Developing Methods for Assessing Trophic Magnification of Perfluoroalkyl Substances within an Urban Terrestrial Avian Food Web.

We investigated the trophic magnification potential of perfluoroalkyl substances (PFAS) in a terrestrial food web by using a chemical activity-based approach, which involved normalizing concentrations of PFAS in biota to their relative biochemical composition in order to provide a thermodynamically accurate basis for comparing concentrations of PFAS in biota. Samples of hawk eggs, songbird tissues, and invertebrates were collected and analyzed for concentrations of 18 perfluoroalkyl acids (PFAAs) and for polar lipid, neutral lipid, total protein, albumin, and water content. Estimated mass fractions of PFCA C8-C11 and PFSA C4-C8 predominantly occurred in albumin within biota samples from the food web with smaller estimated fractions in polar lipids > structural proteins > neutral lipids and insignificant amounts in water. Estimated mass fractions of longer-chained PFAS (i.e., C12-C16) mainly occurred in polar lipids with smaller estimated fractions in albumin > structural proteins > neutral lipids > and water. Chemical activity-based TMFs indicated that PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDA, PFOS, and PFDS biomagnified in the food web; PFOA, PFHxDA, and PFHxS did not appear to biomagnify; and PFBS biodiluted. Chemical activity-based TMFs for PFCA C8-C11 and PFSA C4-C8 were in good agreement with corresponding TMFs derived with concentrations normalized to only total protein in biota, suggesting that concentrations normalized to total protein may be appropriate proxies of chemical activity-based TMFs for PFAS, which predominantly partition to albumin. Similarly, TMFs derived with concentrations normalized to albumin may be suitable proxies of chemical activity-based TMFs for longer-chained PFAS, which predominantly partition to polar lipids.

Fugacity-Based Trophic Magnification Factors Characterize Bioaccumulation of Cyclic Methyl Siloxanes within an Urban Terrestrial Avian Food Web: Importance of Organism Body Temperature and Composition.

Trophic magnification of cyclic volatile methyl siloxanes (cVMS) in a terrestrial food web was investigated by measuring concentrations of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) and two reference chemicals within air and biota samples from an avian food web located in a mixed urban-agricultural landscape. Terrestrial trophic magnification factors derived from lipid normalized concentrations (TMFLs) for D5 and D6 were 0.94 (0.17 SE) and 1.1 (0.23 SE) and not statistically different from 1 (p > 0.05); however, the TMFL of D4 was 0.62 (0.11 SE) and statistically less than 1 (p < 0.001). TMFLs of PCB-153 and p,p'-DDE were 5.6 (2.2 SE) and 6.1 (2.8 SE) and statistically greater than 1 (p < 0.001). TMFLs of cVMS in this terrestrial system were similar to those reported in aquatic systems. However, trophic magnification factors derived on a fugacity basis (TMFFs), which recognize differences in body temperature and lipid composition between organisms, were greater than corresponding TMFLs primarily because a temperature-induced thermodynamic biomagnification of hydrophobic chemicals occurs when endothermic organisms consume poikilothermic organisms. Therefore, we recommend that biomagnification studies of food webs including endothermic and poikilothermic organisms incorporate differences in body temperature and tissue composition to accurately characterize the biomagnification potential of chemicals.

Advancing exposure assessment approaches to improve wildlife risk assessment.

The exposure assessment component of a Wildlife Ecological Risk Assessment aims to estimate the magnitude, frequency, and duration of exposure to a chemical or environmental contaminant, along with characteristics of the exposed population. This can be challenging in wildlife as there is often high uncertainty and error caused by broad-based, interspecific extrapolation and assumptions often because of a lack of data. Both the US Environmental Protection Agency (USEPA) and European Food Safety Authority (EFSA) have broadly directed exposure assessments to include estimates of the quantity (dose or concentration), frequency, and duration of exposure to a contaminant of interest while considering "all relevant factors." This ambiguity in the inclusion or exclusion of specific factors (e.g., individual and species-specific biology, diet, or proportion time in treated or contaminated area) can significantly influence the overall risk characterization. In this review, we identify four discrete categories of complexity that should be considered in an exposure assessment-chemical, environmental, organismal, and ecological. These may require more data, but a degree of inclusion at all stages of the risk assessment is critical to moving beyond screening-level methods that have a high degree of uncertainty and suffer from conservatism and a lack of realism. We demonstrate that there are many existing and emerging scientific tools and cross-cutting solutions for tackling exposure complexity. To foster greater application of these methods in wildlife exposure assessments, we present a new framework for risk assessors to construct an "exposure matrix." Using three case studies, we illustrate how the matrix can better inform, integrate, and more transparently communicate the important elements of complexity and realism in exposure assessments for wildlife. Modernizing wildlife exposure assessments is long overdue and will require improved collaboration, data sharing, application of standardized exposure scenarios, better communication of assumptions and uncertainty, and postregulatory tracking. Integr Environ Assess Manag 2024;20:674-698. © 2023 SETAC.

Methods for assessing the bioaccumulation of hydrocarbons and related substances in terrestrial organisms: A critical review.

This study investigates and reviews methods for the assessment of the terrestrial bioaccumulation potential of hydrocarbons and related organic substances. The study concludes that the unitless biomagnification factor (BMF) and/or the trophic magnification factor (TMF) are appropriate, practical, and thermodynamically meaningful metrics for identifying bioaccumulative substances in terrestrial food chains. The study shows that various methods, including physical-chemical properties like the KOA and KOW , in vitro biotransformation assays, quantitative structure-activity relationships, in vivo pharmacokinetic and dietary bioaccumulation tests, and field-based trophic magnification studies, can inform on whether a substance has the potential to biomagnify in a terrestrial food chain as defined by a unitless BMF exceeding 1. The study further illustrates how these methods can be arranged in a four-tier evaluation scheme for the purpose of screening assessments that aim to minimize effort and costs and expediate bioaccumulation assessment of the vast numbers of organic substances in commerce, identifies knowledge gaps, and provides recommendations for further research to improve bioaccumulation assessment. Integr Environ Assess Manag 2023;19:1433-1456. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).