Todd Gouin

A Thermodynamic Approach for Assessing the Environmental Exposure of Chemicals Absorbed to Microplastic

The environmental distribution and fate of microplastic in the marine environment represents a potential cause of concern. One aspect is the influence that microplastic may have on enhancing the transport and bioavailability of persistent, bioaccumulative, and toxic substances (PBT). In this study we assess these potential risks using a thermodynamic approach, aiming to prioritize the physicochemical properties of chemicals that are most likely absorbed by microplastic and therefore ingested by biota. Using a multimedia modeling approach, we define a chemical space aimed at improving our understanding of how chemicals partition in the marine environment with varying volume ratios of air/water/organic carbon/polyethylene, where polyethylene represents a main group of microplastic. Results suggest that chemicals with log KOW > 5 have the potential to partition >1% to polyethylene. Food-web model results suggest that reductions in body burden concentrations for nonpolar organic chemicals are likely to occur for chemicals with log KOW between 5.5 and 6.5. Thus the relative importance of microplastic as a vector of PBT substances to biological organisms is likely of limited importance, relative to other exposure pathways. Nevertheless, a number of data-gaps are identified, largely associated with improving our understanding of the physical fate of microplastic in the environment.

Modelling the environmental fate of the polybrominated diphenyl ethers

In response to growing alarm over the occurrence of polybrominated diphenyl ethers (PBDEs) in remote regions, this study considers their physical chemistry, environmental partitioning and considerations regarding potential for long-range atmospheric transport (LRAT). Internally consistent physical-chemical property data are presented for five representative congeners (PBDE-15, -28, -47, -99, -153) and used in a multimedia modelling approach. Results of the Level II model indicate that PBDEs will largely partition to organic carbon in soil and sediment and that their persistence will be strongly influenced by degradation rates in these media that are not well known. TaPL3 model estimates of their characteristic travel distance (CTD) suggest limited LRAT potential. The LRAT is also evaluated qualitatively, in terms of surface-air exchange behaviour. PBDEs are shown to be sensitive to seasonally and diurnally fluctuating temperatures. When vegetation is included in the model, 50% of the total mass of PBDE-47 deposited to vegetation returns to the atmosphere, suggesting that it may migrate through a series of deposition/volatilisation hops. Key data that needs to be identified in this evaluation include a better understanding of air-surface exchange, particularly to foliage, and measurements of degradation rates in soil, sediment and vegetation.

Comparison of Four Active and Passive Sampling Techniques for Pesticides in Air

Four sampling systems were evaluated for their ability to determine the concentrations of pesticides in the atmosphere of rural southern Ontario. Two active air samplers (AAS, high-volume and low-volume pumps) and two passive air samplers (PAS, polyurethane foam disks and XAD-resin) were deployed between March 2006 and September 2007 using different sampling frequencies (biweekly to annually) and durations (24 h to 1 yr). Concentrations of nine pesticides in air determined by the different systems were compared at time scales of two weeks, two months, and one year. Agreement in the average concentrations obtained by different techniques improved with increasing length of the comparison period, especially for pesticides with high short-term temporal concentration variability. Such variability was high for the most volatile and reactive pesticides (trifluralin and pendimethalin). Except for these two pesticides, the annually averaged air concentrations determined by the different systems are within a factor of 2.5 for all pesticides and are not statistically different. Even though the PUF-PAS may have approached equilibrium with the atmosphere during deployment, the air concentrations are not statistically significantly different from those determined by AAS when averaged over longer time scales. Two month XAD-PAS deployments during the second summer resulted in sufficient sampling volumes to reliably establish air concentrations. If the sole purpose of collecting air samples is the assessment of long-term air concentration trends, this can be achieved most cost-effectively, i.e., with the least number of samples with year-long XAD-PAS.

Influence of global climate change on chemical fate and bioaccumulation: The role of multimedia models

Multimedia environmental fate models are valuable tools for investigating potential changes associated with global climate change, particularly because thermodynamic forcing on partitioning behavior as well as diffusive and nondiffusive exchange processes are implicitly considered. Similarly, food-web bioaccumulation models are capable of integrating the net effect of changes associated with factors such as temperature, growth rates, feeding preferences, and partitioning behavior on bioaccumulation potential. For the climate change scenarios considered in the present study, such tools indicate that alterations to exposure concentrations are typically within a factor of 2 of the baseline output. Based on an appreciation for the uncertainty in model parameters and baseline output, the authors recommend caution when interpreting or speculating on the relative importance of global climate change with respect to how changes caused by it will influence chemical fate and bioavailability. Environ. Toxicol. Chem. 2013;32:20–31.

The influence of global climate change on the scientific foundations and applications of Environmental Toxicology and Chemistry: Introduction to a SETAC international workshop

This is the first of seven papers resulting from a Society of Environmental Toxicology and Chemistry (SETAC) international workshop titled “The Influence of Global Climate Change on the Scientific Foundations and Applications of Environmental Toxicology and Chemistry.” The workshop involved 36 scientists from 11 countries and was designed to answer the following question: How will global climate change influence the environmental impacts of chemicals and other stressors and the way we assess and manage them in the environment? While more detail is found in the complete series of articles, some key consensus points are as follows: (1) human actions (including mitigation of and adaptation to impacts of global climate change [GCC]) may have as much influence on the fate and distribution of chemical contaminants as does GCC, and modeled predictions should be interpreted cautiously; (2) climate change can affect the toxicity of chemicals, but chemicals can also affect how organisms acclimate to climate change; (3) effects of GCC may be slow, variable, and difficult to detect, though some populations and communities of high vulnerability may exhibit responses sooner and more dramatically than others; (4) future approaches to human and ecological risk assessments will need to incorporate multiple stressors and cumulative risks considering the wide spectrum of potential impacts stemming from GCC; and (5) baseline/reference conditions for estimating resource injury and restoration/rehabilitation will continually shift due to GCC and represent significant challenges to practitioners. Environ. Toxicol. Chem. 2013;32:13–19.

Levels and Seasonal Variability of Pesticides in the Rural Atmosphere of Southern Ontario

Air samples were collected continuously in Egbert, Ontario, which is in a rural agricultural area north of Toronto, between March 2006 and September 2007 and analyzed for pesticides of both current and historic use. The fungicide chlorothalonil was present in highest abundance with levels exceeding 2000 pg x m(-3) in the summer. Almost as abundant, with summer time concentrations around 400 to 600 pg x m(-3), were the herbicides atrazine, alachlor, and metolachlor. Other pesticides in current use, such as trifluralin, pendimethalin, chlorpyrifos, endosulfan, and disulfoton were consistently present at levels approximately 1 order of magnitude lower. Concentrations of banned pesticides (chlordanes and hexachlorocyclohexane) were generally below 10 pg x m(-3), except for hexachlorobenzene, which was present at the global average of approximately 50 pg x m(-3). These levels and the fact that they are generally lower than what has been reported for the area previously are in agreement with pesticide usage data for Ontario. Only the concentrations of chlorothalonil, chlorpyrifos, and HCB were correlated with air mass origin, as determined by back trajectory analysis. All pesticides had higher levels during the growing season compared to those in winter, but the ratio of concentrations during the different seasons is much higher for the pesticides in current use. That ratio may aid in distinguishing seasonal variability caused by pesticide application during the growing season from that caused by temperature-driven revolatilization. Higher concentrations of the banned pesticides during 2007 compared to those in 2006 may be due to higher volatilization rates caused by higher surface temperatures consistent with the El Nino Southern Oscillation.

Using Benchmarking To Strengthen the Assessment of Persistence

Chemical persistence is a key property for assessing chemical risk and chemical hazard. Current methods for evaluating persistence are based on laboratory tests. The relationship between the laboratory based estimates and persistence in the environment is often unclear, in which case the current methods for evaluating persistence can be questioned. Chemical benchmarking opens new possibilities to measure persistence in the field. In this paper we explore how the benchmarking approach can be applied in both the laboratory and the field to deepen our understanding of chemical persistence in the environment and create a firmer scientific basis for laboratory to field extrapolation of persistence test results.

A chemical activity approach to exposure and risk assessment of chemicals

To support the goals articulated in the vision for exposure and risk assessment in the twenty-first century, we highlight the application of a thermodynamic chemical activity approach for the exposure and risk assessment of chemicals in the environment. The present article describes the chemical activity approach, its strengths and limitations, and provides examples of how this concept may be applied to the management of single chemicals and chemical mixtures. The examples demonstrate that the chemical activity approach provides a useful framework for 1) compiling and evaluating exposure and toxicity information obtained from many different sources, 2) expressing the toxicity of single and multiple chemicals, 3) conducting hazard and risk assessments of single and multiple chemicals, 4) identifying environmental exposure pathways, and 5) reducing error and characterizing uncertainty in risk assessment. The article further illustrates that the chemical activity approach can support an adaptive management strategy for environmental stewardship of chemicals where “safe” chemical activities are established based on toxicological studies and presented as guidelines for environmental quality in various environmental media that can be monitored by passive sampling and other techniques.

Policy by analogy: precautionary principle, science and polybrominated diphenyl ethers

Through the acquisition of scientific data, knowledge is gained about the environmental fate and human exposure of chemical substances. From this knowledge, the risk of using chemicals can be assessed. As a means of facilitating the regulatory process, risk assessments can also compare the substance under investigation to other substances that display similar behaviour or structure, especially when the risk assessment involves a substance for which few data exist. For instance, similarities can be drawn between a number of poorly studied chemical substances and those that are currently listed as chemicals of concern. We suggest that policy can be guided, in part, by analogy. By taking advantage of knowledge obtained for the PCBs in the past, we can better implement precautionary measures with respect to similar substances, such as the PBDEs, and do so more quickly and appropriately.