We report experimentally determined first-order rate constants of MeHg photolysis in three waters along a Boreal lake-wetland gradient covering a range of pH (3.8-6.6), concentrations of total organic carbon (TOC 17.5-81 mg L(-1)), total Fe (0.8-2.1 mg L(-1)), specific UV254 nm absorption (3.3-4.2 L mg(-1) m(-1)) and TOC/TON ratios (24-67 g g(-1)). Rate constants determined as a function of incident sunlight (measured as cumulative photon flux of photosynthetically active radiation, PAR) decreased in the order dystrophic lake > dystrophic lake/wetland > riparian wetland. After correction for light attenuation by dissolved natural organic matter (DOM), wavelength-specific (PAR: 400-700 nm, UVA: 320-400 nm and UVB: 280-320 nm) first-order photodegradation rate constants (kpd) determined at the three sites were indistinguishable, with average values (± SE) of 0.0023 ± 0.0002, 0.10 ± 0.024 and 7.2 ± 1.3 m(2) E(-1) for kpdPAR, kpdUVA, and kpdUVB, respectively. The relative ratio of kpdPAR, kpdUVA, and kpdUVB was 1:43:3100. Experiments conducted at varying MeHg/TOC ratios confirm previous suggestions that complex formation with organic thiol groups enhances the rate of MeHg photodegradation, as compared to when O and N functional groups are involved in the speciation of MeHg. We suggest that if the photon fluxes of PAR, UVA, and UVB radiation are separately determined and the wavelength-specific light attenuation is corrected for, the first-order rate constants kpdPAR, kpdUVA, and kpdUVB will be universal to waters in which DOM (possibly in concert with Fe) controls the formation of ROS, and the chemical speciation of MeHg is controlled by the complexation with DOM associated thiols.

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A number of studies have found high levels of mercury (Hg) in deep-sea organisms throughout the world's oceans, but the underlying causes are not clear as there is no consensus on the origin and cycling of Hg in the ocean. Recent findings suggested that Hg accumulation may increase with increasing forage depth and pointed to the deep-water column as the origin of most Hg in marine biota, especially its organic methylmercury (MeHg) form. In the present study, we determined the total mercury (THg) levels in 12 deep-sea fish species and a decapod crustacean and investigated their relationship with the species' nitrogen stable isotope ratio (δ(15)N) as an indicator of their trophic level, average weight and habitat depth. THg levels ranged from 0.27 to 4.42 μg/g w.w. and exceeded in all, except one species, the recommended 0.5 μg/g w.w. guideline value. While THg levels exhibited a strong relationship with δ(15)N values and to a lesser extent with weight, the habitat depth, characterized as the species' depth of maximum abundance (DMA), had also a significant effect on Hg accumulation. The fish species with a shallower depth range exhibited lower THg values than predicted by their trophic level (δ(15)N) and body mass, while measured THg values were higher than predicted in deeper-dwelling fish. Overall, the present results point out a potential risk for human health from the consumption of deep-sea fish. In particular, for both, the red shrimp Aristeus antennatus, which is one of the most valuable fishing resources of the Mediterranean, as well as the commercially exploited fish Mora moro, THg levels considerably exceeded the recommended 0.5μg/g w.w. limit and should be consumed with caution.

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