Biodilution of Organic Species of Arsenic in Freshwater Food Webs.

Arsenic can accumulate in freshwater biota, sometimes reaching potentially harmful levels. However, the toxicity of arsenic strongly depends on which arsenic species are present. Although organic species are considered less harmful than inorganic ones, they have not been extensively studied in freshwater environments, and drivers of variation in arsenic speciation among sites and taxa remain unclear. We assessed concentrations of two organic arsenic species, arsenobetaine (AsB) and dimethylarsinic acid (DMA), in fish and invertebrates from three lakes near Sudbury, Ontario, Canada-a region with widespread mining impacts. Both AsB and DMA were detected in most samples (n = 212), varying across a wide range of concentrations (<0.001-30.144 and <0.006-5.262 mg/kg dry wt, respectively). The lake with the most severe mining impacts typically had the highest concentrations (designated by square brackets []) of AsB and DMA. In contrast, the percentage of total arsenic made up by AsB (%AsB) and DMA (%DMA) did not vary significantly between lakes. Arsenic speciation in fish muscle varied with fish size, selenium concentrations, and trophic elevation (inferred from nitrogen stable isotope ratios δ15N), but relationships with dietary carbon source (inferred from carbon stable isotope ratios δ13C) were more varied. Within all three lake food webs, [AsB] and [DMA] typically underwent biodilution, decreasing with trophic elevation (i.e., δ15N). Although the aforementioned factors explained some variation in arsenic speciation, there remains considerable unexplained variation. Further studies on arsenic speciation in freshwater biota should target a wider diversity of taxa to better understand drivers of variation in arsenic speciation. In addition, research emphasizing the percentage of inorganic arsenic and other organic arsenic species is needed to improve environmental and human health risk assessments. Environ Toxicol Chem 2024;43:833-846. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

The speciation of arsenic in the muscle tissue of inland and coastal freshwater fish from a remote boreal region.

Elevated concentrations of total arsenic (As) have been reported in boreal freshwater fish in both human-impacted and relatively pristine areas. We assessed the arsenic speciation profiles in muscle tissue of six fish species (n = 300) sampled from nine locations across a remote freshwater watershed in northern Ontario, Canada, extending from inland headwater lakes to the coastal marine confluence. Of the five arsenic species measured, only arsenobetaine (AsB) and dimethylarsinic acid (DMA) were detected in these fish. Riverine fish had up to 10-fold higher total [As] when compared to lacustrine fish. On average, these riverine fish also had higher percentages of AsB (%AsB, 60 ± 26%) and lower percentages of unmeasured arsenic (%UNM, 20 ± 21%), compared to lacustrine fish (28 ± 18% and 52 ± 21% %AsB and %UNM, respectively). DMA percentages (%DMA) were relatively consistent across the watershed, averaging 20 ± 21% across all fish. We examined ecological drivers of As speciation and found that %AsB increased slightly with fish weight in large-body predatory fish, but not in forage fish or insectivores. Furthermore, %AsB was positively related to trophic elevation (inferred from δ15N) in lacustrine fish across 3 out of 4 communities and within some populations. Lastly, riverine fish with a more marine-based diet had markedly higher %AsB when compared to fish with more freshwater-based diets, indicating an effect of anadromy on arsenic speciation. Overall, knowledge on arsenic speciation in freshwater fish has been limited and these results indicate potential drivers that can be considered in future studies. Furthermore, the absence of toxic inorganic As species in these boreal fish is an important consideration for future environmental monitoring practices and risk assessments, some of which assume 10-20% of total [As] in fish is present as toxic inorganic As. Additional studies on As bioaccumulation and biotransformation are needed in freshwater systems, particularly at the base of aquatic food webs.

Age, body size, growth and dietary habits: What are the key factors driving individual variability in mercury of lacustrine fishes in northern temperate lakes?

Fish total mercury concentration ([THg]) has been linked to various fish attributes, but the relative importance of these attributes in accounting for among-individual variation in [THg] has not been thoroughly assessed. We compared the contributions of ontogeny (age, length), growth (growth rate, body condition), and food web position (δ13C, δ15N) to among-individual variability in [THg] within populations of seven common fishes from 141 north temperate lakes. Ontogenetic factors accounted for most variation in [THg]; age was a stronger and less variable predictor than length for most species. Adding both indices of growth and food web position to these models increased explained variation (R2) in [THg] by 6-25% among species. Fish [THg] at age increased with growth rate, while fish [THg] at length decreased with growth rate, and the effect of body condition was consistently negative. Trophic elevation (inferred from δ15N) was a stronger predictor than primary production source (inferred from δ13C) for piscivores but not benthivores. Fish [THg] increased with δ15N in all species but showed a more variable relationship with δ13C. Among-individual variation in [THg] is primarily related to age or size in most temperate freshwater fishes, and effects of growth rate and food web position need to be considered in the context of these ontogenetic drivers.

Climate and landscape conditions indirectly affect fish mercury levels by altering lake water chemistry and fish size.

Mercury pollution is a global environmental problem that threatens ecosystems, and negatively impacts human health and well-being. Mercury accumulation in fish within freshwater lakes is a complex process that appears to be driven by factors such as individual fish biology and water chemistry at the lake-scale, whereas, climate, and land-use/land-cover conditions within lake catchments can be influential at relatively larger scales. Nevertheless, unravelling the intricate network of pathways that govern how lake-scale and large-scale factors interact to affect mercury levels in fish remains an important scientific challenge. Using structural equation models (SEMs) and multiple long-term databases we identified direct and indirect effects of lake-scale and larger-scale factors on mercury levels in Walleye and Northern Pike - two species that are valued in inland fisheries. At the lake-level, the most parsimonious path models contained direct effects of fish weight, DOC, and pH, as well as an indirect effect of DOC on fish mercury levels via fish weight. Interestingly, lakeshed-, climate-, and full-path models that combine the effects of both lakeshed and climate revealed indirect effects of surrounding landscape conditions and latitude via DOC, pH, and fish weight but no direct effects on fish mercury levels. These results are generally consistent across species and lakes, except for some differences between stratified and non-stratified lakes. Our findings imply that understanding climate and land-use driven alterations of water chemistry and fish biology will be critical to predicting and mitigating fish mercury bioaccumulation in the future.

Arsenic, chromium, and other elements of concern in fish from remote boreal lakes and rivers: Drivers of variation and implications for subsistence consumption.

Eating fish provides numerous health benefits, but it is also a dominant pathway for human exposure to contaminants. Many studies have examined mercury (Hg) accumulation in fish, but fewer have considered other elements, such as arsenic (As) and chromium (Cr). Recently, freshwater fish from several pristine boreal systems across northern Ontario, Canada, have been reported with elevated concentrations of As and Cr for reasons that are not well understood. Our goal was to investigate the ecological and environmental influences over concentrations of As, Cr, and other elements in these fish to better understand what affects metal uptake and the risk to consumers. We measured 10 elements (including As, Cr, Hg) as well as carbon (δ13C), nitrogen (δ15N), and sulfur (δ34S) stable isotopes in 388 fish from 25 lake and river sites across this remote region. These data were used to determine the effect of: 1) trophic ecology; and 2) watershed geology on piscine elemental content. Overall, most element concentrations were low, often below provincial advisory benchmarks (ABs). However, traces of Hg, As, Cr, and selenium (Se) were detected in most fish. Based on their exceedance of their respective ABs, the most restrictive elements on fish consumption in these boreal systems were Hg > As > Cr. Arsenic and Se, but not Cr concentrations were related to fish size and trophic ecology (inferred from δ13C and δ15N), suggesting bioaccumulation of the former elements. Fish with enriched δ34S values, suggestive of anadromous behaviour, had marginally lower Hg but higher Se concentrations. Modeling results suggested a strong effect of site-specific factors, though we found weak trends between piscine elemental content and geological features (e.g., mafic intrusions), potentially due to the broad spatial scale of this study. Results from this study address gaps in our understanding of As and Cr bioaccumulation and will help to inform fish consumption guidelines.

The trophic niche of sculpins Cottus spp. in forage fish assemblages of boreal lakes.

We compared the trophic niches of freshwater sculpins Cottus spp. with those of other co-habiting forage fishes in two groups of boreal lakes with distinct habitats and fish communities. Near North Lakes (45° 00' to 47° 30' N) were deeper, stratified and contained lake trout Salvelinus namaycush as the apex piscivore, whereas Far North Lakes (51° 10' to 52° 20' N) were shallower, did not stratify and contained pike Esox lucius and walleye Sander vitreus as the apex piscivores. Trophic niches of sculpins and other forage fishes were compared based on niche metrics calculated from muscle stable carbon (δ13 C) and nitrogen (δ15 N) isotope ratios. In Near North Lakes, sculpins were found almost exclusively in deep, offshore waters and their niche positions reflected a greater reliance on pelagic production (lower δ13 C) and a higher trophic elevation (higher δ15 N) compared with most other forage fishes. Furthermore, sculpins in Near North Lakes tended to have larger trophic niches (occupied greater area in δ13 C- δ15 N space), particularly in the food chain (δ15 N) dimension, than other cohabiting forage fishes. In contrast, sculpins in Far North Lakes were commonly found in the nearshore and had trophic niche positions and sizes that were similar to those of the other cohabiting forage fishes. This study illustrates the flexibility in the realised trophic niches of sculpins in relation to habitat availability and fish community composition in boreal lakes.

Percentage of methylmercury in the muscle tissue of freshwater fish varies with body size and age and among species.

It is commonly assumed that most (>95%) of the mercury (Hg) found in fish muscle is the toxic form, methylmercury (MeHg), due to its efficient assimilation and retention in biotic tissue. However, this assumption is largely based on studies examining the percentage of MeHg (%MeHg [the fraction of total Hg as MeHg]) in muscle from mostly large-bodied predatory fish; less is known about the %MeHg in smaller bodied individuals or those of different trophic guilds. The present study analyzed MeHg and total Hg concentrations in the muscle of 2 large-bodied piscivores (walleye and northern pike), one large-bodied benthivore (white sucker), and 2 small-bodied forage fish (sculpins and shiners) across a broad size range. We found substantially lower %MeHg than the commonly assumed 95% in several fish (e.g., 17 individuals had <70% MeHg). Muscle %MeHg significantly increased with size and age in all species except walleye, which had significantly higher %MeHg than pike or suckers, particularly in smaller and younger fish (e.g., 18-21% higher at 10 g; 5-11% higher at 500 g). Results of predictive modeling suggest that muscle %MeHg is higher in pelagic-feeding fish and those with lower lipid content, although model results varied significantly among species. According to our findings, total Hg measurement in muscle is not an appropriate proxy for MeHg in smaller fish from all species, an important consideration for future piscine Hg studies and monitoring. Environ Toxicol Chem 2018;37:2682-2691. © 2018 SETAC.

Characterization and in vivo efficacy of a heptapeptide ODT formulation for the treatment of neurogenic bladder dysfunction.

The objective of this study was to develop oral disintegrating tablet (ODT) formulations of a heptapeptide, [Lys5,MeLeu9,Nle10]-NKA(4-10), for the treatment of neurogenic bladder dysfunction. A design of experiment approach was applied to determine the optimal ratio of chosen excipients: gelatin (X1), glycine (X2), and sorbitol (X3). These formulations were optimized for efficacy studies to produce ODTs exhibiting rapid disintegration times (Y1) and appropriate structural integrity (Y2) using JMP® 12.0.1 software. Based on theoretically predicted values from 12 experimental runs, the optimal ODT formulation was determined to be 3% (w/v) gelatin, 2% (w/v) glycine, and 1% (w/v) sorbitol in deionized water. Using this formulation, blank and drug-loaded ODTs containing 1.5 mg or 5 mg of [Lys5,MeLeu9,Nle10]-NKA(4-10) were manufactured by a lyophilization process. The peptide-loaded tablets disintegrated in less than 30 s and released 97% of the peptide within 15 min. The peptide was stable for 90 days under 25 °C/60% relative humidity (RH) and 40 °C/75% RH. In vivo efficacy of the peptide-loaded ODTs was confirmed in a rat acute spinal cord injury model under isovolumetric bladder pressure recording conditions, concluding that sublingual administration of peptide-containing ODTs evoke a rapid dose-related neurokinin 2-mediated increase in bladder pressure.

Bioavailability of polyphenols from peanut skin extract associated with plasma lipid lowering function.

Peanut skin is a rich source of polyphenols including procyanidins and is shown to have hypolipidemic properties. This study investigated the bioavailability of peanut skin polyphenols using a rat model. First, the bioavailability of peanut skin polyphenols in rat plasma was evaluated. Our results showed procyanidin A2 levels in plasma peaked within 30 min of ingestion. The results of a second study show that peanut skin extract supplemented in addition to oil gavage resulted in significant decrease in plasma triglyceride and VLDL within 5h. In the third study, rats were given a Western type diet for 5 weeks with peanut skin extract at a dose of 150 and 300 mg/kg body weight. The main effects observed were lowering of total blood lipid and reduction of the plasma fatty acids profile. Our results suggest that procyanidin A may impart a key role of hypolipidemic effect seen in peanut skin polyphenols.

Temporal changes in mercury concentrations of large-bodied fishes in the boreal shield ecoregion of northern Ontario, Canada.

Much of the mercury (Hg) in freshwater fish of the boreal shield ecoregion is believed to originate from atmospheric deposition. As such, declines in fish Hg concentrations would be expected in response to recent declines in atmospheric Hg deposition in this ecoregion. We compared recent (2005-2010) and historic (1974-1981) muscle total mercury concentrations ([THg], standardized to a fish body mass of 1 kg) in seven fish species (five piscivores, two benthivores) from 73 lakes in northern Ontario (Canada) using a paired-comparisons approach. The rate of bioaccumulation (i.e., slopes of log(e)[THg] vs log(e) total length relationship) increased for walleye (Sander vitreus) but did not change significantly for any other species. There was no significant decline in mean [THg] between recent and historic time periods for any species. In fact, recent mean [THg] were slightly higher (<0.08 ppm) than historic mean [THg] for all species, and this difference was significant for northern pike (Esox lucius). The magnitude of the temporal change in northern pike declined significantly from south to north over the study area but there were no discernible geographic patterns in the temporal change in [THg] for any other species. This study shows that [THg] of most large-bodied fish species in boreal shield lakes are not declining in response to the decline in atmospheric Hg deposition.

Maternal influences on population dynamics: evidence from an exploited freshwater fish.

We used a field experiment, population modeling, and an analysis of 30 years of data from walleye (Sander vitreus; a freshwater fish) in Lake Erie to show that maternal influences on offspring survival can affect population dynamics. We first demonstrate experimentally that the survival of juvenile walleye increases with egg size (and, to a lesser degree, female energy reserves). Because egg size in this species tends to increase with maternal age, we then model these maternal influences on offspring survival as a function of maternal age to show that adult age structure can affect the maximum rate at which a population can produce new adults. Consistent with this hypothesis, we present empirical evidence that the maximum reproductive rate of an exploited population of walleye was approximately twice as high when older females were abundant as compared to when they were relatively scarce. Taken together, these results indicate that age- or size-based maternal influences on offspring survival can be an important mechanism driving population dynamics and that exploited populations could benefit from management strategies that protect, rather than target, reproductively valuable individuals.

Mercury bioaccumulation in forage fish communities invaded by rainbow smelt (Osmerus mordax).

We compared total mercury concentrations ([Hg]) among 6 forage fish species in 25 central Canadian lakes and related [Hg] to adjusted-delta15N (an index of trophic position), delta13C, growth rate, and a suite of environmental variables. Growth rates were also compared among species and related to environmental variables. We found that rainbow smelt (Osmerus mordax), a recent invader in many of these lakes, had intermediate [Hg] and growth rates relative to other species. Forage fish growth rates differed significantly among species and were related to latitude (inverse relationship) and lake conductivity (positive relationship). Mercury concentrations also differed significantly among species and the strongest predictors were growth rate and lake conductivity; [Hg] was significantly and negatively related to both. Adjusted-delta15N explained very little variation in [Hg] and was significant only when the analysis was restricted to biotic variables. These results indicate that biomagnification may not be observed at fine scales of trophic differentiation and that rainbow smelt are unlikely to cause post-invasion [Hg] increases in most predatory fish species.

Effects of maternally transferred organochlorine contaminants on early life survival in a freshwater fish.

Laboratory research has shown that female fish can pass toxic organochlorines (OCs) from their bodies to their eggs, killing their offspring if sufficient quantities are transferred. We conducted a controlled incubation study using gametes from a wild, OC-contaminated walleye (Sander vitreus) population (Bay of Quinte, Lake Ontario, Canada) in order to assess among-female variation in offspring early life survival in relation to ova concentrations of planar OCs (polychlorinated dibenzo-p-dioxins and furans and planar polychlorinated biphenyls) and a suite of other maternal and ova characteristics. Equal volumes of ova from each female were fertilized, pooled, and incubated together as an experimental cohort. Relative survival of each female's offspring was estimated as the proportion of surviving larvae (at approximately 5 d posthatch) that she contributed to the cohort as determined by microsatellite DNA parentage assignment. Total planar OC concentration (expressed as toxic equivalency of 2,3,7,8-tetrachlorodibenzo-p-dioxin) of ova was positively related to maternal age and size and to ova lipid content. However, early life survival did not decline with increasing ova planar OC concentrations. Similarly, we observed no significant relationships between early life survival and ova thiamine content, ova fatty acid composition, or maternal age or size. Early life survival was more strongly correlated with date of spawn collection, thyroid hormone status of the ova, and ovum size. Maternally transferred planar OCs do not appear to negatively influence female reproductive success in this walleye population.

Temporal changes in mercury bioaccumulation by predatory fishes of boreal lakes following the invasion of an exotic forage fish.

We evaluated the prediction that mercury concentrations of predatory fishes in boreal lakes would rise following the invasion of an exotic forage fish species (rainbow smelt, Osmerus mordax) that was believed to feed at a higher trophic position than native forage fishes. We compared temporal trends (postinvasion minus preinvasion values) in fish mercury bioaccumulation between lakes experiencing recent smelt invasions and reference lakes of central Canada. Piscivore mercury concentrations in this region have remained stable or declined during approximately the last 20 years. These trends were not strongly influenced by the smelt invasion, despite the fact that smelt were a major prey item for all piscivore species examined. The effect of smelt invasion on mercury bioaccumulation in the predator species reflected the importance of smelt in their respective diets (lake trout, Salvelinus namaycush > walleye, Stizostedion vitreum > northern pike, Esox lucius). However, these effects were not statistically significant for any piscivore species. The impact of rainbow smelt invasion on mercury bioaccumulation in native piscivores of this region has been much less than previous food-web studies have predicted.

Variation in organochlorine bioaccumulation by a predatory fish; gender, geography, and data analysis methods.

SigmaPCB and p,p'-DDE levels within and among walleye (Stizostedion vitreum) populations were examined to determine how the method of data analysis could influence the interpretation of (i) gender differences and (ii) geographic variation. In the lower Great Lakes (Huron, Erie, and Ontario) whole-body burdens of both contaminants tended to increase with body mass at a faster rate in males than in females. Thus, males generally had higher burdens than females at large body sizes but not at small body sizes. This result was not strongly influenced by the method of expressing contaminant level (burden, wet mass concentration, or lipid mass concentration) but was influenced by the choice of covariate (body mass, body length, or age) in some cases. Mean sigmaPCB and p,p'-DDE concentrations of walleye muscle declined along a gradient from the lower Great Lakes to the Northwest Territories. Analyses using means adjusted for age yielded a stronger contrast between Great Lakes and non-Great Lakes populations than analyses using means adjusted for body length. The gender composition of fish samples and the type and level of covariate used in statistical analyses should be considered in studies of spatiotemporal variation in organochlorine bioaccumulation in fish.