Mercury isotope compositions in seawater and marine fish revealed the sources and processes of mercury in the food web within differing marine compartments.

Anthropogenic activities and climate change have significantly increased mercury (Hg) levels in seawater. However, the processes and sources of Hg in differing marine compartments (e.g. estuary, marine continental shelf (MCS) or pelagic area) have not been well studied, which makes it difficult to understand Hg cycling in marine ecosystems. To address this issue, the total Hg (THg) concentration, methylmercury (MeHg) concentration and stable Hg isotopes were determined in seawater and fish samples collected from differing marine compartments of the South China Sea (SCS). The results showed that the estuarine seawater exhibited substantially higher THg and MeHg concentrations than those in the MCS and pelagic seawater. Significantly negative δ202Hg (-1.63‰ ± 0.42‰) in estuarine seawater compared with that in pelagic seawater (-0.58‰ ± 0.08‰) may suggest watershed input and domestic sewage discharge of Hg in the estuarine compartment. The Δ199Hg value in estuarine fish (0.39‰ ± 0.35‰) was obviously lower than that in MCS (1.10‰ ± 0.54‰) and pelagic fish (1.15‰ ± 0.46‰), which showed that relatively little MeHg photodegradation occurred in the estuarine compartment. The Hg isotope binary mixing model based on Δ200Hg revealed that approximately 74% MeHg in pelagic fish is derived from atmospheric Hg(II) deposition, and over 60% MeHg in MCS fish is derived from sediments. MeHg sources for estuarine fish may be highly complex (e.g. sediment or riverine/atmospheric input) and further investigations are warranted to clarify the contribution of each source. Our study showed that Hg stable isotopes in seawater and marine fish can be used to identify the processes and sources of Hg in different marine compartments. This finding is of great relevance to the development of marine Hg food web models and the management of Hg in fish.