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The strongest evidence for anthropogenic alterations to the global mercury (Hg) cycle comes from historical records of mercury deposition preserved in lake sediments. Hg isotopes have added a new dimension to these sedimentary archives, promising additional insights into Hg source apportionment and biogeochemical processing. Presently, most interpretations of historical changes are constrained to a small number of locally contaminated ecosystems. Here, we describe changes in natural Hg isotope records from a suite of dated sediment cores collected from various remote lakes of North America. In nearly all cases, the rise in industrial-use Hg is accompanied by an increase in δ(202)Hg and Δ(199)Hg values. These trends can be attributed to large scale industrial emission of Hg into the atmosphere and are consistent with positive Δ(199)Hg values measured in modern-day precipitation and modeled increases in δ(202)Hg values from global emission inventories. Despite similar temporal trends among cores, the baseline isotopic values vary considerably among the different study regions, likely attributable to differences in the fractionation produced in situ as well as differing amounts of atmospherically delivered Hg. Differences among the study lakes in precipitation and watershed size provide an empirical framework for evaluating Hg isotopic signatures and global Hg cycling.

Significance Elevated mercury in fish poses risks to fish-consuming wildlife and humans. Tracing sources of mercury by analyzing stable isotope ratios leads to improved source-receptor understanding and natural resource management. This work utilizes fish and sediment archives to trace the response to recent domestic mercury mitigation actions. Fish and sediments rapidly responded to a source perturbation contemporaneous with the reduction of mercury in the late 1980s. Subsequently, energetic pathways were altered due to dreissenid invasions, which dampened the expected decrease in fish mercury concentration. These findings reveal the importance of domestic mercury sources relative to global mercury to the Great Lakes. Results also show methylmercury concentrations in fish are sensitive to changes in trophic structure and diet driven by invasive species., To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Edlund MB, Schottler SP, Reavie ED, Engstrom DR, Baratono NG, Leavitt PR, Heathcote AJ, Wilson B, Paterson AM. 2017. Historical phosphorus dynamics in Lake of the Woods (USA–Canada) — does legacy phosphorus still affect the southern basin? Lake Reserv Manage. 33:386–402. A historical phosphorus (P) budget was constructed for southern Lake of the Woods. Sediment cores from 7 bays were radioisotopically dated and analyzed for loss-on-ignition, P, Si, diatoms, and pigments. Geochemical records for cores were combined using focusing factors for whole-basin estimates of sediment, total P, and P fraction accumulation. Although historical monitoring shows that external P loads decreased since the 1950s, sediment P has continued to increase since the mid-20th century. Much sediment P is labile and may be mobile within the sediments and/or available for internal loading and resuspension. Two mass-balance models were used to explore historical P loading scenarios and in-lake dynamics, a static one-box model and a dynamic multi-box model. The one-box model predicts presettlement external loads were slightly less than modern loads. The dynamic model shows that water-column P was higher in the 1950s–1970s than today, that the lake is sensitive to external loads because P losses from burial and outflow are high, and that the lake is moving to a new steady state with respect to water-column P and size of the active sediment P pool. The active sediment pool built up in the mid-20th century has been depleted through outflow and burial, such that its legacy effects are now minimal. Comparison of historical nutrient dynamics and sediment records of algal production showed a counterintuitive increase in production after external P loads decreased, suggesting other drivers may now regulate modern limnoecology, including seasonality of P loading, shifting nutrient limitation, and climate warming.

In Chap. 2 of this volume Lange and Frederick evaluate changes in mercury (Hg) concentrations in Everglades biota to identify the occurrence of temporally coherent trends that ideally can be understood and related to changing process dynamics. To the extent such trends occur in the Everglades, processes that are potentially causative include atmospheric deposition of Hg, changing dynamics in key water quality variables such as sulfate and dissolved organic carbon, and changing hydrology. This overall process of trend identification and elucidation of underlying factors can in turn provide insight on possible strategies for mitigating the problem of excessive biota Hg concentrations in the Everglades. This chapter evaluates whether changes in atmospheric deposition of Hg to the Everglades have occurred in recent years using direct evidence from measured wet deposition and gaseous elemental mercury (GEM). The chapter also considers changes in mercury concentrations recorded in bottom sediments as a proxy for longer-term changes in atmospheric deposition. This latter analysis includes a review of changes observed in aquatic ecosystems from North America and Europe as well as south Florida and the Everglades, and whether recent changes in south Florida reflect large scale processes or reductions in local emissions of Hg.

For the Western North America Mercury Synthesis, we compiled mercury records from 165 dated sediment cores from 138 natural lakes across western North America. Lake sediments are accepted as faithful recorders of historical mercury accumulation rates, and regional and sub-regional temporal and spatial trends were analyzed with descriptive and inferential statistics. Mercury accumulation rates in sediments have increased, on average, four times (4×) from 1850 to 2000 and continue to increase by approximately 0.2μg/m(2) per year. Lakes with the greatest increases were influenced by the Flin Flon smelter, followed by lakes directly affected by mining and wastewater discharges. Of lakes not directly affected by point sources, there is a clear separation in mercury accumulation rates between lakes with no/little watershed development and lakes with extensive watershed development for agricultural and/or residential purposes. Lakes in the latter group exhibited a sharp increase in mercury accumulation rates with human settlement, stabilizing after 1950 at five times (5×) 1850 rates. Mercury accumulation rates in lakes with no/little watershed development were controlled primarily by relative watershed size prior to 1850, and since have exhibited modest increases (in absolute terms and compared to that described above) associated with (regional and global) industrialization. A sub-regional analysis highlighted that in the ecoregion Northwestern Forest Mountains

Historical reconstruction of mercury (Hg) accumulation in natural archives, especially lake sediments, has been essential to understanding human perturbation of the global Hg cycle. Here we present a high-resolution chronology of Hg accumulation between 1727 and 1996 in a varved sediment core from the Pettaquamscutt River Estuary (PRE), Rhode Island. Mercury accumulation is examined relative to (1) historic deposition of polycyclic aromatic hydrocarbons (PAHs) and lead (Pb) and its isotopes (206Pb/207Pb) in the same core, and (2) other reconstructions of Hg deposition in urban and remote settings. Mercury deposition in PRE parallels the temporal patterns of PAHs, and both track industrialization and regional coal use between 1850 and 1950 as well as rising petroleum use after 1950. There is little indication of increased Hg deposition from late 19th-century silver and gold mining in the western U.S. A broad maximum of Hg deposition during 1930–1980, and not found in remote sites, is consistent with the pr...

A series of severe droughts during the course of a long-term, atmospheric sulfate-deposition experiment in a boreal peatland in northern Minnesota created a unique opportunity to study how methylmercury (MeHg) production responds to drying and rewetting events in peatlands under variable levels of sulfate loading. Peat oxidation during extended dry periods mobilized sulfate, MeHg, and total mercury (HgT) to peatland pore waters during rewetting events. Pore water sulfate concentrations were inversely related to antecedent moisture conditions and proportional to past and current levels of atmospheric sulfate deposition. Severe drying events caused oxidative release of MeHg to pore waters and resulted in increased net MeHg production likely because available sulfate stimulated the activity of sulfate-reducing bacteria, an important group of Hg-methylating bacteria in peatlands. Rewetting events led to increased MeHg concentrations across the peatland, but concentrations were highest in peat receiving elevated atmospheric sulfate deposition. Dissolved HgT concentrations also increased in peatland pore waters following drought but were not affected by sulfate loading and did not appear to be directly controlled by dissolved organic carbon mobilization to peatland pore waters. Peatlands are often considered to be sinks for sulfate and HgT in the landscape and sources of MeHg. Hydrologic fluctuations not only serve to release previously sequestered sulfate and HgT from peatlands but may also increase the strength of peatlands as sources of MeHg to downstream aquatic systems, particularly in regions that have experienced elevated levels of atmospheric sulfate deposition.

Human activities over the last several centuries have transferred vast quantities of mercury (Hg) from deep geologic stores to actively cycling earth-surface reservoirs, increasing atmospheric Hg deposition worldwide. Understanding the magnitude and fate of these releases is critical to predicting how rates of atmospheric Hg deposition will respond to future emission reductions. The most recently compiled global inventories of integrated (all-time) anthropogenic Hg releases are dominated by atmospheric emissions from preindustrial gold/silver mining in the Americas. However, the geophysical evidence for such large early emissions is equivocal, because most reconstructions of past Hg-deposition have been based on lake-sediment records that cover only the industrial period (1850-present). Here we evaluate historical changes in atmospheric Hg deposition over the last millennium from a suite of lake-sediment cores collected from remote regions of the globe. Along with recent measurements of Hg in the deep ocean, these archives indicate that atmospheric Hg emissions from early mining were modest as compared to more recent industrial-era emissions. Although large quantities of Hg were used to extract New World gold and silver beginning in the 16th century, a reevaluation of historical metallurgical methods indicates that most of the Hg employed was not volatilized, but rather was immobilized in mining waste.

Southeastern Alaska is a remote coastal-maritime ecosystem that is experiencing increased deposition of mercury (Hg) as well as rapid glacier loss. Here we present the results of the first reported survey of total and methyl Hg (MeHg) concentrations in regional streams and biota. Overall, streams draining large wetland areas had higher Hg concentrations in water, mayflies, and juvenile salmon than those from glacially-influenced or recently deglaciated watersheds. Filtered MeHg was positively correlated with wetland abundance. Aqueous Hg occurred predominantly in the particulate fraction of glacier streams but in the filtered fraction of wetland-rich streams. Colonization by anadromous salmon in both glacier and wetland-rich streams may be contributing additional marine-derived Hg. The spatial distribution of Hg in the range of streams presented here shows that watersheds are variably, yet fairly predictably, sensitive to atmospheric and marine inputs of Hg.

It can be advantageous to revisit coring locations in lakes years after an initial paleolimnological study is completed, to assess environmental changes in the intervening time interval. We revisited sediment core sites in Lake Pepin (Minnesota, Wisconsin) more than a decade after an original set of 10 cores was collected, dated radiometrically, and studied in 1996. Prominent magnetic susceptibility features were used to align the new core set with the older set, such that traditional radiometric dating was not necessary to obtain a chronology for the new cores. The procedure used to align the two core sets accounted for compaction of former surface sediments by burial with new sediment. The amount of new sediment, mercury, and phosphorus accumulated at each core site was determined and extrapolated to the depositional area of the lake to estimate recent (1996–2008) whole-basin loads. Recent sediment accumulation in Lake Pepin compared well (within 3%) with monitored inflow data from a gauging station on the upper Mississippi River just before it enters the lake. Bulk sediment accumulation rate remained very high (772,000 t/year) for the recent period (1996–2008), down slightly from the peak in 1990–1996 (876,000 t/year), and almost an order of magnitude above pre-settlement rates. Total phosphorus deposition remained constant since a peak in the 1960s, but was also well above pre-settlement rates. Mercury continued its precipitous decline since peaking in the 1960s.

Our previous work has documented a correlation between Hg concentrations and 210 Pb activity measured in wet deposition that might be used to help apportion sources of Hg in precipitation. Here we present the results of a 27-month precipitation collection effort using co-located samplers for Hg and 210 Pb designed to assess this hypothesis. Study sites were located on the east and west coasts of North America, in the continental interior, and on the Florida Peninsula. Relatively high variability in Hg/ 210 Pb ratios was found at all sites regionally and seasonally (e.g., overall: 0.99–9.13 ng dpm − 1 ). The ratio of average volume-weighted Hg concentrations and 210 Pb activities showed consistent trends (higher in impacted area), with Glacier Bay in southeast Alaska, exhibiting the lowest value. Assuming that Glacier Bay represents a benchmark for a site with no regional contribution, we estimate less than 50% of the Hg input was “global” at the Seattle and Florida sites. Differences in Hg/ 210 Pb in wet deposition could be due to either a regional/local source contribution of Hg, or a regional/local enhancement in the removal of Hg from the atmosphere (i.e., oxidants), however, this approach is not capable of discerning between these two possibilities. Thus, this method of source apportionment represents an estimate of the maximal amount of Hg contributed by regional sources and may be limited in regions of deep convective mixing.

Reavie ED, Edlund MB, Andresen NA, Engstrom DR, Leavitt PR, Schottler S, Cai M. 2017. Paleolimnology of the Lake of the Woods southern basin: continued water quality degradation despite lower nutrient influx. Lake Reserv Manage. 33:369–385. Despite decades of reduced nutrient inputs, Lake of the Woods, a large, shallow boreal lake on the US-Canadian border, shows little evidence of water quality improvements in the pelagic system. Here we analyzed sediments from 6 sites in the southern basin for diverse biogeochemical (loss-on-ignition, biogenic silica, pigments) and microfossil (diatoms, chrysophytes) remains to reconstruct the environmental history of the lake. Our objectives were to quantify the magnitude and direction of historical trophic change and evaluate reasons for an apparent lack of basin recovery following documented nutrient diversion. Evidence came from fossil indicator profiles and comparisons of these long-term trends with historical land use and monitoring data. Results indicate major changes in algal communities during and following peak nutrient loading in the mid-20th century as well as more recent increases in colonial cyanobacteria and high-nutrient diatom taxa. Combined, fossil indicators reflect an anthropogenically enriched system that has undergone substantial ecological change, particularly since ∼1980, due to multiple drivers. Physical changes in lake thermal regime resulting from climate warming may be exacerbating internal phosphorus release from sediments, thereby lowering nitrogen:phosphorus ratios and enhancing cyanobacterial abundance. These drivers of lake condition in the lake may apply to other large shallow lakes that exhibit only limited biological recovery from reduced external nutrient loading.

When discharged into surface waters via wastewater effluents, triclosan, the antimicrobial agent in handsoaps, and chlorinated triclosan derivatives (CTDs, formed during disinfection with chlorine) react photochemically to form polychlorinated dibenzo-p-dioxins. To evaluate the historical exposure of waters to these compounds, the levels of triclosan, CTDs, and their derived dioxins were determined in sediment cores collected from wastewater-impacted Minnesota lakes. The accumulation rates and temporal trends of triclosan, CTDs, and dioxins in aquatic sediments were found to be a function of historical wastewater treatment operations and lake system scale. Cores collected from large-scale riverine systems with many wastewater sources recorded increasing concentrations of triclosan, CTDs, and their derived dioxins since the patent of triclosan in 1964. In small-scale lakes with a single wastewater source, the trends were directly attributed to increased triclosan use, local improvements in treatment, and changes in wastewater disinfection since the 1960s. In the lake with no wastewater input, no triclosan or CTDs were detected. Overall, concentrations of triclosan, CTDs, and their dioxins were higher in small-scale systems, reflecting a greater degree of wastewater impact. In cores collected in northern MN, the four dioxins derived from triclosan are present prior to the patent of triclosan, suggesting a secondary source. It is clear, however, that triclosan and CTDs are the dominant source of these congeners after 1965 in systems impacted by wastewater.

In low-sulfate and sulfate-limited freshwater sediments, sulfate loading increases the production of methylmercury (MeHg), a potent and bioaccumulative neurotoxin. Sulfate loading to anoxic sediments leads to sulfide production that can inhibit mercury methylation, but this has not been commonly observed in freshwater lakes and wetlands. In this study, sediments were collected from sulfate-impacted, neutral pH, surface water bodies located downstream from ongoing and historic mining activities to examine how chronic sulfate loading produces porewater sulfide, and influences MeHg production and transport. Sediments were collected over two years, during several seasons from lakes with a wide range of overlying water sulfate concentration. Samples were characterized for in-situ solid phase and porewater MeHg, Hg methylation potentials via incubations with enriched stable Hg isotopes, and sulfur, carbon, and iron content and speciation. Porewater sulfide reflected historic sulfur loading and was strongly related to the extractable iron content of sediment. Overall, methylation potentials were consistent with the accumulation of MeHg on the solid phase, but both methylation potentials and MeHg were significantly lower at chronically sulfate-impacted sites with a low solid-phase Fe:S ratio. At these heavily sulfate-impacted sites that also contained elevated porewater sulfide, both MeHg production and partitioning are influenced: Hg methylation potentials and sediment MeHg concentrations are lower, but occasionally porewater MeHg concentrations in sediment are elevated, particularly in the spring. The dual role of sulfide as a ligand for inorganic mercury (decreasing bioavailability) and methylmercury (increasing partitioning into porewater) means that elucidating the role of iron and sulfur loads as they define porewater sulfide is key to understanding sulfate's influence on MeHg production and partitioning in sulfate-impacted freshwater sediment.

Data from 104 sediment cores from the Great Lakes and "inland lakes" in the region were compiled to assess historical and recent changes in mercury (Hg) deposition. The lower Great Lakes showed sharp increases in Hg loading c. 1850-1950 from point-source water dischargers, with marked decreases during the past half century associated with effluent controls and decreases in the industrial use of Hg. In contrast, Lake Superior and inland lakes exhibited a pattern of Hg loading consistent with an atmospheric source - gradual increases followed by recent (post-1980) decreases. Variation in sedimentary Hg flux among inland lakes was primarily attributed to the ratio of watershed area:lake area, and secondarily to a lake's proximity to emission sources. A consistent region-wide decrease (∼20%) of sediment-Hg flux suggests that controls on local and regional atmospheric Hg emissions have been effective in decreasing the supply of Hg to Lake Superior and inland lakes.

We report estimates of mercury (Hg) flux to the sediments of Lake Tahoe, California–Nevada: 2 and 15–20 µg/m2/year in preindustrial and modern sediments, respectively. These values result in a modern to preindustrial flux ratio of 7.5–10, which is similar to flux ratios recently reported for other alpine lakes in California, and greater than the value of 3 typically seen worldwide. We offer plausible hypotheses to explain the high flux ratios, including (1) proportionally less photoreduction and evasion of Hg with the onset of cultural eutrophication and (2) a combination of enhanced regional oxidation of gaseous elemental Hg and transport of the resulting reactive gaseous Hg to the surface with nightly downslope flows of air. If either of these mechanisms is correct, it could lead to local/regional solutions to lessen the impact of globally increasing anthropogenic emissions of Hg on Lake Tahoe and other alpine ecosystems.

Long-term changes in sediment and phosphorus loading to the upper Mississippi River were quantified from an array of 25 sediment cores from Lake Pepin, a large natural impoundment downstream of the Minneapolis-St Paul metropolitan area. Cores were dated and stratigraphically correlated using 210Pb, 137Cs, 14C, magnetic susceptibility, pollen analysis, and loss-on-ignition. All cores show a dramatic increase in sediment accumulation beginning with European settlement in 1830. Accumulation rates are highest and show the greatest post-settlement increases in the upper end of the lake. Present-day sediment-phosphorus concentrations are roughly twice those of pre-settlement times, and the Fe/Al-bound fraction makes up a greater portion of the total. Diatom assemblages record a marked increase in nutrient availability over the last 200 years, changing from clear-water benthic forms and mesotrophic planktonic taxa in pre-settlement times to exclusively planktonic assemblages characteristic of highly eutrophic conditions today. Lake-water total-phosphorus concentrations, estimated by weighted averaging regression and calibration, increased from 50 to 200 μg l−1 during this period. Sediment loading to Lake Pepin from the Mississippi River has increased by an order of magnitude since 1830. Modern fluxes are about 900,000 metric tons annually, and are more than 80% detrital mineral matter. About 17% of the lake’s volume in 1830 has been replaced by sediment, and at current accumulation rates the remainder will be filled in another 340 years. Phosphorus accumulation in Lake Pepin sediments has increased 15-fold since 1830, rising from 60 to 900 metric tons annually. This rise represents a sevenfold increase in phosphorus loading from the Mississippi River coupled with more efficient retention of phosphorus inflows by bottom sediments. More efficient trapping of phosphorus in Lake Pepin over the last century resulted from higher rates of sediment burial. The most dramatic changes in nutrient and sediment inputs to Lake Pepin have occurred since 1940, although gradual increases began shortly following European settlement. Sediment accumulation rates rose sharply between 1940 and 1970 and then leveled off, while phosphorus inflows record their largest increases after 1970.

Lake-sediment records across the Northern Hemisphere show increases in atmospheric deposition of anthropogenic mercury (Hg) over the last 150 years. Most of the previous studies have examined remote lakes affected by the global atmospheric Hg reservoir. In this study, we present Hg flux records from lakes in an urban/suburban setting of central New York affected also by local and regional emissions. Sediment cores were collected from the Otisco and Skaneateles lakes from the Finger Lakes region, Cross Lake, a hypereutrophic lake on the Seneca River, and Glacial Lake, a small seepage lake with a watershed that corresponds with the lake area. Sediment accumulation rates and dates were established by 210Pb. The pre-anthropogenic regional atmospheric Hg flux was estimated to be 3.0 μg m−2 yr−1 from Glacial Lake, which receives exclusively direct atmospheric deposition. Mercury fluxes peaked during 1971–2001, and were 3 to more than 30 times greater than pre-industrial deposition. Land use change and urbanization in the Otisco and Cross watersheds during the last century likely enhanced sediment loads and Hg fluxes to the lakes. Skaneateles and Glacial lakes have low sediment accumulation rates, and thus are excellent indicators for atmospheric Hg deposition. In these lakes, we found strong correlations with emission records for the Great Lakes region that markedly increased in the early 1900s, and peaked during WWII and in the early 1970s. Declines in modern Hg fluxes are generally evident in the core records. However, the decrease in sediment Hg flux at Glacial Lake was interrupted and has increased since the early 1990s probably due to the operation of new local emission sources. Assuming the global Hg reservoir tripled since the pre-industrial period, the contribution of local and regional emission sources to central New York lakes was estimated to about 80% of the total atmospheric Hg deposition.

The history of mercury (Hg) inputs to 55 Minnesota (U.S.A.) lakes was reconstructed from 210Pb (lead-210)dated sediment cores to determine if erosion of soils from agriculture and urbanization contributes a significant loading of Hg to lakes, and whether lakes near Hg-emitting facilities receive appreciable local atmospheric deposition. Modern (1994–1997) Hg accumulation and Hg flux ratios (modern : preindustrial) increase significantly with the percentage of watershed area under urban or agricultural land-use. Both past and modern Hg accumulation rates are strongly correlated with the flux of total aluminum (Al), a tracer for soil erosion. Modern Hg accumulation rates are substantially higher in the Minneapolis–St. Paul metropolitan area and in agriculturally dominated south-central Minnesota than in the forested northeastern part of the state, largely because of erosional inputs of soil-bound Hg from disturbed catchments. Modern Hg loading from direct atmospheric deposition is also greater in the metropolitan region than in the rural areas of south-central or northeastern Minnesota. However, some of the excess loading to urban lakes may also be a legacy of formerly high Hg deposition to urban watersheds. A decline in local Hg emissions from peak levels in the 1970s coupled with reduced erosional inputs has cut Hg loading to many metro-area lakes by more than half.

Mercury contamination of fish is a global problem. Consumption of contaminated fish is the primary route of methylmercury exposure in humans and is detrimental to health. Newly mandated reductions in anthropogenic mercury emissions aim to reduce atmospheric mercury deposition and thus mercury concentrations in fish. However, factors other than mercury deposition are important for mercury bioaccumulation in fish. In the lakes of Isle Royale, U.S.A., reduced rates of sulfate deposition since the Clean Air Act of 1970 have caused mercury concentrations in fish to decline to levels that are safe for human consumption, even without a discernible decrease in mercury deposition. Therefore, reductions in anthropogenic sulfur emissions may provide a synergistic solution to the mercury problem in sulfate-limited freshwaters.

Northern forests are important ecosystems for carbon (C) cycling and lakes within them process and bury large amounts of organic-C. Current burial estimates are poorly constrained and may discount other shifts in organic-C burial driven by global change. Here we analyse a suite of northern lakes to determine trends in organic-C burial throughout the Anthropocene. We found burial rates increased significantly over the last century and are up to five times greater than previous estimates. Despite a correlation with temperature, warming alone did not explain the increase in burial, suggesting the importance of other drivers including atmospherically deposited reactive nitrogen. Upscaling mean lake burial rates for each time period to global northern forests yields up to 4.5 Pg C accumulated in the last 100 years—20% of the total burial over the Holocene. Our results indicate that lakes will become increasingly important for C burial under future global change scenarios., The rate at which carbon burial has changed in lakes in response to human-induced global change is poorly understood. Here, the authors show that carbon burial has increased significantly in remote northern lakes along with increased nitrogen deposition and warming over the last century.

Reconstructing recent limnological history often relies on lead-210 dating to accurately ascribe a chronology to a sediment profile. In Lake Okeechobee, Florida, a large, shallow subtropical lake that may experience severe mixing, multiple dating methods are required to confirm that conformable sedimentation has been preserved and that the assumptions of the 210Pb method are satisfied. This study uses stratigraphic profiles of heavy metals, 137Cs, PCBs and pollen as independent dating markers to validate the sediment chronology as determined by 210Pb for three cores from the central mud zone of the lake. Unsupported 210Pb and most dating markers show distinct concentration/depth profiles, suggesting that the sediments have not been severely mixed for at least the last 75 years. Onset and maximum activity of the radioisotope 137Cs in the cores coincides with the 210Pb-dated interval of 1945–1970. This agrees well with the known timing of atmospheric deposition of 137Cs that resulted from above-ground nuclear testing during late 1940s until 1963. Sediment core profiles of atmospherically deposited metals such as Zn and Pb, which reflect regional increases during industrialization and decreases after regulation in the 1970s, exhibit expected concentration increases and peaks coinciding within 5–15 years of the predicted 210Pb dates. Uranium, a contaminant in some phosphate fertilizers, shows large concentration increases at core depths dated to be about 1950 by 210Pb, matching the intensification of agriculture after WWII. PCBs, which are expected to peak in the early 1970s, were measured in one core, and the observed peak corresponds to a 210Pb date of about 1960. Pollen makers were unable to verify specific events, but increases in disturbance taxa and declines in native types correspond generally with the expected dates assigned by 210Pb dating. Conformity between the 210Pb defined dates and independent markers of < ±15 years confirm that Lake Okeechobee sediments do preserve a sequential and reliable stratigraphic history of the lake, useful for reconstructing past limnological conditions.

Mercury (HgT) and methylmercury (MeHg) were measured at 1-2 cm resolution in sediment porewater and sediment cores from Spring Lake in the Marcell Experimental Forest of northern Minnesota. Recent sediment accumulation of HgT was 21.4 microg m(-2) yr(-1) (1990-2000), 2 orders of magnitude greater than the accumulation of MeHg (0.20 microg m(-2) yr(-1)). The highest solid phase concentrations of MeHg were observed persistently at the sediment surface and declined sharply with depth. Porewater profiles showed a small diffusive flux of MeHg from sediment to water (5 ng m(-2) month(-1)). Springtime porewater concentrations of MeHg were relatively low (approximately 0.5 ng L(-1)) and increased by late summer to early fall (1.5-2.2 ng L(-1)), showing distinct peaks roughly correlated with maxima in sulfate reducing activity at 5 and 15 cm. Advective transport carrying MeHg deeper into the sediment was evident in summer and fall. The percent of HgT present as MeHg was highest in the water column above the sediment (10%) and decreased with sediment depth in both the solid and porewater phases. Sediments at this study site are a net sink for MeHg, although diagenetic processes of demethylation and methylation are evident within the lake-sediment environment.

Aqueous production and water-air exchange of elemental mercury (Hg 0 ) are important features of the environmental cycling of Hg. We investigated Hg 0 cycling in ten Arctic Alaskan lakes that spanned a wide range in physicochemical characteristics. Dissolved gaseous Hg (DGM, dominated by Hg 0 ) varied from 40 to 430 fM and averaged 200 fM. All surface waters were supersaturated relative to the atmosphere. DGM averaged 3 ± 2% of dissolved (i.e., filter passing) dissolved total mercury (DTM) and 15 ± 6% of dissolved labile Hg (DLM). In-lake DGM profiles generally followed the vertical distribution of light, indicating photoreduction of Hg(II) complexes as a source of Hg 0 . Additionally, DGM correlated linearly with DLM (r 2 = 0.82, p a (light attenuation coefficient; r 2 = 0.73, p 2 = 0.60, p = 0.02) suggests that solar radiation and dissolved organic matter control DGM production and its cycling. An average rate of DGM formation (0.6 ± 0.2% of DTM d −1 ; range, 0.20.8) was estimated by assuming steady state with the evasional rate. In-lake DGM formation occurs at lower rates in waters with greater suspended particulate matter and dissolved organic carbon (DOC), pointing to the significant role of organic matter plays in controlling DGM formation in these aquatic systems. Estimated evasional fluxes of Hg 0 (average, 140 ± 50 pmol m −2 d −1 ; range, 60–200) were comparable to those of temperate lakes (e.g., Wisconsin, Michigan). In arctic lakes, the rate of evasion during ice-free periods (7 ± 3 nmol m −2 yr −1 ) is similar to the atmospheric input of Hg (wet + dry) to the lakes based on levels in summertime precipitation but not including additional sources, e.g., springtime depletion.

Establishing management targets for lake nutrient inputs remains a major challenge to limnologists and resource managers concerned with the cultural eutrophication of lakes. In this study we used multiple sediment cores to reconstruct pre-Euroamerican (1650–1850) phosphorus (P) loading to Lake Volney, a hypereutrophic lake in Le Sueur County, Minnesota, and compared changes in P inputs to inferred changes in lake productivity based on biogenic silica (bSi). Euroamerican changes in land-use, as abstracted from census and tax records, were also compared with sedimentary proxies for soil erosion – loss-on-ignition and environmental magnetism. Whole-basin P accumulation in Lake Volney ranged from 0.31 – 0.39 g m−2 yr−1 prior to the arrival of Euroamerican agriculture in the 1850s. There-after P accumulation rose nearly three-fold largely due to increased fluxes of organic and non-apatite inorganic P. P inputs were highest (3.9 g m−2 yr−1) when organic, apatite and non-apatite P all peaked. Modern P a...

Lakes across the Northern Hemisphere have experienced enhanced atmospheric deposition of anthropogenically derived Hg for over 100 years. In the present study, we quantified Hg fluxes to the sediments of ten small drainage lakes across Vermont and New Hampshire, USA, for the period ∼1800 to present. Dates were established by 210Pb. Total Hg (HgT) fluxes to sediments ranged from 5 to 17 μg m−2 yr−1 during pre-industrial times, and from 21 to 83 μg m−2 yr−1 presently. Present-day HgT fluxes are between 2.1 to 6.9 times greater than pre-1850 fluxes. Current-day direct atmospheric Hg deposition to the study region was estimated at 21 μg m−2 yr−1, which agrees well with measured HgT deposition, when re-evasion of Hg is accounted for. Our data suggest that Hg fluxes to lake sediments have declined in recent decades, owing to reductions in atmospheric Hg deposition to the lake surface. Watershed export of atmospherically deposited Hg remains elevated relative to present-day deposition rates, which contributes to the impression that Hg retention by watershed soils has declined.

The distribution and deposition of sedimentary mercury in the Sudbury River were linked to an industrial complex (Nyanza site) that operated from 1917 through 1978. In two reservoirs just downstream from the Nyanza site, estimated rates of mercury accumulation increased markedly in the 1920s and 1930s, were greatest during 1976-1982, decreased within 5 years after industrial operations ceased, and have decreased further since capping of contaminated soil at the Nyanza site was completed in 1991. The most contaminated sediments were typically buried, yet the 0- to 1-cm stratum remained substantially contaminated in all cores. Mercury accumulating in the surficial, reservoir sediments was probably from continuing, albeit much lesser, inputs from the Nyanza site, whereas recent inputs to downstream wetland areas were attributed to recycling of sedimentary mercury or to mercury from unidentified local sources. In the reservoirs, burial of highly contaminated sediments is gradually decreasing the amount of sedimentary mercury available for methylation. In downstream wetlands, however, sedimentary mercury seemed to be more available than that in the reservoirs for physical transport and biogeochemical cycling.

An array of sediment cores was analyzed to determine historical trends in mercury (Hg) accumulation in Lake Pepin, a natural lake on the Upper Mississippi River. Whole-basin Hg accumulation rates increased from 3 kg/yr before European settlement (ca. 1830) to a maximum of 357 kg/yr in the 1960s. The recent Hg accumulation rate (110 kg/yr, 1990−1996) is experimentally indistinguishable from measured Hg loadings in the river entering the lake, indicating that accumulation rates in Lake Pepin correspond quantitatively to river loadings. The modern accumulation rate represents a decline of almost 70% from the peak value, reflecting large decreases in Hg inputs to the Mississippi River from industrial and municipal point sources in the metropolitan Minneapolis/St.Paul area upstream. A total of 18.1 t of Hg has been deposited in Lake Pepin since 1800; half of that (9.0 t) was deposited between 1940 and 1970, when regional growth accelerated rapidly but pollution control mechanisms were inadequate. Point sources...

Elevated levels of mercury in aquatic environments remote from industrial sources have been broadly attributed to long-range atmospheric transport and deposition of anthropogenic Hg. Evidence in support of this prevailing scientific viewglobal biogeochemical Hg models, sedimentary archives of historic Hg fluxes, and geographic trends in soil Hghave been challenged as being insuf ficiently rigorous to rule out the alternative explanation that natural geologic sources are the principal contributors of Hg in remote locations. In this review, we examine the weaknesses in interpretation and the choice of information that has been used to argue against atmospheric Hg contamination. Analytical advances in measuring trace levels of environmental Hg have greatly narrowed estimates of natural Hg fluxes, providing a clear measure of the relative magnitude of anthropogenic Hg emissions and deposition. Recent experimental results indicate that diagenetic processes cannot explain the mounting number of lake sediment an...

Phosphorus accumulation rates in depositional zone sediments of Lake Okeechobee were determined in 11 mud-zone cores and two peat-zone cores dated by 210Pb. Although difficulties were encountered in interpreting 210Pb data from some sites, reliable dating of sediments from the mud zone of this shallow lake is possible. Sediment accumulation rates in this zone have increased during the present century by an average of about twofold, and accumulation of organic sediments in the lake during pre-settlement times apparently was much slower than during the past century. Concentrations of all forms of sedimentary P but especially nonapatite inorganic-P and organic-P also have increased since pre-settlement times and especially since about 1940. Annual P accumulation rates in the lake's sediments have increased about fourfold during the 1900s, with most of the increase occurring in the past 40–50 years. The recent accumulation rate of sedimentary P (past ~ 10 years) agrees within a factor of 1.5 with the net retention of P in the lake calculated from published input-output mass balances.

Historic increases in atmospheric mercury deposition caused by anthropogenic emissions have been well documented from sediment cores from lakes and peatlands in North America and Europe. Few previous studies have addressed the question of whether mercury deposition has increased continuously to the present or whether it has declined in recent decades. We present stratigraphic data from a suite of Minnesota lakes that indicate mercury deposition peaked in the 1960s and 1970s, at least for the upper Midwest. Recent declines, which appear in both rural and urban lakes, are not evident in sediment cores from remote coastal lakes in southeastern Alaska. Because the Alaskan sites provide an integrated sample of mercury pollution in the Northern Hemisphere, these results imply that global mercury emissions have not abated and that decreased inputs to Midwestern lakes are caused by reduced emissions from regional sources. U.S. inventory data suggest that decreased emissions likely resulted from reduced industrial...

Both cinnabar (HgS) and metallic mercury (Hg(0)) were important resources throughout Andean prehistory. Cinnabar was used for millennia to make vermillion, a red pigment that was highly valued in pre-Hispanic Peru; metallic Hg(0) has been used since the mid-16th century to conduct mercury amalgamation, an efficient process of extracting precious metals from ores. However, little is known about which cinnabar deposits were exploited by pre-Hispanic cultures, and the environmental consequences of Hg mining and amalgamation remain enigmatic. Here we use Hg isotopes to source archeological cinnabar and to fingerprint Hg pollution preserved in lake sediment cores from Peru and the Galapagos Islands. Both pre-Inca (pre-1400 AD) and Colonial (1532-1821 AD) archeological artifacts contain cinnabar that matches isotopically with cinnabar ores from Huancavelica, Peru, the largest cinnabar-bearing district in Central and South America. In contrast, the Inca (1400-1532 AD) artifacts sampled are characterized by a unique Hg isotopic composition. In addition, preindustrial (i.e., pre-1900 AD) Hg pollution preserved in lake sediments matches closely the isotopic composition of cinnabar from the Peruvian Andes. Industrial-era Hg pollution, in contrast, is distinct isotopically from preindustrial emissions, suggesting that pre- and postindustrial Hg emissions may be distinguished isotopically in lake sediment cores.

Between 2001 and 2008 we experimentally manip- ulated atmospheric sulfate-loading to a small boreal peatland and monitored the resulting short and long-term changes in methylmercury (MeHg) production. MeHg concentrations and %MeHg (fraction of total-Hg (HgT) present as MeHg) in the porewaters of the experimental treatment reached peak values within a week of sulfate addition and then declined as the added sulfate disappeared. MeHg increased cumulatively over time in the solid-phase peat, which acted as a sink for newly produced MeHg. In 2006 a "recovery" treatment was created by discon- tinuing sulfate addition to a portion of the experimentally treated section to assess how MeHg production might respond to decreased sulfate loads. Four years after sulfate additions ceased, MeHg concentrations and %MeHg had declined significantly from 2006 values in porewaters and peat, but remained elevated relative to control levels. Mosquito larvae collected from each treatment at the end of the experiment exhibited HgT concentra- tions reflective of MeHg levels in the peat and porewaters where they were collected. The proportional responses of invertebrate HgT to sulfate deposition rates demonstrate that further controls on sulfur emissions may represent an additional means of miti- gating Hg contamination in fish and wildlife across low-sulfur landscapes.

Mercury (Hg) is of great environmental concern due to its transformation into the toxic methylmercury (MeHg) form that bioaccumulates within the food chain and causes health concerns for both humans and wildlife (U.S. Environmental Protection Agency 2002). Mercury can affect neurological development in fetuses and young children. In adults, exposure to Hg can lead to the deterioration of the nervous system, decreased sensory abilities, and a lack of muscle control (Ratcliffe et al. 1996). Methylmercury in fish poses a severe health risk for fish-eating animals such as otter, mink, bald eagle, kingfisher, osprey, and the common loon (Walcek et al. 2003), and even for fish themselves (Sandheinrich and Miller 2006). CONTENTS

We analyzed sediment cores collected from three equatorial zone lakes in the Rwenzori Mountains of Uganda for Hg and dated them using 210Pb. The results show that the lakes have been contaminated by anthropogenic Hg from atmospheric deposition and that the onset of Hg pollution in the region began at least by the late 19th century. Mercury accumulation in all sediment cores increased by about 3-fold since the mid-19th century, a similar increase to that shown in other remote regions worldwide. These results from tropical high-elevation sites are the first for this region and contribute to our understanding of global Hg pollution trends. The atmospheric boundary layer is at a higher altitude in equatorial areas than at midlatitudes, and therefore, Hg deposition in these regions may not be enhanced by diurnal penetration of tropospheric air and associated reactive gaseous mercury as has been reported for mountain lakes at higher latitudes. Furthermore, the relatively low abundance of atmospheric oxidants may limit the amount of gaseous elemental mercury oxidized to the reactive gaseous form in equatorial Africa. These Rwenzori Hg records therefore have important implications for the understanding of Hg dynamics at high elevations in equatorial regions.

Mercury contamination of remote lakes has been attributed to increasing deposition of atmospheric mercury, yet historic deposition rates and inputs from terrestrial sources are essentially unknown. Sediments of seven headwater lakes in Minnesota and Wisconsin were used to reconstruct regional modern and preindustrial deposition rates of mercury. Whole-basin mercury fluxes, determined from lake-wide arrays of dated cores, indicate that the annual deposition of atmospheric mercury has increased from 3.7 to 12.5 micrograms per square meter since 1850 and that 25 percent of atmospheric mercury deposition to the terrestrial catchment is exported to the lake. The deposition increase is similar among sites, implying regional or global sources for the mercury entering these lakes.

A peat core from a calcareous fen was used to assess past metal accumulation from atmospheric sources in northern Indiana. Total concentrations of Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, and Zn were measured at intervals along the core, which were dated by {sup 210}Pb, radiocarbon, and pollen analysis. The deposition of airborne metal particulates rose dramatically from presettlement levels as industrialization occurred upwind, with accumulation rates for some metals increasing by 2 orders of magnitude. Recent accumulation rates are about half of the peak rates of the 1970s, presumably because of emission controls and reduced production. This study, the first such record from a calcareous fen, should be less affected by postdepositional mobility than records from acidic peatlands. This method of retrospective, long-term monitoring of airborne particulates can be applied in many areas lacking such records.

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

Historical records of mercury (Hg) accumulation in lake sediments and peat bogs are often used to estimate human impacts on the biogeochemical cycling of mercury. On the basis of studies of lake sediments, modern atmospheric mercury deposition rates are estimated to have increased by a factor of 3-5 compared to background values: i.e., from about 3-3.5 microg Hg m(-2) yr(-1) to 10-20 microg Hg m(-2) yr(-1). However, recent studies of the historical mercury record in peat bogs suggest significantly higher increases (9-400 fold, median 40x), i.e., from about 0.6-1.7 microg Hg m(-2) yr(-1) to 8-184 microg Hg m(-2) yr(-1). We compared published data of background and modern mercury accumulation rates derived from globally distributed lake sediments and peat bogs and discuss reasons for the differences observed in absolute values and in the relative increase in the industrial age. Direct measurements of modern wet mercury deposition rates in remote areas are presently about 1-4 microg m(-2) yr(-1), but were possibly as high as 20 microg Hg m(-2) yr(-1) during the 1980s. These values are closer to the estimates of past deposition determined from lake sediments, which suggests that modern mercury accumulation rates derived from peat bogs tend to overestimate deposition. We suggest that smearing of 210Pb in the uppermost peat sections contributes to an underestimation of peat ages, which is the most important reason for the overestimation of mercury accumulation rates in many bogs. The lower background mercury accumulation rates in peat as compared to lake sediments we believe is the result of nonquantitative retention and loss of mercury during peat diagenesis. As many processes controlling time-resolved mercury accumulation in mires are still poorly understood, lake sediments appear to be the more reliable archive for estimating historical mercury accumulation rates.

Concentrations of methylmercury in game fish from many interior lakes in Voyageurs National Park (MN, U.S.A.) substantially exceed criteria for the protection of human health. We assessed the importance of atmospheric and geologic sources of mercuryto interior lakes and watersheds within the Park and identified ecosystem factors associated with variation in methylmercury contamination of lacustrine food webs. Geologic sources of mercury were small, based on analyses of underlying bedrock and C-horizon soils, and nearly all mercury in the 0- and A-horizon soils was derived from atmospheric deposition. Analyses of dated sediment cores from five lakes showed that most (63% +/- 13%) of the mercury accumulated in lake sediments during the 1900s was from anthropogenic sources. Contamination of food webs was assessed by analysis of whole, 1-year-old yellow perch (Perca flavescens), a regionally important prey fish. The concentrations of total mercury in yellow perch and of methylmercury in lake water varied substantially among lakes, reflecting the influence of ecosystem processes and variables that affect the microbial production and abundance of methylmercury. Models developed with the information-theoretic approach (Akaike Information Criteria) identified lake water pH, dissolved sulfate, and total organic carbon (an indicator of wetland influence) as factors influencing methylmercury concentrations in lake water and fish. We conclude that nearly all of the mercury in fish in this seemingly pristine

Atmospheric mercury is the dominant Hg source to fish in northern Minnesota and elsewhere. However, atmospherically derived Hg must be methylated prior to accumulating in fish. Sulfate-reducing bacteria are thought to be the primary methylators of Hg in the environment. Previous laboratory and field mesocosm studies have demonstrated an increase in methylmercury (MeHg) levels in sediment and peatland porewaters following additions of sulfate. In the current ecosystem-scale study, sulfate was added to half of an experimental wetland at the Marcell Experimental Forest located in northeastern Minnesota, increasing annual sulfate load by approximately four times relative to the control half of the wetland. Sulfate was added on four separate occasions during 2002 and delivered via a sprinkler system constructed on the southeast half (1.0 ha) of the S6 experimental wetland. MeHg levels were monitored in porewater and in outflow from the wetland. Prior to the first sulfate addition, MeHg concentrations (filtered, 0.7 microm) were not statistically different between the control (0.47 +/- 0.10 ng L(-1), n = 12; mean +/- one standard error) and experimental 0.52 +/- 0.05 ng L(-1), n = 18) halves. Following the first addition in May 2002, MeHg porewater concentrations increased to 1.63 +/- 0.27 ng L(-1) two weeks after the addition, a 3-fold increase. Subsequent additions in July and September 2002 did not raise porewater MeHg, but the applied sulfate was not observed in porewaters 24 h after addition. MeHg concentrations in outflow from the wetland also increased leading to an estimated 2.4x increase of MeHg flux from the wetland. Our results demonstrate enhanced methylation and increased MeHg concentrations within the wetland and in outflow from the wetland suggesting that decreasing sulfate deposition rates would lower MeHg export from wetlands.

We reconstruct from lake-sediment archives atmospheric Hg deposition to Arctic Alaska over the last several centuries and constrain a contemporary lake/watershed mass-balance with real-time measurement of Hg fluxes in rainfall, runoff, and evasion. Results indicate that (a) anthropogenic Hg impact in the Arctic is of similar magnitude to that at temperate latitudes; (b) whole-lake Hg sedimentation determined from 55 210Pb-dated cores from the five small lakes demonstrates a 3-fold increase in atmospheric Hg deposition since the advent of the Industrial Revolution; (c) because of high soil Hg concentrations and relatively low atmospheric deposition fluxes, erosional inputs to these lakes are more significant than in similar temperate systems; (d) volatilization accounts for about 20% of the Hg losses (evasion and sedimentation); and (e) another source term is needed to balance the evasional and sedimentation sinks. This additional flux (1.21+/-0.74 microg m(-2) yr(-1)) is comparable to direct atmospheric Hg deposition and may be due to some combination of springtime Arctic depletion and more generalized deposition of reactive gaseous Hg species.

[1] Using two different natural archiving media from remote locations, we have reconstructed the atmospheric deposition of mercury (Hg) over the last 800–1000 years in both hemispheres. This effort was designed (1) to quantify the historical variation and distributional patterns of atmospheric Hg fluxes in the midlatitudes of North America at Nova Scotia (N.S.) and at a comparable midlatitude region in the Southern Hemisphere at New Zealand (N.S.), (2) to identify and quantify the influence of anthropogenic and natural Hg contributions to atmospheric Hg fluxes, (3) to further investigate the suitability and comparability of our two selected media (lake sediments and ombrotrophic peat) for Hg depositional reconstructions, and (4) to assess the relative importance of wet and dry deposition to the study areas. Significant findings from the study include the following: (1) The lake sediments examined appear to faithfully record the contemporary flux of Hg from the atmosphere (e.g., 1997: N.S. Lakes: approximately 8 ± 3 μg m−2 yr−1; N.S. Rain: 8 μg m−2 yr−1). The upper 10 cm (approximately 10 yr) of ombrotrophic peat cores from Nova Scotia were dated using a biological chronometer (Polytrichum) and were also consistent with the flux data provided by current direct sampling of precipitation. These observations place limits on the contribution of dry deposition (40 ± 50% of wet flux). Unfortunately, the peat samples could not be dated below 10 cm. This was due to the apparent diagenetic mobility of the geochronological tracer (210Pb). (2) There is no evidence of a significant enhancement in the atmospheric Hg flux as a result of preindustrial (