitable food patch because larvae can survive starvation for at least 2 d. In addition to drifting, mayflies retreated from upper, exposed substrate surfaces to concealed interstitial crevices immediately after a predator encounter, or subsequent to resettlement on the substrate after predator-induced drift. A latency period was associated with this response and mayflies remained in these concealed locations for at least 3 h after dace foraging ceased. Because this mayfly feeds at night and food levels are significantly lower in field refugia under stones, relative to exposed stone surfaces, predator avoidance activity may limit foraging time and, ultimately, reduce the food intake of this stream mayfly.

Effects of pulp mill effluent on benthic assemblages in mesocosms along the Saint John River, Canada.

We used mesocosms to examine the impact of different concentrations of pulp mill effluent (PME) on structural and functional endpoints of a benthic assemblage in the Saint John River (NB, Canada) during 1999 and 2000. Previous studies on this effluent's effects produced conflicting results, with field surveys suggesting a pattern of mild nutrient enrichment, while laboratory toxicity tests linked effluent exposure to moderate contaminant effects. Experimental treatments included three concentrations of sulfite pulp mill effluent (0, 5, 10% v/v PME). Endpoints for the assessment included algal biomass and taxonomic composition, benthic invertebrate abundance and composition, and insect emergence. Low concentrations of PME increased periphyton biomass and caused changes in community structure within the diatom-dominated community. Pulp mill effluent addition had little effect on several structural endpoints measured for benthic invertebrates, including abundance and taxonomic richness, but significantly changed community composition. For both periphyton and benthic invertebrates, community composition endpoints were more sensitive indicators of PME exposure. Insect emergence was a highly relevant functional endpoint. When benthic and emerged insects were combined, total abundance increased with PME addition. Results from two trophic levels, which provided multiple lines of evidence, indicated that the main impact of these PME concentrations is nutrient enrichment rather than effluent toxicity. Our findings also suggest that benthic invertebrate and periphyton assemblages, algal biomass production, and insect emergence are sensitive response measures. Future studies may confirm this observation. The consideration of both functional and structural endpoints at different trophic levels can greatly improve our understanding the effects of discharges to rivers. Such an understanding could not have been obtained using standard assessment techniques and illustrates the value of mesocosms and the benthic community assemblage approach in environmental assessment.

Occurrence of glyphosate and acidic herbicides in select urban rivers and streams in Canada, 2007.

INTRODUCTION: Public and scientific concern has grown over the last decade in Canada over the cosmetic use of pesticides in urban centers. With this in mind, a national survey was designed to monitor eight commonly used herbicides in urban rivers and streams across Canada. MATERIALS AND METHODS: To coordinate sample collections across the country, samples were collected monthly on one of two predetermined dates from April to September, 2007 from 19 sites within 16 watersheds, including 15 sites downstream of urban lands and two reference sites. Water samples were also collected approximately three times from each watershed during or after precipitation events. All samples were collected using a common sampling protocol and all were analyzed using the same analytical laboratories. RESULTS AND DISCUSSION: The herbicides 2,4-D, mecoprop, dicamba, glyphosate and its major metabolite aminomethylphosphonic acid (AMPA) were most frequently detected. Using either herbicide concentrations upstream/downstream of urban centers or bromoxynil and clopyralid as indictors of agricultural inputs of herbicides to streams, it was clear that environmental concentrations of these herbicides downstream of urban areas were linked to urban use in Canada. Herbicide concentrations in streams draining urban areas were greater during or after significant rainfall events and, with the exception of glyphosate, were significantly greater in the Province of Ontario. Herbicide concentrations were not correlated to the proportion of the watersheds in urban land use. Also, there was no difference in seasonal patterns of herbicide concentrations across urban centers when grouped in five geographic areas. None of the herbicide concentrations measured exceeded existing Canadian Water Quality Guidelines for the protection of aquatic life. CONCLUSIONS: This is the first time a national survey of pesticides in urban rivers has been carried out in a consistent fashion across Canada. Concentrations of 2,4-D, mecoprop, dicamba, glyphosate, and AMPA were linked to urban use and frequently detected in all geographic areas. However, geographic differences in concentration suggested differences in usage or stream connectivity patterns among urban centers. Some jurisdictions in Canada have recently restricted cosmetic use of pesticides and it would be interesting to determine whether such restrictions will lead to reduced pesticide concentrations in urban streams.

Northern Rivers Ecosystem Initiative: nutrients and dissolved oxygen - issues and impacts.

Anthropogenic inputs of nitrogen (N), phosphorus (P) and oxygen-consuming material to aquatic ecosystems can change nutrient dynamics, deplete oxygen, and change abundance and diversity of aquatic plants and animals. The Northern Rivers Ecosystem Initiative required a research and assessment program to establish the contribution of pulp mill and sewage discharges to eutrophication and depressions in dissolved oxygen (DO) in the Athabasca and Wapiti rivers of northern Alberta, Canada and examine the adequacy of existing guidelines for protecting these systems. Analysis of long-term data showed that total N (TN) and total P (TP) concentrations in exposed river reaches exceeded concentrations in reference reaches by < or = 2 times for the Athabasca River, and by 9.6 (TP) and 2.6 (TN) times for the Wapiti River. Results from nutrient limitation experiments conducted in situ and in mesocosms showed that benthic algal production was nutrient sufficient downstream of pulp mill discharges but constrained in upper river reaches by insufficient P (Athabasca River) or N + P (Wapiti River). Dissolved oxygen (DO) concentrations in both rivers declined during winter such that median concentrations in the Athabasca River 945 km downstream of the headwaters were approximately 8 mg L(-1) in mid-February. Although water column DO rarely approached the guideline of 6.5 mg L(-1), DO studies undertaken in the Wapiti River showed that pore water DO often failed to meet this guideline and could not be predicted from water column DO. Results from this integrated program of monitoring and experimentation have improved understanding of the interactions between nutrients, DO and aquatic ecosystem productivity and resulted in recommendations for revisions to nutrient and DO guidelines for these northern rivers.