Gordon Paterson

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5mgL(-1) in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water>Plastic Lake water>dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.

Bioamplification as a Bioaccumulation Mechanism for Persistent Organic Pollutants (POPs) in Wildlife

Persistent organic pollutant bioaccumulation models have generally been formulated to predict bioconcentration and biomagnification. A third bioaccumulation process that can mediate chemical fugacity in an organism is bioamplification.Bioamplification occurs when an organism loses body weight and the chemical partitioning capacity occurs at a rate that is faster than the chemical can be eliminated.Although bioamplification has not been widely recognized as a bioaccumulation process, the potential consequences of this process are significant. Bioamplification causes an increase in chemical fugacity in the animals tissues and results in there distribution of contaminants from inert storage sites to more toxicologically sensitive tissues. By reviewing laboratory and field studies, we have shown in this paper that bioamplification occurs across taxonomic groups that include, invertebrates,amphibians, fishes, birds, and mammals. Two case studies are presented, and constitute multi-life stage non-steady state bioaccumulation models calibrated for yellow perch and herring gulls. These case studies were used to demonstrate that bioamplification is predicted to occur under realistic scenarios of animal growth and seasonal weight loss. Bioamplification greatly enhances POP concentrations and chemical fugacities during critical physiological and behavioral events in an animals life history, e.g., embryo development, juvenile stages, metamorphosis, reproduction, migration, overwintering, hibernation, and disease. Consequently,understanding the dynamics of bioamplification, and how different life history scenario scan alter tissue residues, may be helpful and important in assessing wildlife hazards and risks.

Age‐related polychlorinated biphenyl dynamics in immature bull sharks (Carcharhinus leucas)

Polychlorinated biphenyls (PCBs) were quantified in liver tissues of bull sharks (Carcharhinus leucas) ranging in age from <4 wk to >3 yr. Summed values of PCBs (ΣPCBs) ranged from 310 ng/g to 22 070 ng/g (lipid wt) across age classes with ΣPCB concentrations for the youngest sharks in the present study (<4 wk; 5230 ± 2170 ng/g lipid wt) determined to not significantly differ from those quantified in >3-yr-old sharks, highlighting the extent of exposure of this young life stage to this class of persistent organic pollutants (POPs). Age normalization of PCB congener concentrations to those measured for the youngest sharks demonstrated a significant hydrophobicity (log octanol/water partition coefficient [KOW ]) effect that was indicative of maternal offloading of highly hydrophobic (log KOW ≥6.5) congeners to the youngest individuals. A distinct shift in the PCB congener profiles was also observed as these young sharks grew in size. This shift was consistent with a transition from the maternally offloaded signal to the initiation of exogenous feeding and the contributions of mechanisms including growth dilution and whole-body elimination. These results add to the growing pool of literature documenting substantially high concentrations of POPs in juvenile sharks that are most likely attributable to maternal offloading. Collectively, such results underscore the potential vulnerability of young sharks to POP exposure and pose additional concerns for shark-conservation efforts.

Contrasting PCB bioaccumulation patterns among Lake Huron lake trout reflect basin specific ecology

This study collected multiple age classes of lake trout from Lake Hurons Main Basin, Georgian Bay, and North Channel regions to compare and contrast top predator polychlorinated biphenyl (PCB) bioaccumulation patterns in separate compartments of the same ecosystem. Sum PCB concentrations were highest for Main Basin (260 ± 24.9 ng g(-1) wet wt) fish, followed by Georgian Bay (74.6 ± 16.2 ng g(-1) ) and North Channel (42.0 ± 3.3 ng g(-1)) fish. Discriminant functions analysis of lake trout PCB profiles and stable carbon (δ(13)C) and nitrogen (δ(15)N) isotope values clearly distinguished fish by location, indicating high degrees of basin fidelity throughout their lifetimes in addition to highly contrasting PCB bioaccumulation profiles. These unique profiles were not attributable to significant differences in lake trout lipid contents (p = 0.856) or trophic position (δ(15)N; p = 0.334), with rainbow smelt representing the primary prey across the basins. Furthermore, significant differences were observed among the basins for the relationships between PCB biomagnification factors and hydrophobicity. An empirical model for predicting PCB biomagnification in Lake Huron lake trout indicated that basin-specific population growth rates and prey abundances were significant for explaining these contrasting patterns of PCB bioaccumulation. The results of the present study are fundamental for understanding the role of ecology in legacy persistent organic pollutant (POP) bioaccumulation. Specifically, ecosystem characteristics such as prey abundances, foraging ecology, and ultimately consumer growth can regulate the variability of legacy POP bioaccumulation as observed within and among a wide range of freshwater ecosystems.

Importance of growth rate on mercury and polychlorinated biphenyl bioaccumulation in fish

To evaluate the effect of fish growth on mercury (Hg) and polychlorinated biphenyl (PCB) bioaccumulation, a non-steady-state toxicokinetic model, combined with a Wisconsin bioenergetics model, was developed to simulate Hg and PCB bioaccumulation in bluegill (Lepomis macrochirus). The model was validated by comparing observed with predicted Hg and PCB 180 concentrations across 5 age classes from 5 different waterbodies across North America. The non-steady-state model generated accurate predictions for Hg and PCB bioaccumulation in 3 of 5 waterbodies: Apsey Lake (ON, Canada), Sharbot Lake (ON, Canada), and Stonelick Lake (OH, USA). The poor performance of the model for the Detroit River (MI, USA/ON, Canada) and Lake Hartwell (GA/SC, USA), which are 2 well-known contaminated sites with possibly high heterogeneity in spatial contamination, was attributed to changes in feeding behavior and/or prey contamination. Model simulations indicate that growth dilution is a major component of contaminant bioaccumulation patterns in fish, especially during early life stages, and was predicted to be more important for hydrophobic PCBs than for Hg. Simulations that considered tissue-specific growth provided some improvement in model performance particularly for PCBs in fish populations that exhibited changes in their whole-body lipid content with age. Higher variation in lipid growth compared with that of lean dry protein was also observed between different bluegill populations, which partially explains the greater variation in PCB bioaccumulation slopes compared with Hg across sampling sites. Environ Toxicol Chem 2018;37:1655-1667.

PCB Food web dynamics quantify nutrient and energy flow in aquatic ecosystems

Measuring in situ nutrient and energy flows in spatially and temporally complex aquatic ecosystems represents a major ecological challenge. Food web structure, energy and nutrient budgets are difficult to measure, and it is becoming more important to quantify both energy and nutrient flow to determine how food web processes and structure are being modified by multiple stressors. We propose that polychlorinated biphenyl (PCB) congeners represent an ideal tracer to quantify in situ energy and nutrient flow between trophic levels. Here, we demonstrate how an understanding of PCB congener bioaccumulation dynamics provides multiple direct measurements of energy and nutrient flow in aquatic food webs. To demonstrate this novel approach, we quantified nitrogen (N), phosphorus (P) and caloric turnover rates for Lake Huron lake trout, and reveal how these processes are regulated by both growth rate and fish life history. Although minimal nutrient recycling was observed in young growing fish, slow growing, older lake trout (>5 yr) recycled an average of 482 Tonnes·yr(-1) of N, 45 Tonnes·yr(-1) of P and assimilated 22 TJ yr(-1) of energy. Compared to total P loading rates of 590 Tonnes·yr(-1), the recycling of primarily bioavailable nutrients by fish plays an important role regulating the nutrient states of oligotrophic lakes.