Kristofer R. Rolfhus

Mercury in the North Atlantic

Abstract Reactive mercury (Hg) concentrations (0.80±0.44 pM), measured during a cruise in the sub-polar North Atlantic (50–70°N) in August 1993 were lower those of more southerly regions of this ocean. A large fraction of the Hg in the surface waters was elemental Hg (Hg°; 88% of the reactive Hg, on average; 0.65±0.50 pM). Little dimethylmercury (DMHg) or monomethylmercury (MMHg) was found in surface waters but higher concentrations were found at depth. The high surface water Hg° concentrations likely reflect production of Hg° in concert with the short season of primary production in these waters. Overall, gas exchange plays a dominant role in the cycle of Hg in the upper waters of this region. For the sub-thermocline waters, a comparison of the Hg speciation in different water masses suggests that surface waters accumulate reactive Hg and methylated Hg—due to input of reactive Hg via remineralization and conversion of reactive Hg to methylated Hg—after sinking during winter to form North Atlantic deep water. Reactive Hg concentrations varied between water masses with the lowest concentrations being found in the waters north of Iceland (the source waters for deep water formation). DMHg was found throughout the sub-thermocline water column and the limited data set for MMHg suggests that this species was also prevalent. These observations suggest that methylated Hg production in the ocean is not confined to low oxygen or anoxic regions, as has been found in lakes. Concentrations of DMHg (0.08±0.07 pM, on average) were lower than those previously measured in the equatorial Pacific. Total Hg concentrations averaged 2.4±1.6 pM but little of this was particulate Hg ( −1 , typically). There was evidence of colloidally-bound Hg in surface waters. Overall, the data strengthen our hypotheses concerning Hg biogeochemical cycling in the ocean and confirm the importance of gas exchange and Hg methylation in the fate and transport of Hg in the ocean.

Atmospheric mercury in northern Wisconsin: Sources and species

The atmospheric chemistry, deposition and transport of mercury (Hg) in the Upper Great Lakes region is being investigated at a near-remote sampling location in northern Wisconsin. Intensive sampling over two years and various seasons has been completed. A multi-phase collection strategy (gas-, particle- and precipitation-phases) was employed to gain insight into the processes controlling concentrations and chemical/physical speciation of atmospheric Hg. Additional chemical and physical atmospheric determinations (e.g. ozone, particulate constituents, meteorology) were also made during these periods to aid in the interpretation of the Hg determinations. For example, correlations of Hg with ozone, sulfur dioxide and synoptic-scale meteorological features suggest a regionally discernible signal in Hg. Comparison to isosigma backward air parcel trajectories confirms this regionality and implicates the areas south, southeast and northwest of the site to be sources; for Hg. Particle-phase Hg (Hgp) was found to be approximately 40% in an oxidized form, or operationally defined as “reactive”. However, this was quite variable from year-to-year. Hgp and other particle constituents (esp. sulfate) show significant correlation and similarity in behavior (concentration ratios in precipitation and in particles). These observations are part of the growing evidence to support the hypothesis that precipitation-phase Hg arises in large part from the scavenging of atmospheric particulates bearing Hg. Observed concentrations of rain and particle-Hg fit broadly the theoretical expectations for nucleation and below-cloud scavenging. Significant increases in the Hg/aerosol mass ratio appear to take place during transport Enrichment of aerosols is taken as evidence of gas/particle conversion which could represent the step linking gas-phase Hg with rain. The refined budget indicates ca. 24% of total deposition is from summer particle dry deposition, and that this deposition also contributes ca. 24% of all reactive Hg deposition. Additionally, almost all (86%) deposition (wet and dry) occurs during the summer months.

The atmospheric cycling and air–sea exchange of mercury species in the South and equatorial Atlantic Ocean

Measurements of gas-, particle- and precipitation-phases of atmospheric mercury (Hg) were made in the South and equatorial Atlantic Ocean as part of the 1996 IOC Trace Metal Baseline Study (Montevideo, Uruguay to Barbados). Total gaseous mercury (TGM) ranged from 1.17 to 1.99 ng m−3, with a weighted mean of 1.61±0.09 ng m−3. These values compare well with Pacific Ocean data and earlier results from the Atlantic. The open-ocean samples recorded a distinctive inter-hemispheric gradient, which is consistent with a long-lived trace gas emitted to a greater extent from the Northern than from the Southern Hemisphere. Correlations with surface 222Rn measurements indicate an influence of regional terrestrial sources on open-ocean TGM concentrations. Total Hg in precipitation ranged from 10 to 99 pM (volume-weighted average: 17.8±2.9 pM). On average, about 72% of the total Hg was “reactive” (i.e., reducible by SnCl2). The data showed an apparent rapid nonlinear decrease in concentration with event size (“washout curve”). The wet depositional flux was estimated at 18–36 nmol m−2 yr−1 (4–7 μg m−2 yr−1), which is slightly lower than that found in mid-continental locations of North America (6–12 μg m−2 yr−1). 210Pb analyses indicate a strong impact of particles on rain Hg concentrations. Particle-phase Hg (range 5–25 fmol m−3; mean 12±1 fmol m−3; 66% “reactive”) was comparable to values over the equatorial Pacific. The dry depositional flux is ca. 0.4 nmol m−2 yr−1, or 0.4–1.0% of the wet flux. Particle-phase Hg concentrations did not change significantly when African dust was present during sampling. However, the Hg/Al ratios were consistent with crustal values during the dust periods. The residence time of TGM was calculated to be 1.3–3.4 yr in this region, based on standing stock estimates. Incubation of rainwater added to surface seawater gave reduction rates [i.e., production of elemental Hg (Hg°); 1.6–4.3% d of total Hg added] comparable to additions of inorganic ionic standards, indicating that Hg+2 from precipitation is reduced in a similar manner in surface waters. Thus, precipitation-phase Hg is generally available for evasion to the atmosphere following deposition to the surface ocean, effectively enhancing the mobility and residence time of Hg at the Earths surface.

Methylated and elemental mercury cycling in surface and deep ocean waters of the North Atlantic

Biogeochemical cycling of mercury (Hg) in the ocean and air-sea exchange are integral parts of the global Hg cycle. Ionic Hg (i.e. reactive Hg-Hg°) is converted in ocean surface waters to elemental Hg (Hg°) with the subsequent loss, via gas evasion, of the Hg° to the atmosphere. During a recent cruise in the North Atlantic Ocean, Hg° in surface waters was a substantial fraction of the reactive Hg (85%, on average) and there was a relationship between photosynthetic pigment concentration and Hg°. In addition, there was evidence of Hg bound to “collodial” material (of greater than 1,000 molecular weight). Ionic Hg concentrations were around 0.15 pM, similar to the average colloidal Hg concentration of 0.2 pM. Methylated Hg compounds, both dimethylHg (DMHg) and monomethylHg (MMHg), were found in the deeper waters with DMHg being the predominant methylated species. This contrasts with freshwater lakes where MMHg is the principal species and no DMHg has been found. Preliminary modelling, using estimated rate constants for the formation and decomposition of DMHg and MMHg, predicts an enhanced stability of DMHg in ocean waters relative to fresh water. Deep ocean waters, formed by sinking of surface waters, can preserve DMHg that was produced in the more productive surface regime.

Linkages between atmospheric mercury deposition and the methylmercury content of marine fish

Enhanced Hg deposition to productive marine systems may result in concurrent increases in monomethyl Hg (MMHg) concentrations of marine fish. Consequently, it is important to understand what effects an increasing Hg supply may have on the marine food chain. A simple ocean model is employed to estimate the fraction of total Hg inputs which is required to sustain “average” marine fish MMHg concentrations annually. Calculations show that upwelling zones require 20% of total annual Hg inputs, coastal zones 5%, and open-ocean regions only 0.02%. The value for coastal areas is similar to that calculated for the acidified basin of Little Rock Lake, Wisconsin, a small fresh water seepage lake. These calculations point to Hg source strength and rates of particle scavenging as being key factors in controlling the rate of transport to sites of methylation (and subsequent entry into the marine food chain). If biological variables (scavenging rates, primary productivity) remain constant while anthropogenically-derived Hg deposition increases, it is likely that concentrations in marine biota (including fish) will rise in accord.

Assessment of mercury bioaccumulation within the pelagic food web of lakes in the western Great Lakes region

While mercury is a health hazard to humans and wildlife, the biogeochemical processes responsible for its bioaccumulation in pelagic food webs are still being examined. Previous studies have indicated both “bottom-up” control of piscivorous fish Hg content through methylmercury.(MeHg) supply, as well as site-specific trophic factors. We evaluated ten studies from the western Great Lakes region to examine the similarity of MeHg trophic transfer efficiency within the pelagic food web, and assessed regional-scale spatial variability. Analyses of bioaccumulation and biomagnification factors between water, seston, zooplankton, and preyfish indicated that the largest increases in MeHg occurred at the base of the food web, and that the relative extent of trophic transfer was similar between sites. Positive correlations were observed between aqueous unfiltered MeHg, total Hg, and dissolved organic carbon, and measures of the efficiency of MeHg trophic transfer were consistent across widely disparate systems (both natural and experimentally manipulated) throughout North America. Such similarity suggests that the aqueous supply of MeHg is largely controlling bioaccumulation in pelagic food webs, while local, lake-specific variability can result from an array of trophic (biological) factors.

Burrowing Dragonfly Larvae as Biosentinels of Methylmercury in Freshwater Food Webs

We assessed the utility of larval burrowing dragonflies (Odonata: Anisoptera: Gomphidae) as biosentinels of methylmercury (MeHg) contamination. Gomphids were the most abundant family of dragonflies sampled during 2008-2010 from 17 lakes in four national parks of the northwestern Laurentian Great Lakes region. Ten species of burrowing gomphids were sampled; 13 lakes contained 3 or more species, and 2 species of Gomphus co-occurred in 12 lakes. Most of the total Hg (THg) in whole, late-instar larvae was MeHg, with mean percent MeHg exceeding 60% in 16 lakes. Mean MeHg in larvae of a given species varied greatly among lakes, ranging from 4 to 109 ng g(-1) dry weight. Methylmercury levels in larvae, however, were much less variable within a given lake and species. The mean concentration of MeHg in burrowing gomphids was positively correlated with mean MeHg concentration in unfiltered lake water. Mean concentrations of THg and MeHg in multispecies assemblages of Gomphus were also positively correlated with mean THg in coexisting prey fish and game fishes. We recommend-and provide guidance on-the application of burrowing gomphids as biosentinels of MeHg contamination, which can extend the bioassessment of MeHg to fishless fresh waters.

Production and Retention of Methylmercury in Inundated Boreal Forest Soils

The Flooded Uplands Dynamics Experiment (FLUDEX) was an ecosystem-scale study examining the production of methylmercury (MeHg) and greenhouse gases from reservoirs constructed on an upland boreal forest landscape in order to quantify their dependence upon carbon stores. We detail the within-reservoir production and storage of MeHg before, during, and nine years after the experiment. The reservoirs were net MeHg producers during the first two years of flooding, and net demethylating systems afterward. During years 1-3, a rapid pulse of MeHg and total Hg was observed in floodwater, followed by substantial increases in MeHg in seston and sediment. Resampling of the dry reservoirs nine years after the experiment ended indicated that organic soil MeHg was still 8 to 52-fold higher than preflood conditions, and averaged 86% of the levels recorded at the end of the third flooding year. Both total Hg and MeHg retention in soil were a strong function of organic carbon content. The time scale of soil MeHg retention may help explain the decadal time lag frequently observed for the decrease of piscivorous fish Hg concentrations in new reservoirs. Predicted extreme precipitation events associated with climate change may serve to make landscapes more susceptible to this process.

Mercury in streams at Grand Portage National Monument (Minnesota, USA): Assessment of ecosystem sensitivity and ecological risk

Mercury (Hg) in water, sediment, soils, seston, and biota were quantified for three streams in the Grand Portage National Monument (GRPO) in far northeastern Minnesota to assess ecosystem contamination and the potential for harmful exposure of piscivorous fish, wildlife, and humans to methylmercury (MeHg). Concentrations of total Hg in water, sediment, and soil were typical of those in forest ecosystems within the region, whereas MeHg concentrations and percent MeHg in these ecosystem components were markedly higher than values reported elsewhere in the western Great Lakes Region. Soils and sediment were Hg-enriched, containing approximately 4-fold more total Hg per unit of organic matter. We hypothesized that localized Hg enrichment was due in part to anthropogenic pollution associated with historic fur-trading activity. Bottom-up forcing of bioaccumulation was evidenced by MeHg concentrations in larval dragonflies, which were near the maxima for dragonflies sampled concurrently from five other national park units in the region. Despite its semi-remote location, GRPO is a Hg-sensitive landscape in which MeHg is produced and bioaccumulated in aquatic food webs to concentrations that pose ecological risks to MeHg-sensitive piscivores, including predatory fish, belted kingfisher, and mink.