With the phase-out of legacy halogenated flame retardants (HFRs), such as decabromodiphenyl ether (BDE-209), emerging ones, such as decabromodiphenyl ethane (DBDPE), are being widely produced. We conducted field campaigns to assess the trophic transfer of legacy and emerging HFRs in estuarine and coastal food webs of Laizhou Bay, which are located near the largest HFR manufacturing base in China. Seawater, sediment, plankton, invertebrates, and fish were collected from both sites. BDE-209 was the predominant compound in the estuary, whereas DBDPE was the main contributor to HFRs in the bay, followed by BDE-209. Invertebrates, especially bivalves and sea cucumbers, showed higher levels of BDE-209 and DBDPE than fish. The HFR levels in the organisms of the two coastal zones were comparable to each other, although their concentrations in the estuarine water were one order of magnitude higher than those in the bay. The HFR profiles in benthic organisms were similar to those in the sediments, indicating that the bioaccumulation of HFRs in coastal food webs depended on the habitat. The ΣHFR concentrations followed the order filter-feeding > carnivorous for invertebrates, and demersal non-migratory fish showed higher HFR levels than oceanodromous fish. The trophic magnification factors estimated for BDE-209, dechlorane plus, and DBDPE were lower than 1, suggesting biodilution potential in both food webs, whereas several PBDE congeners exhibited biomagnification capacity. Feeding habits, habitats, hydrophobicity, bioavailability, and metabolism may be the main factors impacting the bioaccumulation of HFRs in organisms in estuarine–coastal ecosystems of northern China.

Research on per- and polyfluoroalkyl substances (PFAS) in freshwater ecosystems has focused primarily on legacy compounds and little is still known on the presence of emerging PFAS. Here, we investigated the occurrence of 60 anionic, zwitterionic, and cationic PFAS in a food web of the St. Lawrence River (Quebec, Canada) near a major metropolitan area. Water, sediments, aquatic vegetation, invertebrates, and 14 fish species were targeted for analysis. Levels of perfluorobutanoic acid (PFBA) in river water exceeded those of perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS), and a zwitterionic betaine was observed for the first time in the St. Lawrence River. The highest mean PFAS concentrations were observed for the benthopelagic top predator Smallmouth bass (Micropterus dolomieu, Σ₆₀PFAS ∼ 92 ± 34 ng/g wet weight whole-body) and the lowest for aquatic plants (0.52–2.3 ng/g). Up to 33 PFAS were detected in biotic samples, with frequent occurrences of emerging PFAS such as perfluorobutane sulfonamide (FBSA) and perfluoroethyl cyclohexane sulfonate (PFECHS), while targeted ether-PFAS all remained undetected. PFOS and long-chain perfluorocarboxylates (C10–C13 PFCAs) dominated the contamination profiles in biota except for insects where PFBA was predominant. Gammarids, molluscs, and insects also had frequent detections of PFOA and fluorotelomer sulfonates, an important distinction with fish and presumably due to different metabolism. Based on bioaccumulation factors >5000 and trophic magnification factors >1, long-chain (C10–C13) PFCAs, PFOS, perfluorodecane sulfonate, and perfluorooctane sulfonamide qualified as very bioaccumulative and biomagnifying. Newly monitored PFAS such as FBSA and PFECHS were biomagnified but moderately bioaccumulative, while PFOA was biodiluted.

Freshwater ecosystems are negatively impacted by various pollutants, from agricultural, urban and industrial wastewater, with metals being one of the largest concerns. Moreover, freshwater ecosystems are often affected by alien species introductions that can modify habitats and trophic relationships. Accordingly, the threat posed by metals interacts with those by alien species, since the latter can accumulate and transfer these substances across the food web to higher trophic levels. How metals transfer within such communities is little studied. We analysed the concentration of 14 metals/metalloids (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Se, Zn, hereafter ‘metal(s)’) of eight fish and three crustacean species co-existing in the Arno River (Central Italy), most of which were alien. To assess the pathway of contaminants within the community, we coupled metal analysis with carbon and nitrogen stable isotope analysis derived from the same specimens. Crustaceans showed higher metal concentration than fish, except for Cd, Hg and Se that were higher in fish. We found evidence of trophic transfer for six metals (Cd, Cr, Hg, Mg, Se, Zn). Additionally, ontogenetic differences and differences among various fish tissues (muscle, liver, and gills) were found in metals concentration. Considerable biomagnification along the trophic chain was found for Hg, while other metals were found to biodilute. Using stable isotopes and Hg as a third diet tracer, we refined the estimations of consumed preys in the diet previously reconstructed with stable isotope mixing models. Alien species reach high biomass and can both survive to and accumulate high pollutants concentrations, potentially posing a risk for their predators and humans. A combined effect of environmental filtering and increased competition may potentially contribute to the disappearance of native species with lower tolerances.

Mercury (Hg), a potent neurotoxic element, can biomagnify through food webs once converted into methylmercury (MeHg). Some studies have found that selenium (Se) exposure may reduce MeHg bioaccumulation and toxicity, though this pattern is not universal. Se itself can also be toxic at elevated levels. We experimentally manipulated the relative concentrations of dietary MeHg and Se (as selenomethionine [SeMet]) for an aquatic grazer (the mayfly, Neocloeon triangulifer) and its food source (diatoms). Under low MeHg treatment (0.2 ng/L), diatoms exhibited a quadratic pattern, with decreasing diatom MeHg concentration up to 2.0 μg Se/L and increasing MeHg accumulation at higher SeMet concentrations. Under high MeHg treatment (2 ng/L), SeMet concentrations had no effect on diatom MeHg concentrations. Mayfly MeHg concentrations and biomagnification factors (concentration of MeHg in mayflies: concentration of MeHg in diatoms) declined with SeMet addition only in the high MeHg treatment. Mayfly MeHg biomagnification factors decreased from 5.3 to 3.3 in the high MeHg treatment, while the biomagnification factor was constant with an average of 4.9 in the low MeHg treatment. The benefit of reduced MeHg biomagnification was offset by non-lethal effects and high mortality associated with ‘protective’ levels of SeMet exposure. Mayfly larvae escape behavior (i.e., startle response) was greatly reduced at early exposure days. Larvae took nearly twice as long to metamorphose to adults at high Se concentrations. The minimum number of days to mayfly emergence did not differ by SeMet exposure, with an average of 13 days. We measured an LC50SₑMₑₜ for mayflies of 3.9 μg Se/L, with complete mortality at concentrations ≥6.0 μg Se/L. High reproductive mortality occurred at elevated SeMet exposures, with only 0–18% emergence at ≥4.12 μg Se/L. Collectively, our results suggest that while there is some evidence that Se can reduce MeHg accumulation at the base of the food web at specific exposure levels of SeMet and MeHg, Se is also toxic to mayflies and could lead to negative effects that extend across ecosystem boundaries.

Mercury (Hg) is a neurotoxic element with severe effects on humans and wildlife. Widely distributed by atmospheric deposition, it can also be localized near point sources such as mines. Mercury has been shown to reduce the reproduction of bird populations in field observations in North America and Europe, but studies are needed in Asia, where the majority of emissions now occur. We investigated the reproduction of two passerines, Japanese Tit (Parus minor) and Russet Sparrow (Passer rutilans), in a large-scale Hg mining district, and a non-mining district, both in Guizhou, southwest China. Concentrations of Hg were elevated in the mining district (blood levels of 2.54 ± 2.21 [SD] and 0.71 ± 0.40 μg/g, in adult tits and sparrows, respectively). However, we saw no evidence of decreased breeding there: metrics such as egg volume, nestling weight, hatching and fledgling success, were all similar between the different districts across two breeding seasons. Nor were there correlations at the mining district between Hg levels of adults or juveniles, and hatching or fledgling success, or nestling weight. Nest success was high even in the mining district (tit, 64.0%; sparrow: 83.1%). This lack of reproductive decline may be related to lower blood levels in nestlings (means < 0.15 μg/g for both species). Concentrations of selenium (Se), and Se-to-Hg molar ratio, were also not correlated to breeding success. Although blood levels of 3.0 μg/g have been considered as a threshold of adverse effects in birds, even leading to severe effects, we detected no population-level reproductive effects, despite ~25% of the adult tits being above this level. Future work should investigate different locations in the mining district, different life-stages of the birds, and a wider variety of species. The hypothesis that bird populations can evolve resistance to Hg in contaminated areas should also be examined further.

Marine animals often accumulate various harmful substances through the foods they ingest. The bioaccumulation levels of these harmful substances are affected by the degrees of pollution in the food and of biomagnification; however, which of these sources is more important is not well-investigated for mercury (Hg) bioaccumulation. Here we addressed this issue in fishes that inhabit the waters around Minamata Bay, located off the west coast of Kyushu Island in Kumamoto Prefecture, Japan. The total Hg concentration (hereafter [THg]) and carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) were analyzed in the muscle tissue of 10 fish species, of which more than five individuals were caught by gillnet. Except one species, each was separated into two trophic groups with respective lower and higher δ¹³C values ranging from −17‰ to −16‰ and −15‰ to −14‰, which suggested that the fishes depended more on either phytoplankton- and microphytobenthos-derived foods (i.e., pelagic and benthic trophic pathways), respectively. Linear mixed effects models showed that the Hg levels were significantly associated with both δ¹⁵N and the differences in the trophic groups. [THg] increased with δ¹⁵N (i.e., indicative of higher trophic levels), but the slopes did not differ between the two trophic groups. [THg] was significantly higher in the group with higher δ¹³C values than in those with lower δ¹³C values. The effect size from marginal R squared (R²) values showed that the variation in [THg] was strongly ascribed to the trophic group difference rather than δ¹⁵N. These results suggest that the substantial Hg bioaccumulation in the fishes of Minamata Bay is mainly an effect of ingesting the microphytobenthos-derived foods that contain Hg, and that the subsequent biomagnification is secondary.

Methylmercury (MeHg) is a globally pervasive contaminant with known toxicity to humans and wildlife. Several sources of variation can lead to spatial differences in MeHg bioaccumulation within a species including: biogeochemical processes that influence MeHg production and availability within an organism’s home range; trophic positions of consumers and MeHg biomagnification efficiency in food webs; and individual prey preferences that influence diet composition. To better understand spatial variation in MeHg bioaccumulation within a species, we evaluated the effects of habitat biogeochemistry, food web structure, and diet composition in the wetland-obligate California black rail (Laterallus jamaicensis coturniculus) at three wetlands along the Petaluma River in northern San Francisco Bay, California, USA. The concentration of MeHg in sediments differed significantly among wetlands. We identified three sediment and porewater measurements that contributed significantly to a discriminant function explaining differences in habitat biogeochemistry among wetlands: the porewater concentration of ferrous iron, the percent organic matter, and the sediment MeHg concentration. Food web structure and biomagnification efficiency were similar among wetlands, with trophic magnification factors for MeHg ranging from 1.84 to 2.59. In addition, regurgitation samples indicated that black rails were dietary generalists with similar diets among wetlands (percent similarity indices > 70%). Given the similarities in diet composition, food web structure, and MeHg biomagnification efficiency among wetlands, we concluded that variation in habitat biogeochemistry and associated sediment MeHg production was the primary driver of differences in MeHg concentrations among black rails from different wetlands.

Biomagnification of some persistent organic pollutants (POPs) has been found in marine and freshwater food chains; however, due to the relatively short food chains in high-altitude alpine lakes, whether trophic transfer would result in the biomagnification of POPs is not clear. The transfer of various POPs, including organochlorine pesticides and polychlorinated biphenyls (PCBs), along the aquatic food chain in Nam Co Lake (4700 m), in the central Tibetan Plateau, was studied. The POPs levels in the water, sediment and biota [plankton, invertebrates and fish (Gymnocypris namensis)] of Nam Co were generally low, with concentrations comparable to those reported for the remote Arctic. The composition profiles of POPs in the fish were different from that in the water, but similar to their food. DDEs, DDDs, PCB 138, 153 and 180 displayed significant positive correlations with trophic levels, with trophic magnification factors (TMFs) ranged between 1.5 and 4.2, implying these chemicals can undergo final biomagnification along food chain. A fugacity-based dynamic bioaccumulation model was applied to the fish with localized parameters, by which the simulated concentrations were comparable to the measured data. Modeling results showed that most compounds underwent net gill loss and net gut uptake; only when the net result of the combined gut and gill fluxes would be positive, bioaccumulation could eventually occur. The net accumulation flux increased with fish age, which was caused by the continuous increase of gut uptake by aged fish. Due to the oligotrophic condition, efficient food absorption is likely the key factor that influences the gut POPs uptake. Long residence times with half-lives up to two decades were found for the higher chlorinated PCBs in Gymnocypris namensis.

Bioaccumulation and trophic transfer in ecosystems is an important criterion for assessing environmental risks of contaminants. This study investigated bioaccumulation and biomagnification of 13 organic ultraviolet absorbents (UVAs) in marine wildlife organisms in the Pearl River Estuary, South China Sea. The UVAs could accumulate in the organisms with biota - sediment accumulation factors (BSAF) of 0.003–2.152. UV531 was the most abundant and showed the highest tendency to accumulate in the organisms with a median BSAF of 1.105. The UVAs demonstrated species - and compound-specific accumulation in the marine organism. Fishes showed significantly higher capability than the cephalopods and crustaceans in accumulation of the UVAs. Habitat did not demonstrate obvious impact on accumulation of the UVA. On the other hand, benzophenone-3, UV328, and UV234 showed significantly higher concentration in the detritus feeding fishes than carnivorous and planktivorous fishes, suggesting governing effect of dietary habits of the organisms on bioaccumulation of these UVAs. Direct uptake from growth media was a significant exposure pathway of the organisms to the UVAs. The estimated trophic magnification factors and biomagnification factors revealed that UV329, UV531, and octocrylene could potentially biomagnify in the marine food web.