Holger Hintelmann

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Measurement of mercury methylation in sediments by using enriched stable mercury isotopes combined with methylmercury determination by gas chromatography–inductively coupled plasma mass spectrometry

A novel technique for the calculation of mercury methylation rates in sediments by using enriched stable mercury isotopes is described. The method takes advantages of the ability of an inductively coupled plasma mass spectrometry (ICP-MS) instrument to measure individual isotopes. An ICP-MS instrument was used as a detector for the determination of methylmercury compounds after separation by gas chromatography (GC). CH3Hg+ was isolated from sediments by distillation, converted to methylethylmercury by sodium tetraethylborate and analysed after purge-and-trap pre-collection on a Tenax adsorber and thermodesorption onto the GC column. Detection limits were found to be ≈ 1 pg (as Hg) absolute or 0.02 ng g–1 dry sediment. The precision was ≈ 4% relative standard deviation when 250 pg of methylmercury were processed. The accuracy of the GC–ICP-MS technique was demonstrated by analysis of an International Atomic Energy Agency certified reference material (IAEA CRM 356) Harbor Sediment, giving a concentration of 5.40 ± 0.40 ng g–1, compared with the certified value of 5.46 ± 0.38 ng g–1. Mercury methylation was investigated by spiking sediments with stable enriched mercury isotopes at in situ mercury concentrations not perturbing the system. More than 3% of the mercury added to a lake sediment was methylated during a 21 d incubation period. Isotope ratios of total mercury differed significantly from isotope ratios of methylmercury at the end of the experiment, suggesting that the system was still not in equilibrium after 21 d.

Mercury isotope fractionation during volatilization of Hg(0) from solution into the gas phase

The objective of this work was to determine the magnitude of mercury isotope fractionation during volatilization of Hg(0) dissolved in aqueous solution to the gas phase and to develop a method for the precise determination of isotope ratios of gaseous Hg(0) by multi-collector ICP-MS. Hg(0) was generated in situ by reducing Hg(II) using SnCl2 and subsequently purged into a trapping solution. A 316 μM KMnO4 trapping solution, acidified by 0.9 M sulfuric acid, recovered 96.1 ± 4.0% of Hg (2 SD, n = 20). The observed δ202Hg of −0.049 ± 0.065‰ (2 SD, n = 17) relative to the initial Hg standard was not greater than the daily external precision of the isotope ratio measurement, which is typically <0.100‰ (2 SD). The volatilization experiments were conducted by reducing Hg(II) completely using SnCl2, letting the developed Hg(0) evaporate from solution and purging the Hg(0) vapor in the headspace over the solution into the trapping solutions. The concentration and isotope ratios of Hg in both the trapping solutions and the Hg(0) remaining in solution were measured at different time intervals. The kinetics of the volatilization was found to be a first order process. The pattern of isotope fractionation during volatilization followed a Rayleigh fractionation with an observed maximum δ202Hg value of 1.48 ± 0.07‰ (2 SD). Fractionation factors of 1.00044 and 1.00047 were obtained in two independent experiments. These results provide the first experimental proof for, and quantified the pattern and magnitude of, the Hg isotope fractionation during volatilization of Hg(0) from solution into the gas phase.

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

How does climate change influence arctic mercury

Recent studies have shown that climate change is already having significant impacts on many aspects of transport pathways, speciation and cycling of mercury within Arctic ecosystems. For example, the extensive loss of sea-ice in the Arctic Ocean and the concurrent shift from greater proportions of perennial to annual types have been shown to promote changes in primary productivity, shift foodweb structures, alter mercury methylation and demethylation rates, and influence mercury distribution and transport across the ocean-sea-ice-atmosphere interface (bottom-up processes). In addition, changes in animal social behavior associated with changing sea-ice regimes can affect dietary exposure to mercury (top-down processes). In this review, we address these and other possible ramifications of climate variability on mercury cycling, processes and exposure by applying recent literature to the following nine questions; 1) What impact has climate change had on Arctic physical characteristics and processes? 2) How do rising temperatures affect atmospheric mercury chemistry? 3) Will a decrease in sea-ice coverage have an impact on the amount of atmospheric mercury deposited to or emitted from the Arctic Ocean, and if so, how? 4) Does climate affect air-surface mercury flux, and riverine mercury fluxes, in Arctic freshwater and terrestrial systems, and if so, how? 5) How does climate change affect mercury methylation/demethylation in different compartments in the Arctic Ocean and freshwater systems? 6) How will climate change alter the structure and dynamics of freshwater food webs, and thereby affect the bioaccumulation of mercury? 7) How will climate change alter the structure and dynamics of marine food webs, and thereby affect the bioaccumulation of marine mercury? 8) What are the likely mercury emissions from melting glaciers and thawing permafrost under climate change scenarios? and 9) What can be learned from current mass balance inventories of mercury in the Arctic? The review finishes with several conclusions and recommendations.

Comparison of different extraction techniques used for methylmercury analysis with respect to accidental formation of methylmercury during sample preparation

Abstract Different techniques commonly used to extract monomethylmercury (MMHg) from various matrices have been screened regarding their potential to accidentally generate MMHg from inorganic Hg2+ during sample preparation. Most of the tested techniques, among them alkaline and acidic leaching as well as atmospheric pressure distillation, were prone to spurious formation of CH3200Hg+ from 200Hg2+ added to certified reference materials. 0.006–0.05 % of the added stable inorganic Hg isotope was converted to MMHg. Only leaching using a H2SO4/KBr/CuSO4 mixture did not cause any artifacts. In certain sediment samples where the MMHg fraction is less than 190, the degree of artifactual formation observed can be significant. To calculate the original MMHg content in such samples the application of a species specific isotope addition method (SSIA) is proposed and was evaluated.

Tracing Mercury Contamination Sources in Sediments Using Mercury Isotope Compositions

Mercury (Hg) isotope ratios were determined in two sediment cores collected from two adjacent reservoirs in Guizhou, China, including Hongfeng Reservoir and Baihua Reservoir. Hg isotope compositions were also analyzed in a soil sample collected from the catchment of Hongfeng Reservoir and three cinnabar samples collected from the Wanshan Hg mine. Baihua Reservoir was contaminated with runoff from Guizhou Organic Chemical Plant (GOCP) when metallic Hg was used as a catalyst to produce acetic acid. Hongfeng Reservoir, located upstream of Baihua, receives Hg from runoff and atmospheric deposition. We demonstrated that delta(202)Hg values relative to NIST 3133 of sediment in Baihua Reservoir ranging from -0.60 to -1.10 per thousand were distinctively different from those in Hongfeng Reservoir varying from -1.67 to -2.02 per thousand. While sediments from both Baihua and Hongfeng Reservoirs were characterized by mass dependent variation (MDF), only Hongfeng Reservoir sediments were characterized by mass independent variation (MIF). Moreover, by using a binary mixing model, we demonstrated the major source of Hg in sediment of Hongfeng Reservoir was from runoff due to soil erosion, which was consistent with the conclusion obtained from a previous Hg balance study. This study demonstrates Hg isotope data are valuable tracers for determining Hg contamination sources in sediments.

Anomalous mercury isotopic compositions of fish and human hair in the Bolivian Amazon.

We report mercury (Hg) mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in hair samples of the Bolivian Esse Ejjas native people and in several tropical fish species that constitute their daily diet. MDF with delta(202)Hg ranging from -0.40 to -0.92 per thousand for fish and +1.04 to +1.42 per thousand for hair was observed. Hair samples of native people with a fish-dominated diet are enriched by +2.0 +/- 0.2 per thousand in delta(202)Hg relative to the fish consumed. Both odd Hg isotopes, (199)Hg and (201)Hg, display MIF in fish (from -0.14 to +0.38 per thousand for Delta(201)Hg and from -0.09 to +0.55 per thousand for Delta(199)Hg) and in hair (from +0.12 to +0.66 per thousand for Delta(201)Hg and from +0.14 to +0.81 per thousand for Delta(199)Hg). No significant difference in MIF anomalies is observed between Hg in fish and in human hair, suggesting that the anomalies act as conservative source tracers between upper trophic levels of the tropical food chain. Fish Hg MIF anomalies are 10-fold lower than those published for fish species from midlatitude lakes. Grouping all Amazonian fish species per location shows that Delta(199)Hg:Delta(201)Hg regression slopes for the clear water Itenez River basin (0.95 +/- 0.08) are significantly lower than those for the white water Beni River basin (1.28 +/- 0.12). Assuming that the observed MIF originates from aquatic photoreactions, we calculated limited photodemethylation of monomethylmercury (MMHg) in the Beni River floodplains and insignificant photodemethylation in the Itenez River floodplains. This is possibly related to lower residence times of MMHg in the Itenez compared to the Beni River floodplains. Finally, a significantly negative Delta(201)Hg of -0.14 per thousand in Beni River fish suggests that the inorganic Hg precursor to the MMHg that bioaccumulates up the food chain defines an ecosystem specific non-zero Delta(201)Hg baseline. Calculation of photodemethylation intensities from Hg or MMHg MIF, therefore, requires a baseline correction.

Levels of total mercury and methylmercury compounds in sediments of the polluted Elbe River: influence of seasonally and spatially varying environmental factors

The Elbe River system in Germany is severely polluted with mercury, including methylmercury compounds. In the vicinity of the city of Hamburg, content of total mercury and methylmercury compounds in sediments of 12 mg/kg and 35 μg/kg (d.w.), respectively, are observed. Analyses of sediment samples from selected sites during different seasons indicate that levels of methylmercury compounds are dependent on microbial activity. CH3Hg+ content is high under conditions that stimulate Hg(II)-methylating microorganisms. Thus, levels are elevated where nutrient supplies and biological productivity are greatest. In addition, methylmercury content in the sediments increases with increasing abundance of acid volatile sulfide (AVS). Examination of seasonal effects shows larger amounts of methylmercury compounds under warm summer conditions than in cold winter and spring weather. Additional evidence indicates the importance of microbial activity for the production and occurrence of methylmercury compounds in sediments. A more detailed local cycle for mercury compounds is proposed, taking into account the data presented in this paper.

Importance of sulfate reducing bacteria in mercury methylation and demethylation in periphyton from Bolivian Amazon region

Sulfate reducing bacteria (SRB) are important mercury methylators in sediments, but information on mercury methylators in other compartments is ambiguous. To investigate SRB involvement in methylation in Amazonian periphyton, the relationship between Hg methylation potential and SRB (Desulfobacteraceae, Desulfobulbaceae and Desulfovibrionaceae) abundance in Eichhornia crassipes and Polygonum densiflorum root associated periphyton was examined. Periphyton subsamples of each macrophyte were amended with electron donors (lactate, acetate and propionate) or inhibitors (molybdate) of sulfate reduction to create differences in SRB subgroup abundance, which was measured by quantitative real-time PCR with primers specific for the 16S rRNA gene. Mercury methylation and demethylation potentials were determined by a stable isotope tracer technique using 200HgCl and CH3(202)HgCl, respectively. Relative abundance of Desulfobacteraceae (<0.01-12.5%) and Desulfovibrionaceae (0.01-6.8%) were both highly variable among samples and subsamples, but a significant linear relationship (p<0.05) was found between Desulfobacteraceae abundance and net methylmercury formation among treatments of the same macrophyte periphyton and among all P. densiflorum samples, suggesting that Desulfobacteraceae bacteria are the most important mercury methylators among SRB families. Yet, molybdate only partially inhibited mercury methylation potentials, suggesting the involvement of other microorganisms as well. The response of net methylmercury production to the different electron donors and molybdate was highly variable (3-1104 pg g(-1) in 12 h) among samples, as was the net formation in control samples (17-164 pg g(-1) in 12 h). This demonstrates the importance of community variability and complexity of microbial interactions for the overall methylmercury production in periphyton and their response to external stimulus.