High manganese and nickel concentrations in human hair and well water and low calcium concentration in blood serum in a pristine area with sulphide-rich bedrock.

We report the trace element status of residents living in areas with naturally sulphide-rich bedrock and soil in two municipalities in Finland, Sotkamo and Kaavi. Altogether, 225 people from these sparsely populated regions participated voluntarily by providing hair and blood samples. The concentrations of calcium, zinc and copper in serum as well as selenium and cadmium in whole blood did not show correlation with those concentrations in hair samples. Calcium concentration in serum was slightly lower in the sulphide-rich areas (median value 91.4 mg/l, n = 103) than in the areas with adjacent sulphur-poor bedrock (median value 93.6 mg/l, n = 82). The concentrations of Ni and Mn in hair correlated with those in drinking water. The highest Mn and Ni concentrations in the water samples from private wells were 1620 µg/l and 51 µg/l and the highest concentrations in human hair samples 36.44 mg/kg and 12.3 mg/kg, respectively. The challenge with elevated trace element concentrations in some well waters is well documented. In northern countries (Finland, Sweden, Norway and Canada), only 10% of the population depend on private well water, and 90% have access to monitored municipal water supplies. Compared with data available from sulphide mine sites globally, the nickel and manganese concentrations in human hair samples were high in our sulphide-rich study area at Sotkamo representing the trace element status of residents under natural conditions.

Impacts of forest harvesting on mobilization of Hg and MeHg in drained peatland forests on black schist or felsic bedrock.

Forest harvesting, especially when intensified harvesting method as whole-tree harvesting with stump lifting (WTHs) are used, may increase mercury (Hg) and methylmercury (MeHg) leaching to recipient water courses. The effect can be enhanced if the underlying bedrock and overburden soil contain Hg. The impact of stem-only harvesting (SOH) and WTHs on the concentrations of Hg and MeHg as well as several other variables in the ditch water was studied using a paired catchment approach in eight drained peatland-dominated catchments in Finland (2008-2012). Four of the catchments were on felsic bedrock and four on black schist bedrock containing heavy metals. Although both Hg and MeHg concentrations increased after harvesting in all treated sites according to the randomized intervention analyses (RIAs), there was only a weak indication of a harvest-induced mobilization of Hg and MeHg into the ditches. Furthermore, no clear differences between WTHs and SOH were found, although MeHg showed a nearly significant difference (p = 0.06) between the harvesting regimes. However, there was a clear bedrock effect, since the MeHg concentrations in the ditch water were higher at catchments on black schist than at those on felsic bedrock. The pH, suspended solid matter (SSM), dissolved organic carbon (DOC), and iron (Fe) concentrations increased after harvest while the sulfate (SO4-S) concentration decreased. The highest abundances of sulfate-reducing bacteria (SRB) were found on the sites with high MeHg concentrations. The biggest changes in ditch water concentrations occurred first 2 years after harvesting.

Determination of low methylmercury concentrations in peat soil samples by isotope dilution GC-ICP-MS using distillation and solvent extraction methods.

Most often, only total mercury concentrations in soil samples are determined in environmental studies. However, the determination of extremely toxic methylmercury (MeHg) in addition to the total mercury is critical to understand the biogeochemistry of mercury in the environment. In this study, N2-assisted distillation and acidic KBr/CuSO4 solvent extraction methods were applied to isolate MeHg from wet peat soil samples collected from boreal forest catchments. Determination of MeHg was performed using a purge and trap GC-ICP-MS technique with a species-specific isotope dilution quantification. Distillation is known to be more prone to artificial MeHg formation compared to solvent extraction which may result in the erroneous MeHg results, especially with samples containing high amounts of inorganic mercury. However, methylation of inorganic mercury during the distillation step had no effect on the reliability of the final MeHg results when natural peat soil samples were distilled. MeHg concentrations determined in peat soil samples after distillation were compared to those determined after the solvent extraction method. MeHg concentrations in peat soil samples varied from 0.8 to 18 µg kg(-1) (dry weight) and the results obtained with the two different methods did not differ significantly (p=0.05). The distillation method with an isotope dilution GC-ICP-MS was shown to be a reliable method for the determination of low MeHg concentrations in unpolluted soil samples. Furthermore, the distillation method is solvent-free and less time-consuming and labor-intensive when compared to the solvent extraction method.