Nearly all ecosystems are contaminated with highly toxic methylmercury (MeHg), but the specific sources and pathways leading to the uptake of MeHg within and among food webs are not well understood. In this study, we report stable mercury (Hg) isotope compositions in food webs in a river and an adjacent forest in northern California and demonstrate the utility of Hg isotopes for studying MeHg sources and cross-habitat transfers. We observed large differences in both δ(202)Hg (mass-dependent fractionation) and Δ(199)Hg (mass-independent fractionation) within both food webs. The majority of isotopic variation within each food web could be accounted for by differing proportions of inorganic Hg [Hg(II)] and MeHg along food chains. We estimated mean isotope values of Hg(II) and MeHg in each habitat and found a large difference in δ(202)Hg between Hg(II) and MeHg (∼2.7‰) in the forest but not in the river (∼0.25‰). This is consistent with in situ Hg(II) methylation in the study river but suggests Hg(II) methylation may not be important in the forest. In fact, the similarity in δ(202)Hg between MeHg in forest food webs and Hg(II) in precipitation suggests that MeHg in forest food webs may be derived from atmospheric sources (e.g., rainfall, fog). Utilizing contrasting δ(202)Hg values between MeHg in river food webs (-1.0‰) and MeHg in forest food webs (+0.7‰), we estimate with a two-source mixing model that ∼55% of MeHg in two riparian spiders is derived from riverine sources while ∼45% of MeHg originates from terrestrial sources. Thus, stable Hg isotopes can provide new information on subtle differences in sources of MeHg and trace MeHg transfers within and among food webs in natural ecosystems.

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In Experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on un-amended food pellets (0.1 µg/g MeHg), or was switched to food pellets with 1.0 µg/g or 4.0 µg/g of added MeHg, for a period of 2 months. The difference in δ202Hg (MDF) and Δ199Hg (MIF) between fish tissues and food pellets with added MeHg were within the analytical uncertainty (δ202Hg; 0.07 ‰, Δ199Hg; 0.06 ‰) indicating no isotope fractionation. In Experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets, and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ202Hg and Δ199Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting re-equilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.

We measured mercury (Hg) isotope ratios in sediments and various estuarine organisms (green crab, blue mussel, killifish, eider) to investigate methylmercury (MMHg) sources and exposure pathways in five Northeast coast (U.S.) estuaries. The mass independent Hg isotopic compositions (MIF; Δ199Hg) of the sediments were linearly correlated with the sediment 1/Hg concentrations (Δ199Hg: r2 = 0.77, p < 0.05), but the mass dependent isotope compositions (MDF; δ202Hg) were not (r2 = 0.26, p = 0.16), reflecting inputs of anthropogenic Hg sources with varying δ202Hg. The estuarine organisms all display positive Δ199Hg values (0.21 to 0.98 ‰) indicating that MMHg is photodegraded to varying degrees (5–12%) prior to entry into the food web. The δ202Hg and Δ199Hg values of most organisms can be explained by a mixture of MMHg and inorganic Hg from sediments. At one contaminated site mussels have anomalously high δ202Hg, indicating exposure to a second pool of MMHg, compared to sediment, crabs and fish. Eiders have similar Δ199Hg as killifish but much higher δ202Hg, suggesting that there is an internal fractionation of δ202Hg in birds. Our study shows that Hg isotopes can be used to identify multiple anthropogenic inorganic Hg and MMHg sources and determine the degree of photodegradation of MMHg in estuarine food webs.

Feeding experiments were performed to investigate mercury (Hg) isotope fractionation during trophic transfer and internal distribution of total Hg (THg) in marine fish on exposure to natural seafood. Young-of-the-year amberjack (Seriola dumerili) were fed with either blackfin tuna (Thunnus atlanticus; 2647 ng/g THg) or brown shrimp (Farfantepenaeus aztecus; 25.1 ng/g THg) for 80 d or 50 d, respectively, and dissected for muscle, liver, kidney, brain, and blood. After 30 d of tuna consumption, Hg isotopes (δ(202) Hg and Δ(199)Hg) of the amberjack organs shifted to the tuna value (δ(202)Hg = 0.55‰, Δ(199)Hg = 1.54‰,), demonstrating the absence of Hg isotope fractionation. When amberjack were fed a shrimp diet, there was an initial mixing of the amberjack organs toward the shrimp value (δ(202)Hg = -0.48‰, Δ(199)Hg = 0.32‰), followed by a cessation of further shifts in Δ(199)Hg and a small shift in δ(202)Hg. The failure of Δ(199)Hg to reach the shrimp value can be attributed to a reduction in Hg bioaccumulation from shrimp resulting from feeding inhibition and the δ(202)Hg shift can be attributed to a small internal fractionation during excretion. Given that the feeding rate and Hg concentration of the diet can influence internal Hg isotope distribution, these parameters must be considered in biosentinel fish studies.

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