Biogeochemical Processes and Microbial Dynamics Governing Phosphorus Retention and Release in Sediments: A Case Study in Lower Great Lakes Headwaters.

The ability of headwater bed and suspended sediments to mitigate non-point agricultural phosphorus (P) loads to the lower Great Lakes is recognized, but the specific biogeochemical processes promoting sediment P retention or internal P release remain poorly understood. To elucidate these mechanisms, three headwater segments located within priority watersheds of Southern Ontario, Canada, were sampled through the growing season of 2018-2020. The study employed equilibrium P assays along with novel assessments of legacy watershed nutrients, nitrogen (N) concentrations, sediment redox, and microbial community composition. 20-year data revealed elevated total P (TP) and total Nitrogen (TN) at an inorganic fertilizer and manure fertilizer-impacted site, respectively. Overall, sampled sites acted as P sinks; however, agricultural sediments exhibited significantly lower buffering capacity compared to a reference forested watershed. Collection of fine suspended sediment (<63 µm) through time-integrated sampling showed the suspended load at the inorganic-fertilized site was saturated with P, indicating a greater potential for P release into surface waters compared to bed sediments. Through vertical microsensor profiling and DNA sequencing of the sediment microbial community, site-specific factors associated with a distinct P-source event were identified. These included rapid depletion of dissolved oxygen (DO) across the sediment water interface (SWI), as well as the presence of nitrate-reducing bacterial and ammonia-oxidizing archaeal (AOA) genera. This research provides valuable insights into the dynamics of P in headwaters, shedding light on P retention and release. Understanding these processes is crucial for effective management strategies aimed at mitigating P pollution to the lower Great Lakes.

Evidence for Microbial Community Effect on Sediment Equilibrium Phosphorus Concentration (EPC0).

Batch equilibrium phosphorus concentration (EPC0) methods were applied to determine phosphorus capacity of sediments from three agriculturally influenced tributaries in southern Ontario - Belle River, Big Creek, and Nissouri Creek. Aliquots of sediments were amended with soluble reactive phosphorus and incubated at four temperatures (5, 15, 25, and 35°C). Batches of sediments from each location and temperature were also subjected to a treatment; gamma (γ)-irradiated at 28 kGy over 24-h (sterilized) and compared to non-sterilized biotic samples. Treatment showed a significant effect on EPC0 in Belle River and Nissouri Creek but non-significant effect in Big Creek. Temperature showed a significant effect in Belle River, Nissouri Creek, and the biotic subset of Big Creek. While direction of shift was not consistent in all cases, the biotic subsets of all three locations showed a significant effect of temperature.

Prediction of Mercury Elimination Rate Coefficients of Fish is Improved by Incorporating Fish Temperature Classification into Models.

This study evaluated the dependence of mercury (Hg) elimination by fish on species specific fish metabolic rate in order to generate improved algorithms of Hg elimination rate coefficients. Mercury elimination rate coefficient observations were collected by literature review and fish routine metabolic rate (RMR) estimates calculated using the Wisconsin Fish Bioenergetics Model. Three models were compared that considered body weight, temperature, thermal category, Hg depuration period and RMR as predictors of Hg elimination. The best performing model incorporated body size, temperature and fish thermal category, explaining 79% of the variation of the calibration data and between 20% and 69% of the variation of validation data sets. The results support the conclusion that species-specific differences in metabolic rate influence mercury elimination by fish but also highlight major data gaps in the mercury toxicokinetic literature necessary to develop robust models Hg elimination by fish.

Polybrominated Diphenyl Ethers (PBDEs) in Sediments of the Huron-Erie Corridor.

Polybrominated diphenyl ethers (PBDEs) were measured in 182 sediments from the Huron-Erie Corridor, North America. The median (5-95 percentile) Corridor ∑PBDE concentration was 1.03 ng/g dry wt (0.25-13.48 ng/g dry wt). Dry weight ∑PBDEs were elevated in U.S. waters of the Detroit River (US DR) and lowest in Canadian waters of Lake St. Clair (CA LSC). Sediment total organic carbon (TOC) explained some of the variation in ∑PBDEs, particularly in upstream waterbodies except for the Detroit River where local sources were apparent in the US DR and TOC-dilution occurred in CA DR. Canadian Federal Sediment Quality guidelines were exceeded at 19 stations, 14 occurring in the US DR. ∑Hazard Quotients (∑HQ) had a median (5-95 percentile) Corridor value of 0.46 (ND to 2.27). By strata, 43.2% of US DR stations had ∑HQ's greater than 1 while 21.3% of US SCR stations exceeded a value of 1.

Effect of Microplastic Amendment to Food on Diet Assimilation Efficiencies of PCBs by Fish.

Diet assimilation efficiencies (AEs) of polychlorinated biphenyls (PCBs) absorbed to microplastics and food were determined in goldfish ( Carassius auratus). Microplastics were spiked with 14 environmentally rare PCBs and incorporated into fish pellets previously spiked with a technical PCB mixture (Aroclor 1254). Five diet treatments were created having microplastic contents of 0, 5, 10, 15, 20, and 25% and fed to fish within 24 h of the diet creation. Fish from each treatment were fed a microplastic amended food pellet and PCB AEs were determined by mass balance. Microplastic-associated PCBs had lower AEs (geomean 13.36%) compared to food matrix-associated PCBs (geomean 51.64%). There were interactions between PCB AEs and the microplastic content of the diet. PCBs affiliated with microplastics became more bioavailable with increasing microplastic content of food while food matrix-associated PCB bioavailability declined when microplastic contents exceeded 5%. Despite controlling for microplastic-food contact time, there was some evidence for redistribution of lower KOW food matrix-associated PCBs onto microplastics causing a decrease in their AE relative to nonplastic and low plastic containing diets. The low bioavailability of microplastic-associated PCBs observed in the present study provides further support to indicate that microplastics are unlikely to increase POPs bioaccumulation by fish in aquatic systems.

Polychlorinated Biphenyl Bioaccumulation Patterns Among Lake Erie Lower Trophic Level Consumers Reflect Species Ecologies.

Polychlorinated biphenyl (PCB) concentrations were quantified in lower trophic level consumers of the Lake Erie western basin food web to assess the capacity of PCBs to discriminate among trophically similar species inhabiting different compartments of the same ecosystem. Zooplankton were characterized by higher proportions of less chlorinated and hydrophobic homologs relative to zebra mussel (Dreissena polymorpha), mayfly (Hexagenia limbata) and emerald shiner (Notropis atherinoides) samples. PCB biota-sediment accumulation factors (BSAF) differed significantly among species with zebra mussels and emerald shiners having the highest BSAFs. Principal components analysis of sample PCB profiles reflected the contrasting pelagic and benthic habitats occupied by filter-feeding zooplankton and zebra mussel samples. Benthic mayfly PCB profiles were characterized by increasingly hydrophobic (logK OW ≥ 6.9) congeners with more variable emerald shiner profiles reflecting the greater mobility and extent of spatial habitat integration achieved by this secondary consumer. These results contribute to growing evidence for the use of PCBs as ecological tracers in aquatic ecosystems.

Ships' Ballast Water Treatment by Chlorination Can Generate Toxic Trihalomethanes.

The International Maritime Organization (IMO) will enforce a new abundance-based performance standard for ballast water in September, 2017. Strong oxidants, like chlorine, have been proposed as a method for achieving this standard. However chlorine treatment of ballast water can produce hazardous trihalomethanes. We assessed maximum trihalomethane production from one chlorine dose for three types of ballast water (fresh, brackish and marine) and three levels of total organic carbon (TOC) concentration (natural, filtered, enhanced). While the current standard test considers a 5 day voyage, there is a high possibility of shorter trips and sudden change of plans that will release treated waters in the environment. Water source and TOC significantly affected trihalomethane production, with the highest amounts generated in brackish waters and enhanced TOC concentration. The concentration of brominated trihalomethanes increased from background levels and was highest in brackish water, followed by marine and fresh water.

Bioaccumulation of Polychlorinated Biphenyls (PCBs) in Atlantic Sea Bream (Archosargus rhomboidalis) from Kingston Harbour, Jamaica.

Multiple sizes of Sea bream were collected from Kingston Harbour, Jamaica, to assess steady state bioaccumulation of polychlorinated biphenyls (PCBs) in a tropical fish. Sea beam fork lengths ranged from 7.3 to 21.5 cm (n = 36 fish) and tissue lipids decreased with body length. Larger fish had lower δ13C isotopes compared to smaller fish, suggesting a change in diet. Linear regressions showed no differences in lipid equivalent sum PCB concentrations with size. However, differences in individual congener bioaccumulation trajectories occurred. Less hydrophobic PCBs decreased with increasing body length, intermediate PCBs showed no trend, whereas highly hydrophobic (above log KOW of 6.5) PCBs increased. The different congener patterns were interpreted to be a result of decreases in overall diet PCB concentrations with increased fish length coupled with differences in PCB toxicokinetics as a function of hydrophobicity yielding dilution, pseudo-steady state and non-steady state bioaccumulation patterns.

Ecological Implications of Steady State and Nonsteady State Bioaccumulation Models.

Accurate predictions on the bioaccumulation of persistent organic pollutants (POPs) are critical for hazard and ecosystem health assessments. Aquatic systems are influenced by multiple stressors including climate change and species invasions and it is important to be able to predict variability in POP concentrations in changing environments. Current steady state bioaccumulation models simplify POP bioaccumulation dynamics, assuming that pollutant uptake and elimination processes become balanced over an organism's lifespan. These models do not consider the complexity of dynamic variables such as temperature and growth rates which are known to have the potential to regulate bioaccumulation in aquatic organisms. We contrast a steady state (SS) bioaccumulation model with a dynamic nonsteady state (NSS) model and a no elimination (NE) model. We demonstrate that both the NSS and the NE models are superior at predicting both average concentrations as well as variation in POPs among individuals. This comparison demonstrates that temporal drivers, such as environmental fluctuations in temperature, growth dynamics, and modified food-web structure strongly determine contaminant concentrations and variability in a changing environment. These results support the recommendation of the future development of more dynamic, nonsteady state bioaccumulation models to predict hazard and risk assessments in the Anthropocene.

Short-term fasts increase levels of halogenated flame retardants in tissues of a wild incubating bird.

Many species are adapted for fasting during parts of their life cycle. For species undergoing extreme fasts, lipid stores are mobilized and accumulated contaminants can be released to exert toxicological effects. However, it is unknown if short-term fasting events may have a similar effect. The objective of this study was to determine if short successive fasts are related to contaminant levels in liver and plasma of birds. In ring-billed gulls (Larus delawarensis), both members of the pair alternate between incubating the nest for several hours (during which they fast) and foraging, making them a useful model for examining this question. Birds were equipped with miniature data loggers recording time and GPS position for two days to determine the proportion and duration of time birds spent in these two activities. Liver and plasma samples were collected, and halogenated flame retardants (HFRs) (PBDEs and dechlorane plus) and organochlorines (OCs) (PCBs, DDTs, and chlordane-related compounds) were determined. Most birds (79%) exhibited plasma lipid content below 1%, indicating a likely fasted state, and plasma lipid percent declined with the number of hours spent at the nest site. The more time birds spent at their nest site, the higher were their plasma and liver concentrations of HFRs. However, body condition indices were unrelated to either the amount of time birds fasted at the nest site or contaminant levels, suggesting that lipid mobilization might not have been severe enough to affect overall body condition of birds and to explain the relationship between fasting and HFR concentrations. A similar relationship between fasting and OC levels was not observed, suggesting that different factors are affecting short-term temporal variations in concentrations of these two classes of contaminants. This study demonstrates that short fasts can be related to increased internal contaminant exposure in birds and that this may be a confounding factor in research and monitoring involving tissue concentrations of HFRs in wild birds.

Determination of PCB Elimination Coefficients in Round Goby and Tubenose Goby.

Whole-body elimination coefficients of polychlorinated biphenyls (PCBs) were determined in two Great Lakes invasive fish species, round goby (Neogobius melanostomus) and tubenose goby (Proterorhinus semilunaris). Elimination rates were determined for a set of model PCB congeners (n = 12 congeners) dosed to fish by intraperitoneal injection and allowed to depurate at a temperature of 21.4°C for 90 days. Eight PCBs (PCB 6, 21, 57, 62, 68, 89, 112 and 125) exhibited significant elimination by round goby and had corresponding half lives ranging from 13 to 39.8 days. For tubenose goby, four congeners (PCBs 21, 57, 62 and 68) exhibited significant elimination with half lives in the range from 18.8 to 48.8 days. Whole-body elimination rate coefficients were significantly higher for round gobies compared to tubenose goby. In both cases, PCB elimination rate coefficients were negatively related to chemical log KOW.

Quantitative Biomonitoring in the Detroit River Using Elliptio complanata: Verification of Steady State Correction Factors and Temporal Trends of PCBs in Water Between 1998 and 2015.

Quantitative biomonitoring methods were applied to determine PCB concentrations in water from the Detroit River over a 17 year period. During 2014, mussels were deployed for and extended duration (21-364 days) and time dependent PCB concentrations were fit to a bioaccumulation model to estimate elimination coefficients (ktot) and provide site specific calibration of mussel toxicokinetics. The site specific calibration and different ktot versus KOW relationships from the literature were used to correct for steady state. ∑PCB concentrations in water were not significantly dependent on the ktot values used indicating that individual variation exceeds error contributed by steady state correction factors. The model was then applied to estimate ∑PCB concentrations in water using the long term (1998-2015) data. ∑PCBs concentrations in water exhibited a significant decreasing trend with a half life of 9.12 years resulting in a drop in yearly geometric mean residues from 198.1 to 43.6 pg/L.

Comparison of the Toxicokinetics and Bioaccumulation Potential of Mercury and Polychlorinated Biphenyls in Goldfish (Carassius auratus).

Both mercury (Hg) and polychlorinated biphenyls (PCBs) demonstrate food web biomagnification in aquatic ecosystems, yet their toxicokinetics have not been simultaneously contrasted within a common fish species. This study quantifies uptake and elimination rates of Hg and PCBs in goldfish. Fish were exposed to contaminated food containing PCBs and Hg to determine dietary chemical assimilation efficiencies (AEs) and elimination coefficients (ktot). To test first-order kinetics, three exposure regimes were established by varying the proportion of contaminated fish incorporated into the food. Dietary AEs were 98 ± 10, 75 ± 12, and 40 ± 9% for MeHg, THg, and PCBs, respectively. The ktot values were 0.010 ± 0.003 and 0.010 ± 0.002 day(-1) for THg and MeHg, respectively. No significant differences were found in ktot among the dosing levels for either THg or MeHg, confirming that Hg elimination is a first-order process. For PCB, ktot ranged from 0.007 to 0.022 day(-1) and decreased with an increase in hydrophobicity. This study revealed that Hg had an AE higher than that of PCBs, while the ktot of Hg was similar to those measured for the most hydrophobic PCBs. We conclude that Hg has a bioaccumulation potential in goldfish 118% higher than the highest PCB BMF observed for congeners with a log KOW of >7.

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.

Evaluation and interconversion of various indicator PCB schemes for ∑PCB and dioxin-like PCB toxic equivalent levels in fish.

Polychlorinated biphenyls (PCBs) remain chemicals of concern more than three decades after the ban on their production. Technical mixture-based total PCB measurements are unreliable due to weathering and degradation, while detailed full congener specific measurements can be time-consuming and costly for large studies. Measurements using a subset of indicator PCBs (iPCBs) have been considered appropriate; however, inclusion of different PCB congeners in various iPCB schemes makes it challenging to readily compare data. Here, using an extensive data set, we examine the performance of existing iPCB3 (PCB 138, 153, and 180), iPCB6 (iPCB3 plus 28, 52, and 101) and iPCB7 (iPCB6 plus 118) schemes, and new iPCB schemes in estimating total of PCB congeners (∑PCB) and dioxin-like PCB toxic equivalent (dlPCB-TEQ) concentrations in sport fish fillets and the whole body of juvenile fish. The coefficients of determination (R(2)) for regressions conducted using logarithmically transformed data suggest that inclusion of an increased number of PCBs in an iPCB improves relationship with ∑PCB but not dlPCB-TEQs. Overall, novel iPCB3 (PCB 95, 118, and 153), iPCB4 (iPCB3 plus 138) and iPCB5 (iPCB4 plus 110) presented in this study and existing iPCB6 and iPCB7 are the most optimal indicators, while the current iPCB3 should be avoided. Measurement of ∑PCB based on a more detailed analysis (50+ congeners) is also overall a good approach for assessing PCB contamination and to track PCB origin in fish. Relationships among the existing and new iPCB schemes have been presented to facilitate their interconversion. The iPCB6 equiv levels for the 6.5 and 10 pg/g benchmarks of dlPCB-TEQ05 are about 50 and 120 ng/g ww, respectively, which are lower than the corresponding iPCB6 limits of 125 and 300 ng/g ww set by the European Union.

The changing face of BECT: a citation analysis covering 1966-2009.

A citation analysis was completed on articles published in Bulletin of Environmental Contamination and Toxicology over the period of 1966-2009. Articles were grouped into 5 year intervals and the top 50 most-cited papers in each year interval were categorized according to research theme. Over the journal's history, articles in the toxicity research theme dominated top-cited articles published by the journal followed by articles in the environmental concentration theme and the mechanistic theme. The geographic area of submission of top-cited articles has shown large changes with time, initially being dominated by papers from North American and now dominated by papers from Asia. An examination of the citation history for the highest cited paper in each year interval indicated that the average time to achieve 90 % of total citations is 25 years.

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 animal's 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 animal's 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.

Use of a vial equilibration technique to measure the change in fugacity capacity of avian food and feces samples for 1,2,3,4-tetrachlorobenzene.

A vial equilibration technique was used to estimate the fugacity capacities of food and feces samples for 1,2,3,4-tetrachlorobenzene (TCB). The method was calibrated using different volumes of n-octanol and by comparing the measured and predicted fugacity capacity (Zoct) of n-octanol for TCB. The vial equilibration technique showed linearity with increasing amounts of n-octanol added to the vial. However, the measured Zoct was on average 8.5 times lower than the literature estimate and interpreted to be influenced by co-solvent effects. The ratio of fugacity capacities of food/feces was 2.9 and was consistent with the ratio estimated using Zt calculation methods (4.3) which considers partitioning capacity of both lipids and non-lipid organic matter. These results provide experimental support to the use of lipid equivalent approaches as opposed to lipid normalization when estimating the partition capacity of biological samples containing low lipid contents.

Increasing mercury bioaccumulation and biomagnification rates of Nile perch (Lates niloticus L.) in Winam Gulf, Lake Victoria, Kenya.

The Nile perch (Lates niloticus L.) commercial fishery for Lake Victoria in East Africa is an important source of revenue and employment. We focused on shifts in food web structure and total mercury (THg) bioaccumulation and biomagnification in Nile perch, and lower food web items collected from Winam Gulf (Kenya) sampled 24 years apart (1998 and 2022). Stable isotope carbon (δ13C) values were higher in all species from 2022 compared to 1998. Stable nitrogen isotope (δ15N) values in baseline organisms were lower in 2022 compared to 1998. In Nile perch, δ15N values were correlated with total length, but the δ15N-length regressions were steeper in 1998 compared to 2022 except for one large (158 cm) Nile perch from 1998 with an uncharacteristically low δ15N value. Total Hg concentrations were lower in lower trophic species from 2022 compared to 1998. However, the THg bioaccumulation rate (as a function of fish length) in Nile perch was greater in 2022 compared to 1998 resulting in 24.2 % to 42.4 % higher wet weight dorsal THg concentrations in 2022 Nile perch for market slot size (50 to 85 cm) fish. The contrasting observations of increased THg bioaccumulation with size in 2022 against decreases in the rate of trophic increase with size and lower THg concentrations of lower food web items imply reduced fish growth and potential bioenergetic stressors on Winam Gulf Nile perch. All samples except 1 large Nile perch (139 cm total length collected in 2022) had THg concentrations below the European Union trade limit (500 ng/g wet weight). However, for more vulnerable individuals (women, children and frequent fish eaters), we recommend a decrease in maximum monthly meal consumption for 55-75 cm Nile perch from 16 meals per month calculated for 1998 to a limit of 8 meals per month calculated for 2022.

Investigation of hydrophobic organic carbon (HOC) partitioning to 1 kDa fractionated municipal wastewater colloids.

Natural organic matter from the aquatic environment passing a 1 kDa filter has been hypothesized to not contribute appreciably to hydrophobic organic compound (HOC) partitioning; however, to our knowledge this limit has not been verified experimentally for any sorbate/sorbent system. Presently, colloidal organic carbon (COC) < 1 kDa approached 70% of the total COC (<1.5 µm) mass in primary effluent (PE) from a municipal wastewater treatment plant. Partitioning of HOCs 1,2,4,5-tetrachlorobenzene, pentachlorobenzene, and hexachlorobenzene to COC for both 1.5 µm and 1 kDa filtrates of PE was investigated using the gas-stripping technique. Contrary to the hypothesis, significant HOC-COC partitioning to the 1 kDa filtrate was observed with organic carbon-normalized partitioning coefficients (logKCOC) of 4.30, 4.36, and 3.74 for 1,2,4,5-TeCB, PeCB, and HCB, respectively. Further, partitioning to COC < 1 kDa dominated the overall partitioning of the three chlorobenzenes in the 1.5 µm filtrate, and the partitioning behavior did not follow the trend based on hydrophobicity (KOW). The results show that significant partitioning of HOC may occur to OC < 1 kDa and highlights the need for further experiments with other HOCs and COC characterization to better understand and explain the observed partitioning.