Melissa Gledhill

Pesticide Multiresidues in Waters of the Lower Fraser Valley, British Columbia, Canada. Part I. Surface Water

In Part I of this work we presented pesticide levels in the surface waters of the Lower Fraser Valley (LFV) region of British Columbia, Canada. In Part II pesticide levels in the groundwater of the LFV are presented. During the period 2003 to 2005 a study was conducted to determine the occurrence and spatial distribution of 78 pesticides in the groundwater of the LFV. Samples were collected and analyzed from one reference, nine agricultural, one urban, and three urban-agriculture mixed sites. Overall 24 different pesticides were detected in the sites monitored. The maximum single pesticide concentration observed was for simazine (90 ng L(-1)) at one of the agricultural sites. All concentrations of pesticides detected in groundwater samples were below Canadian surface water quality criteria and below available drinking water quality criteria set by World Health Organization (WHO), Health Canada, USEPA, and the European Union (EU). Pesticide levels in surface and groundwater were compared in the Abbotsford area. Generally, a pesticide with a high groundwater concentration tended to also have a high surface water concentration (Simazine 29 ng L(-1) in groundwater and 58 ng L(-1) in surface water, atrazine 5.5 ng L(-1) in groundwater and 14 ng L(-1) in surface water). For pesticides that were detected above 1 ng L(-1) concentration the only exception to this was desethylatrazine that showed greater concentration in groundwater (2.2 ng L(-1)) than surface water (1.5 ng L(-1)). Herbicides were the predominant pesticides detected in the agricultural sites and insecticides were predominant in the urban sites. Pesticide data presented in this study provide reference levels for future pesticide monitoring programs in the region.

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

IntroductionPublic 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 methodsTo 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 discussionThe 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.ConclusionsThis 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.

Perfluoroalkyl acids in the Canadian environment: multi-media assessment of current status and trends.

In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions.

Evidence for behavioral preference toward environmental concentrations of urban‐use herbicides in a model adult fish

Fish live in waters of contaminant flux. In three urban, fish-bearing waterways of British Columbia, Canada, we found the active ingredients of WeedEx, KillEx, and Roundup herbicide formulations (2,4-D, dicamba, glyphosate, and mecoprop) at low to high ng/L concentrations (0.26 to 309 ng/L) in routine conditions, i.e., no rain for at least one week. Following rain, these concentrations increased by an average of eightfold, suggesting runoff as a major route of herbicide introduction in these waterways. To determine whether fish might be able to limit point-source exposures through sensory-driven behaviors, we introduced pulses of representative herbicide mixtures to individual adult zebrafish (a model species) in flow-through tanks. Fish did the opposite of limit exposure; they chose to spend more time in pulses of herbicide mixtures representative of those that may occur with rain events. This attraction response was not altered by a previous 4-d exposure to lower concentrations of the mixtures, suggesting fish will not learn from previous exposures. However, previous exposures did alter an attraction response to an amino acid prevalent in food (L-alanine). The present study demonstrates that fish living within urban waterways may elect to place themselves in herbicide-contaminated environments and that these exposures may alter their behavioral responses to cues necessary for survival.

Spatial trends of polybrominated diphenyl ethers in Canadian fish and implications for long-term monitoring

A nationwide study was conducted to examine concentrations of polybrominated diphenyl ethers (PBDEs) in top predatory fish, with a focus on lake trout (Salvelinus namaycush), across Canada, and to explore possible influences of food web processes. Concentrations of the three most abundant PBDE homolog groups (tetra-, penta-, and hexa-PBDEs) were, for the most part, higher in Great Lakes and Lake Champlain fish compared with fish from other systems. The Canadian Federal Environmental Quality Guideline for the penta-homolog was exceeded in 70% of the fish examined. However, virtually no guideline exceedances were found for other congeners. In general, PBDE-47 (a representative lower brominated congener) was significantly and positively correlated with fish length, weight, age, lipid content, and stable isotopes of nitrogen and carbon. Significant differences in the slopes of the PBDE-47/covariate relationships between sites prevented concentrations from being adjusted using an analysis of covariance (ANCOVA). However, plots showed that elevated concentrations of PBDE-47 in Great Lakes and Lake Champlain fish remained after accounting for the influence of covariates. In contrast, for PBDE-183 (a representative higher brominated congener), the relationships between fish concentrations and covariates were not consistent, which could be a result of biotransformation being more important in controlling its bioaccumulation. The data from the current study show an overall disconnect between fish PBDE concentrations and likely loadings, which may be caused by differences in food web processes between systems. Continued long-term fish contaminant monitoring is needed to evaluate potential risk to fish and their consumers. However, we also recommend sediment sampling and focused food web studies to provide information on PBDE inputs to the systems and mechanisms of biomagnification, respectively.

1 - Organic Contaminants and Fish

Fish have been exposed to naturally occurring xenobiotics in their environments through evolutionary history and have adapted to disturbances in chemical homeostasis through various mechanisms. This chapter focuses on a new threat: anthropogenic contamination that includes historic persistent organic pollutants (organochorine pesticides and dioxins), current contaminants (hydrocarbons and organometallics), and emerging threats (endocrine disruptors, pharmaceuticals, and personal care products). The toxic effects that result from chemical exposure are directly related to concentrations of the compound at susceptible receptor sites. These final target site concentrations are determined by a complex interplay between chemical uptake, distribution throughout the body, biotransformation, and elimination. The current knowledge for each of these processes in fish is described and characterized. In an applied approach, models for chemical partitioning between the environment and fish are described for chemical uptake, bioaccummulation, and food-web transfer of contaminants.

Environmental concentrations of agricultural-use pesticide mixtures evoke primary and secondary stress responses in rainbow trout.

The present study sought to determine whether environmentally realistic mixtures of agriculturally important pesticides are stressful to fish. Juvenile rainbow trout were exposed for 96 h to concentrations of a pesticide mixture found in a waterway that is the focus of salmon restoration efforts (Nicomekl River, BC, Canada). This mixture contained organochlorine, organophosphorus, phenylurea, and triazine classes of pesticides. Fish given a realistic mixture exposure (total concentration, 1.01 µg/L) had increased plasma cortisol concentration, packed red cell volume, hematocrit (Hct), as well as decreased white cell volume, leukocrit (Lct). Similar changes in Hct and Lct were apparent after exposure to a lower concentration (0.186 µg/L). Interestingly, no changes in plasma cortisol concentration, Hct, or Lct were noted after exposure to a higher concentration (13.9 µg/L). This suggests that the exposure likely impaired the mechanisms enabling the stress response. Across all exposures, plasma glucose concentration was related to plasma cortisol concentration, not to pesticide mixture concentration. This suggests that a secondary stress response may be more related to variability in individual primary stress response than to differences in pesticide exposure concentrations. In summary, the present study indicates that salmon living in agrichemical-contaminated waterways may be experiencing stress, and this may pose a threat to their survival.

Isomer-Specific Hexabromocyclododecane (HBCDD) Levels in Top Predator Fish from Across Canada and 36-Year Temporal Trends in Lake Ontario

Hexabromocyclododecane (HBCDD) is a high concern environmental pollutant due to its persistent, bioaccumulative, and toxic properties. The spatial distribution of HBCDD was investigated in top predator fish (lake trout, walleye, or brook trout) collected in 2013 ( n = 165) from 19 sampling sites and in 2015 ( n = 145) from 20 sites across Canada. HBCDD was measurable in at least one sample at each sampling site regardless of sampling year with the exception of walleye from the south basin of Lake Winnipeg (2013). Sampling sites in or near the Laurentian Great Lakes had greater ΣHBCDD concentrations compared to locations to the west or east. The greatest mean ΣHBCDD concentration was 72.6 ng/g lw in fish from Lake Huron-Goderich (2015). Regardless of the sampling sites, α-HBCDD was the dominant congener followed by γ-HBCDD, whereas β-HBCDD was barely detectable. In fish from the same waterbody there were comparable α/γ isomer concentration ratios. The greatest ratio was 20.8 in fish from Lake Ontario, whereas the lowest ratio was 6.3 for fish from Lac Memphrémagog (Québec) likely related to more recent emissions of a technical HBCDD mixture. Temporal trends of HBCDD in lake trout from Lake Ontario showed a significant decreasing trend for γ-HBCDD with a half-life estimate of 10 years over a 36-year period (1979-2015), and for α-HBCDD with a half-life of 11 years over the years of 2008 to 2015. The proportion of α-HBCDD to ΣHBCDD increased significantly during 1979 to 2015. The present study provided novel information on the isomer-specific HBCDDs in Canada freshwater fish.