New Insights on Ecosystem Mercury Cycling Revealed by Stable Isotopes of Mercury in Water Flowing from a Headwater Peatland Catchment

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a relatively large variation in mass-dependent fractionation (δ²⁰²Hg; from −2.12 to −1.32‰) and a smaller, but significant, variation of mass-independent fractionation (Δ¹⁹⁹Hg; from −0.35 to −0.12‰) during two years of sampling with streamflow varying from 0.003 to 7.8 L s^–1. Large variations in δ²⁰²Hg occurred only during low streamflow (<0.6 L s^–1), which suggest that under high streamflow conditions a peatland lagg zone between the bog (3.0 ha) and uplands (6.7 ha) becomes the dominant source of Hg in downstream waters. Further, a binary mixing model showed that except for the spring snowmelt period, Hg in streamwater from the catchment was mainly derived from dry deposition of gaseous elemental Hg (73–95%). This study demonstrates the usefulness of Hg isotopes for tracing sources of Hg deposition, which can lead to a better understanding of the biogeochemical cycling and hydrological transport of Hg in headwater catchments

Tracking the Fate of Mercury in the Fish and Bottom Sediments of Minamata Bay, Japan, Using Stable Mercury Isotopes

Between 1932 and 1968, industrial wastewater containing methylmercury (MeHg) and other mercury (Hg) compounds was discharged directly into Minamata Bay, Japan, seriously contaminating the fishery. Thousands of people who consumed tainted fish and shellfish developed a neurological disorder now known as Minamata disease. Concentrations of total mercury (THg) in recent fish and sediment samples from Minamata Bay remain higher than those in other Japanese coastal waters, and elevated concentrations of THg in sediments in the greater Yatsushiro Sea suggest that Hg has moved beyond the bay. We measured stable Hg isotope ratios in sediment cores from Minamata Bay and the southern Yatsushiro Sea and in archived fish from Minamata Bay dating from 1978 to 2013. Values of δ²⁰²Hg and Δ¹⁹⁹Hg in Yatsushiro Sea surface sediments were indistinguishable from those in highly contaminated Minamata Bay sediments but distinct from and nonoverlapping with values in background (noncontaminated) sediments. We conclude that stable Hg isotope data can be used to track Minamata Bay Hg as it moves into the greater Yatsushiro Sea. In addition, our data suggest that MeHg is produced in bottom sediments and enters the food web without substantial prior photodegradation, possibly in sediment porewaters or near the sediment-water interface

Variation in Terrestrial and Aquatic Sources of Methylmercury in Stream Predators as Revealed by Stable Mercury Isotopes

Mercury (Hg) is widely distributed in the environment, and its organic form, methylmercury (MeHg), can extensively bioaccumulate and biomagnify in aquatic and terrestrial food webs. Concentrations of MeHg in organisms are highly variable, and the sources in natural food webs are often not well understood. This study examined stable isotope ratios of MeHg (mass-dependent fractionation, as δ²⁰²Hg_MeHg; and mass-independent fractionation, as Δ¹⁹⁹Hg_MeHg) in benthic invertebrates, juvenile steelhead trout (Oncorhynchus mykiss), and water striders (Gerris remigis) along a stream productivity gradient, as well as carnivorous terrestrial invertebrates, in a forested watershed at the headwater of South Fork Eel River in northern California. Throughout the sampling sites, δ²⁰²Hg_MeHg (after correction due to the effect of MeHg photodegradation) was significantly different between benthic (median = −1.40‰; range, −2.34 to −0.78‰; total number of samples = 29) and terrestrial invertebrates (median = +0.51‰; range, −0.37 to +1.40‰; total number of samples = 9), but no major difference between these two groups was found for Δ¹⁹⁹Hg_MeHg. Steelhead trout (52 individual fishes) have MeHg of predominantly aquatic origins, with a few exceptions at the upstream locations (e.g., 1 fish collected in a tributary had a purely terrestrial MeHg source and 4 fishes had mixed aquatic and terrestrial MeHg sources). Water striders (seven pooled samples) derive MeHg largely from terrestrial sources throughout headwater sections. These data suggest that direct terrestrial subsidy (e.g., terrestrial invertebrates falling into water) can be important for some stream predators in headwater streams and could represent an important means of transfer of terrestrially derived MeHg (e.g., in situ methylation within forests, atmospheric sources) to aquatic ecosystems. Moreover, these findings show that terrestrial subsidies can enhance MeHg bioaccumulation of consumers in headwater streams where aqueous MeHg levels are very low

Assessing bias in total mercury results after removing a subsample from the bottle

<p>U.S. EPA Method 1631 for total mercury (THg) analysis in water recommends that bromine monochloride (BrCl) be added to the original bottle in which the sample was collected, to draw into solution any Hg that may have adsorbed to the bottle walls. The method also allows for the removal of a subsample of water from the sample bottle for methylmercury (MeHg) analysis prior to adding BrCl. We have demonstrated that the removal of a subsample from the sample bottle prior to THg analysis can result in a positive concentration bias. The proposed mechanism for the bias is that ‘excess’ inorganic Hg, derived from the subsample that was removed from the bottle, adsorbs to the bottle walls and is then drawn into solution when BrCl is added. To test for this bias, we conducted an interlaboratory comparison study in which nine laboratories analysed water samples in fluorinated polyethylene (FLPE) bottles for THg after removing a subsample from the sample bottle, and analysed a replicate sample bottle from which no subsample was removed. We received seven complete data sets, or 63 unique sample pairs. The positive concentration bias between the bottles was significant when comparing all samples in aggregate (1.76 ± 0.53 ng/L after subsample removal, 1.57 ± 0.58 ng/L with no subsample removal, <i>P</i> < 0.05), however when comparing each of the three samples individually, the only significant bias was in the saline sample (Site UJ; 1.51 ± 0.31 ng/L after subsample removal, 1.32 ± 0.47 ng/L with no subsample removal, <i>P</i> < 0.05). Based on the findings presented here, we conclude that water chemistry, volume of water poured off, and the sample storage temperature explain some but not all of the observed bias, and we recommend collecting THg and MeHg samples in separate bottles whenever possible.</p