Marine Hg Research Articles

Positive Δ199Hg anomalies in Mesozoic porphyry Mo deposits of Northeastern China and their implications to the metallogeny of arc-related hydrothermal systems at convergent margins

Mercury (Hg) isotopes display unique mass-independent isotope fractionation (MIF, reported as Δ199Hg), which is primarily generated via Hg photochemical processes in the land-ocean-atmosphere system. Magmatic and hydrothermal processes do not trigger MIF of Hg isotopes, therefore, Hg-MIF signals detected in deep reservoirs (mantle and crust) are theoretically sourced from recycled surface materials. Here, we observed positive Δ199Hg signals (0.10 ± 0.07‰, SD) in Mesozoic porphyry Mo deposits of NE China. These values correspond to the recently reported Δ199Hg signature of Mesozoic epithermal AuAg systems in NE China (Δ199Hg: 0.11 ± 0.07‰, SD), suggesting that both mineral systems receive large amounts of Hg from subducted marine materials, given that marine Hg has positive Δ199Hg composition. Our study thus provides novel geochemical evidence on the linkage between oceanic plate subduction and metallogeny of various hydrothermal systems at convergent margins. Subduction contributes large amounts of volatiles to arc magmas, which then release metal-rich magmatic-hydrothermal fluids of the porphyry to epithermal ore deposit spectrum.

Mercury isotope compositions in seawater and marine fish revealed the sources and processes of mercury in the food web within differing marine compartments.

Anthropogenic activities and climate change have significantly increased mercury (Hg) levels in seawater. However, the processes and sources of Hg in differing marine compartments (e.g. estuary, marine continental shelf (MCS) or pelagic area) have not been well studied, which makes it difficult to understand Hg cycling in marine ecosystems. To address this issue, the total Hg (THg) concentration, methylmercury (MeHg) concentration and stable Hg isotopes were determined in seawater and fish samples collected from differing marine compartments of the South China Sea (SCS). The results showed that the estuarine seawater exhibited substantially higher THg and MeHg concentrations than those in the MCS and pelagic seawater. Significantly negative δ202Hg (-1.63‰ ± 0.42‰) in estuarine seawater compared with that in pelagic seawater (-0.58‰ ± 0.08‰) may suggest watershed input and domestic sewage discharge of Hg in the estuarine compartment. The Δ199Hg value in estuarine fish (0.39‰ ± 0.35‰) was obviously lower than that in MCS (1.10‰ ± 0.54‰) and pelagic fish (1.15‰ ± 0.46‰), which showed that relatively little MeHg photodegradation occurred in the estuarine compartment. The Hg isotope binary mixing model based on Δ200Hg revealed that approximately 74% MeHg in pelagic fish is derived from atmospheric Hg(II) deposition, and over 60% MeHg in MCS fish is derived from sediments. MeHg sources for estuarine fish may be highly complex (e.g. sediment or riverine/atmospheric input) and further investigations are warranted to clarify the contribution of each source. Our study showed that Hg stable isotopes in seawater and marine fish can be used to identify the processes and sources of Hg in different marine compartments. This finding is of great relevance to the development of marine Hg food web models and the management of Hg in fish.

Chemostratigraphy and source of mercury in the Tropical Western Pacific over the past 600 kyr

To characterize the geochemical records of mercury (Hg) in the western tropical Pacific in the last 600 ka, the total concentration of Hg, and its isotopic compositions in Hole B at Site U1486 from the Western Pacific Warm Pool (WPWP) were determined. Some marked positive values of Δ199Hg in this core, and some Δ200Hg also exhibit significant positive, which resultes from the photoreduction of the volcanic Hg deposits through the long-range atmospheric transportation. In addition, dual odd-even Hg isotopes (Δ199Hg and Δ200Hg) database was also compiled to account for quantitative contributions to potential Hg sources, including marine Hg source, atmospheric Hg deposition, volcanic Hg source, and terrigenous Hg inputs. This study presents that sedimentary Hg in the core Hole B at Site U1486 originates mainly from the marine Hg source with a mean of 64.13%, which is similar to the changes of paleo-productivity in the WPWP with a character of the glacial-interglacial variation. The contributions of atmospheric Hg deposition, volcanic Hg source, and terrigenous Hg inputs represented approximately 17.88%, 10.37%, and 7.87% of the total Hg burden in this core, respectively. During the last 100 ka, the contribution of volcanic Hg source has increased overall, suggesting the increase of volcanic activity. And the amount of atmospheric Hg deposition in this core also generally increased during this period, which was in resonance with the eolian dust in the western Pacific. Furthermore, terrigenous Hg inputs in this study could be related to intensity of monsoon precipitation with an overall increasing trend. In this study, volcanic activities in sediment cores from the western Pacific can provide an additional and independent tool for the precise dating and synchronization of paleoenvironmental changes in these climatically significant regions.

Climate-driven changes of global marine mercury cycles in 2100

Human exposure to monomethylmercury (CH3Hg), a potent neurotoxin, is principally through the consumption of seafood. The formation of CH3Hg and its bioaccumulation in marine food webs experience ongoing impacts of global climate warming and ocean biogeochemistry alterations. Employing a series of sensitivity experiments, here we explicitly consider the effects of climate change on marine mercury (Hg) cycling within a global ocean model in the hypothesized twenty-first century under the business-as-usual scenario. Even though the overall prediction is subjected to significant uncertainty, we identify several important climate change impact pathways. Elevated seawater temperature exacerbates elemental Hg (Hg0) evasion, while decreased surface wind speed reduces air-sea exchange rates. The reduced export of particulate organic carbon shrinks the pool of potentially bioavailable divalent Hg (HgII) that can be methylated in the subsurface ocean, where shallower remineralization depth associated with lower productivity causes impairment of methylation activity. We also simulate an increase in CH3Hg photodemethylation potential caused by increased incident shortwave radiation and less attenuation by decreased sea ice and chlorophyll. The model suggests that these impacts can also be propagated to the CH3Hg concentration in the base of the marine food web. Our results offer insight into synergisms/antagonisms in the marine Hg cycling among different climate change stressors.

Mantle Hg isotopic heterogeneity and evidence of oceanic Hg recycling into the mantle

The geochemical cycle of mercury in Earth’s surface environment (atmosphere, hydrosphere, biosphere) has been extensively studied; however, the deep geological cycling of this element is less well known. Here we document distinct mass-independent mercury isotope fractionation (expressed as Δ199Hg) in island arc basalts and mid-ocean ridge basalts. Both rock groups show positive Δ199Hg values up to 0.34‰ and 0.22‰, respectively, which deviate from recent estimates of the primitive mantle (Δ199Hg: 0.00 ± 0.10‰, 2 SD)1. The positive Δ199Hg values indicate recycling of marine Hg into the asthenospheric mantle. Such a crustal Hg isotope signature was not observed in our samples of ocean island basalts and continental flood basalts, but has recently been identified in canonical end-member samples of the deep mantle1, therefore demonstrating that recycling of mercury can affect both the upper and lower mantle. Our study reveals large-scale translithospheric Hg recycling via plate tectonics.

Anthropogenic and Climatic Drivers of Long-Term Changes of Mercury and Feeding Ecology in Arctic Beluga (Delphinapterus leucas) Populations.

We assessed long-term changes in the feeding ecology and mercury (Hg) accumulation in Eastern High Arctic-Baffin Bay beluga (Delphinapterus leucas) using total Hg and stable isotope (δ13C, δ15N) assays in teeth samples from historical (1854-1905) and modern (1985-2000) populations. Mean δ13C values in teeth declined significantly over time, from -13.01 ± 0.55‰ historically to -14.41 ± 0.28‰ in 2000, while no consistent pattern was evident for δ15N due to high individual variability within each period. The temporal shift in isotopic niche is consistent with beluga feeding ecology changing in recent decades to a more pelagic and less isotopically diverse diet or an ecosystem wide change in isotope profiles. Mercury concentrations in modern beluga teeth were 3-5 times higher on average than those in historical beluga. These results are similar to the long-term trends of Hg and feeding ecology reported in other beluga populations and in other Arctic marine predators. Similar feeding ecology shifts across regions and species indicate a consistent increased pelagic diet response to climate change as the Arctic Ocean progressively warmed and lost sea ice. Previously, significant temporal Hg increase in beluga and other Arctic animals was attributed solely to direct inputs of anthropogenic Hg from long-range sources. Recent advances in understanding the Arctic marine Hg cycle suggest an additional, complementary possibility─increased inputs of terrestrial Hg of mixed anthropogenic-natural origin, mobilized from permafrost and other Arctic soils by climate warming. At present, it is not possible to assign relative importance to the two processes in explaining the rise of Hg concentrations in modern Arctic marine predators.

Coprecipitation of Mercury from Natural Iodine-Containing Seawater for Accurate Isotope Measurement.

Oceans play a key role in the global mercury (Hg) cycle, but studies on Hg isotopes in seawater are rare due to the extremely low Hg concentration and the lack of a good preconcentration method. Here, we introduce a new coprecipitation method for separating and preconcentrating Hg from seawater for accurate isotope measurement. The coprecipitation was achieved by sequential addition of 0.5 mL of 0.5 M CuSO4, 1 mL of 0.5 M Na2S, and 1 mL of 0.5 M CuSO4 reagents, which allowed for quantitatively precipitating Hg from up to 10 L of seawater. The protocol was validated by testing synthetic solutions with varying Hg and iodide (I-) concentrations and by comparing the reaction times of various reagents added. The method resulted in a quantitative recovery of 98 ± 12% (n = 32, two standard deviations, 2 SD) and a relatively low procedure blank (103 pg of Hg, n = 8). The precipitates were filtrated and analyzed for Hg isotopes. Repeated measurements of synthetic seawaters spiked with certificated standard materials (NIST 3133 and 3177) using the entire method gave identical Hg isotope ratios with near-quantitative Hg recovery, indicating no isotope fractionation during preconcentration. A total of six nearshore seawater samples from the Yellow Sea and the Bohai Sea (China) were analyzed using the coprecipitation method. The data showed a large fractionation of Hg isotopes and revealed the possible impact of both atmospheric and anthropogenic inputs to the coastal seawater Hg budget, implying the potential application of this method in studying marine Hg systematics and global Hg cycling.

Mercury stable isotopes constrain atmospheric sources to the ocean.

Human exposure to toxic mercury (Hg) is dominated by the consumption of seafood1,2. Earth system models suggest that Hg in marine ecosystems is supplied by atmospheric wet and dry Hg(II) deposition, with a three times smaller contribution from gaseous Hg(0) uptake3,4. Observations of marine Hg(II) deposition and Hg(0) gas exchange are sparse, however5, leaving the suggested importance of Hg(II) deposition6 ill-constrained. Here we present the first Hg stable isotope measurements of total Hg (tHg) in surface and deep Atlantic and Mediterranean seawater and use them to quantify atmospheric Hg deposition pathways. We observe overall similar tHg isotope compositions, with median Δ200Hg signatures of 0.02‰, lying in between atmospheric Hg(0) and Hg(II) deposition end-members. We use a Δ200Hg isotope mass balance to estimate that seawater tHg can be explained by the mixing of 42% (median; interquartile range,24-50%) atmospheric Hg(II) gross deposition and 58% (50-76%) Hg(0) gross uptake. We measure and compile additional, global marine Hg isotope data including particulate Hg, sediments and biota and observe a latitudinal Δ200Hg gradient that indicates larger ocean Hg(0) uptake at high latitudes. Our findings suggest that global atmospheric Hg(0) uptake by the oceans is equal to Hg(II) deposition, which has implications for our understanding of atmospheric Hg dispersal and marine ecosystem recovery.

Mercury methylation by metabolically versatile and cosmopolitan marine bacteria

Microbes transform aqueous mercury (Hg) into methylmercury (MeHg), a potent neurotoxin that accumulates in terrestrial and marine food webs, with potential impacts on human health. This process requires the gene pair hgcAB, which encodes for proteins that actuate Hg methylation, and has been well described for anoxic environments. However, recent studies report potential MeHg formation in suboxic seawater, although the microorganisms involved remain poorly understood. In this study, we conducted large-scale multi-omic analyses to search for putative microbial Hg methylators along defined redox gradients in Saanich Inlet, British Columbia, a model natural ecosystem with previously measured Hg and MeHg concentration profiles. Analysis of gene expression profiles along the redoxcline identified several putative Hg methylating microbial groups, including Calditrichaeota, SAR324 and Marinimicrobia, with the last the most active based on hgc transcription levels. Marinimicrobia hgc genes were identified from multiple publicly available marine metagenomes, consistent with a potential key role in marine Hg methylation. Computational homology modelling predicts that Marinimicrobia HgcAB proteins contain the highly conserved amino acid sites and folding structures required for functional Hg methylation. Furthermore, a number of terminal oxidases from aerobic respiratory chains were associated with several putative novel Hg methylators. Our findings thus reveal potential novel marine Hg-methylating microorganisms with a greater oxygen tolerance and broader habitat range than previously recognized.

Unequal Anthropogenic Enrichment of Mercury in Earth’s Northern and Southern Hemispheres

Remote Northern Hemisphere (NH) and Southern Hemisphere (SH) lake sediment and peat records of mercury (Hg) deposition have shown a ×3 to ×5 Hg enrichment since pre-industrial times (<1880 AD), leading to the perception that global atmospheric Hg enrichment is moderate and uniform across the hemispheres. Anthropogenic Hg emissions in the NH are, however, approximately 4 times higher than those in the SH. Here, we reconstruct atmospheric Hg deposition in four remote SH peatlands and review sediment and peat Hg records from both hemispheres. We observe a ×4 all-time enrichment in SH Hg deposition from pre-anthropogenic (<1450 AD) to the late 20th-century periods, which is lower than the large ×16 all-time enrichment in NH Hg deposition. We attribute this difference to lower anthropogenic Hg emissions in the SH, and higher natural atmospheric SH Hg concentrations, supported by ×2 higher natural background Hg accumulation in SH peat records. We suggest that the higher SH natural atmospheric Hg deposition reflects the SH land-ocean distribution, and is driven by important SH marine Hg emissions. Our findings indicate that atmospheric Hg background levels and anthropogenic enrichment in both hemispheres are different and should be taken into account in international Hg assessments and environmental policy.

Distribution of mercury species in the Western Arctic Ocean (U.S. GEOTRACES GN01)

Mercury (Hg) in the Arctic Ocean is a concern due to unusually high concentrations of monomethylmercury (MMHg) in fish and marine animals. Increased human exposure from consumption of these animals is a significant health concern that is related to Hg contamination in nature. Most Arctic marine Hg research has investigated the amounts, distributions, and cycling in animals, snow, and ice, while few studies have examined the aqueous behavior and fate of Hg in the polar ocean. Here we present the most comprehensive dataset published to date detailing Hg speciation and distribution of elemental Hg (Hg0), dimethylmercury (DMHg), and filtered and particulate total Hg and MMHg in the western Arctic Ocean. This data was obtained as part of the U.S. Arctic GEOTRACES cruise (GN01) in 2015. Many water masses sampled appeared to be enriched with anthropogenic Hg. The Transpolar Drift supplied HgT and Hg0 to the central Arctic Ocean, but not methylated Hg. Gaseous Hg0, but not DMHg, was elevated in surface waters under the ice cover. Monomethylmercury levels, which averaged 0.054 ± 0.050 pM, are lower than other major ocean basins, suggesting ambient MMHg levels in western Arctic Ocean seawater do not by themselves explain anomalously high Hg in Arctic animals.

Dissolved Gaseous Mercury Production at a Marine Aquaculture Site in the Mercury-Contaminated Marano and Grado Lagoon, Italy.

Dissolved gaseous mercury (DGM) production was examined in relation to ultraviolet radiation within a marine aquaculture site in the contaminated Marano and Grado Lagoon (Italy). The measured rates of DGM production relative to time elapsed (17.06 and 20.68pgh-1, respectively) were substantially (6-20 times) higher than what has been observed in other marine Hg studies. We measured similar levels of DGM relative to dissolved total mercury (THgD) (0.84%-8.91%) at these sites in comparison to uncontaminated marine sites, however relative to other moderately-contaminated marine sites in Portugal the % DGM/THgD was high. These results suggest a substantial capacity for Hg volatilization from these highly contaminated lagoons to the atmosphere due to photoreduction mechanisms.

Modelling the mercury stable isotope distribution of Earth surface reservoirs: Implications for global Hg cycling

Abstract Mercury (Hg) stable isotopes are useful to understand Hg biogeochemical cycling because physical, chemical and biological processes cause characteristic Hg isotope mass-dependent (MDF) and mass-independent (MIF) fractionation. Here, source Hg isotope signatures and process-based isotope fractionation factors are integrated into a fully coupled, global atmospheric-terrestrial-oceanic box model of MDF (δ202Hg), odd-MIF (Δ199Hg) and even-MIF (Δ200Hg). Using this bottom-up approach, we find that the simulated Hg isotope compositions are inconsistent with the observations. We then fit the Hg isotope enrichment factors for MDF, odd-MIF and even-MIF to observational Hg isotope constraints. The MDF model suggests that atmospheric Hg0 photo-oxidation should enrich heavy Hg isotopes in the reactant Hg0, in contrast to the experimental observations of Hg0 photo-oxidation by Br. The fitted enrichment factor of terrestrial Hg0 emission in the odd-MIF model (5‰) is likely biased high, suggesting that the terrestrial Hg0 emission flux (160 Mg yr−1) used in our standard model is underestimated. In the even-MIF model, we find that a small positive atmospheric Hg0 photo-oxidation enrichment factor (0.22‰) along with enhanced atmospheric HgII photo-reduction and atmospheric Hg0 dry deposition (foliar uptake) fluxes to the terrestrial reservoir are needed to match Δ200Hg observations. Marine Hg isotope measurements are needed to further expand the use of Hg isotopes in understanding global Hg cycling.

Transfer of marine mercury to mountain lakes

Stocking is a worldwide activity on geographical and historical scales. The rate of non-native fish introductions have more than doubled over the last decades yet the effect on natural ecosystems, in the scope of biologically mediated transport and biomagnification of Hg and Hg-isotopes, is unknown. Using geochemistry (THg) and stable isotopes (N, Sr and Hg), we evaluate natal origin and trophic position of brown trout (Salmo trutta fario), as well as mercury biomagnification trends and potential pollution sources to three high-altitude lakes. Farmed trout show Hg-isotope signatures similar to marine biota whereas wild trout shows Hg-isotope signatures typical of fresh water lakes. Stocked trout initially show Hg-isotope signatures similar to marine biota. As the stocked trout age and shifts diet to a higher trophic level, THg concentrations increase and the marine Hg isotope signatures, induced via farm fish feed, shift to locally produced MeHg with lower δ202Hg and higher Δ199Hg. We conclude that stocking acts a humanly induced biovector that transfers marine Hg to freshwater ecosystems, which is seen in the Hg-isotopic signature up to five years after stocking events occurred. This points to the need of further investigations of the role of stocking in MeHg exposure to freshwater ecosystems.

Mercury content in Atlantic sediments as a new indicator of the enlargement and reduction of Northern Hemisphere ice sheets

ABSTRACTThe total mercury content of Quaternary sediments over the last 1.1 Ma from IODP Site U1308 drilled in the North Atlantic Ocean has changed, varying with periodicities of 100 000 and 41 000 years. The Hg content of the sediment increased during glacial periods, associated with increases in ice‐rafted debris (IRD), and correlates positively with the total organic carbon (TOC) content and inversely with the absolute abundance of surface‐dwelling nannoplankton species. TOC/total nitrogen ratios and δ13Corg values of TOC indicate that the TOC deposited during glacial periods was marine and associated with increased Hg deposition. These observations suggest that marine Hg is incorporated into the organic matter produced by deep‐dwelling phytoplankton in the lower photic zone. Mercury‐ and IRD‐bearing icebergs flowed out to this area during glacial periods melt, increasing the Hg content of photic water, and depositing IRD on the ocean floor, where increased marine Hg during glacial periods was consumed by deep‐dwelling phytoplankton. Therefore, the change in the sediment Hg content from the North Atlantic Ocean is controlled by climatic change and can be used as a chemical indicator of Northern Hemisphere ice sheet variability.

Hg Stable Isotope Time Trend in Ringed Seals Registers Decreasing Sea Ice Cover in the Alaskan Arctic

Decadal time trends of mercury (Hg) concentrations in Arctic biota suggest that anthropogenic Hg is not the single dominant factor modulating Hg exposure to Arctic wildlife. Here, we present Hg speciation (monomethyl-Hg) and stable isotopic composition (C, N, Hg) of 53 Alaskan ringed seal liver samples covering a period of 14 years (1988-2002). In vivo metabolic effects and foraging ecology explain most of the observed 1.6 ‰ variation in liver δ(202)Hg, but not Δ(199)Hg. Ringed seal habitat use and migration were the most likely factors explaining Δ(199)Hg variations. Average Δ(199)Hg in ringed seal liver samples from Barrow increased significantly from +0.38 ± 0.08‰ (±SE, n = 5) in 1988 to +0.59 ± 0.07‰ (±SE, n = 7) in 2002 (4.1 ± 1.2% per year, p < 0.001). Δ(199)Hg in marine biological tissues is thought to reflect marine Hg photochemistry before biouptake and bioaccumulation. A spatiotemporal analysis of sea ice cover that accounts for the habitat of ringed seals suggests that the observed increase in Δ(199)Hg may have been caused by the progressive summer sea ice disappearance between 1988 and 2002. While changes in seal liver Δ(199)Hg values suggests a mild sea ice control on marine MMHg breakdown, the effect is not large enough to induce measurable HgT changes in biota. This suggests that Hg trends in biota in the context of a warming Arctic are likely controlled by other processes.

Shallow methylmercury production in the marginal sea ice zone of the central Arctic Ocean.

Methylmercury (MeHg) is a neurotoxic compound that threatens wildlife and human health across the Arctic region. Though much is known about the source and dynamics of its inorganic mercury (Hg) precursor, the exact origin of the high MeHg concentrations in Arctic biota remains uncertain. Arctic coastal sediments, coastal marine waters and surface snow are known sites for MeHg production. Observations on marine Hg dynamics, however, have been restricted to the Canadian Archipelago and the Beaufort Sea (<79°N). Here we present the first central Arctic Ocean (79–90°N) profiles for total mercury (tHg) and MeHg. We find elevated tHg and MeHg concentrations in the marginal sea ice zone (81–85°N). Similar to other open ocean basins, Arctic MeHg concentration maxima also occur in the pycnocline waters, but at much shallower depths (150–200 m). The shallow MeHg maxima just below the productive surface layer possibly result in enhanced biological uptake at the base of the Arctic marine food web and may explain the elevated MeHg concentrations in Arctic biota. We suggest that Arctic warming, through thinning sea ice, extension of the seasonal sea ice zone, intensified surface ocean stratification and shifts in plankton ecodynamics, will likely lead to higher marine MeHg production.

Concentrations of mercury in tissues of striped dolphins suggest decline of pollution in Mediterranean open waters

The Mediterranean is a semi-enclosed sea subject to high mercury (Hg) pollution from both natural and anthropogenic sources. With the objective of discerning temporal changes in marine Hg pollution in the oceanic waters of the northwestern Mediterranean Sea, we analysed liver and kidney from striped dolphins (Stenella coeruleoalba) collected during 2007–2009 and compared them with previous results from a similar sample from 1990–1993. The effect of body length and sex on tissue Hg concentrations was investigated to ensure an unbiased comparison between the periods. The Hg concentrations did not show significant sex-related differences in any tissue or period but were correlated positively with body length. Using body length as a covariate, Hg concentrations in liver and kidney were higher in 1990–1993 than in 2007–2009. This result suggests that measures to reduce emissions in Western European countries have been effective in reducing mercury pollution in Mediterranean open waters.

Mercury content as a new indicator of ocean stratification and primary productivity in Quaternary sediments off Bahama Bank in the Caribbean Sea

We report the first evidence of Hg content in marine sediments changing in connection with the climate-driven changes in ocean stratification during the Quaternary Period based on core samples from ODP Hole 1006A off Great Bahama Bank in the Caribbean Sea. The Hg content ranged from 5.9 to 60.7ng/g with an average value of 33.1ng/g during 350 and 1330ka and changed inversely with δ18Oplanktonic values. The change in Hg content was positively correlated with total organic carbon (TOC) content, indicating connections between the δ15Norg and δ13Corg values of organic matter and the absolute abundance of a deep-dwelling calcareous nannoplankton (Florisphaera profunda). The marine Hg is thought to have been incorporated into the organic matter produced by deep-dwelling phytoplankton. Based on these results, we propose a mechanism by which marine Hg can collect in a thermocline formed in the stratified lower photic zone. Mercury content and nannoplankton assemblage in marine sediment provide information about the extent of stratification of the oceanic photic zone and the role of surface- and deep-dwelling phytoplankton in producing marine organic matter and changing its δ15Norg and δ13Corg values.

Millennial scale impact on the marine biogeochemical cycle of mercury from early mining on the Iberian Peninsula

The high‐resolution mercury record of a Posidonia oceanica mat in the northwest Mediterranean provides an unprecedented testimony of changes in environmental mercury (Hg) loading to the coastal marine environment over the past 4315 yr BP. The period reconstructed made it possible to establish tentative preanthropogenic background Hg levels for the area (6.8 ± 1.5 ng g–1 in bulk sediments). A small, but significant, anthropogenic Hg increase was identifiable by ~2500 yr BP, in agreement with the beginning of intense mining in Spain. Changes in the record suggest four major periods of anthropogenic Hg pollution inputs to the Mediterranean: first, during the Roman Empire (2100–1800 yr BP); second, in the Late Middle Ages (970–650 yr BP); third, in the modern historical era (530–380 yr BP); and fourth, in the industrial period (last 250 years), with Hg concentrations two‐, four‐, five‐, and tenfold higher than background concentrations, respectively. Hg from anthropogenic sources has dominated during the last millennium (increase from ~12 to ~100 ng g–1), which can be related to the widespread historical exploitation of ore resources on the Iberian Peninsula. The chronology of Hg concentrations in the mat archive, together with other Hg pollution records from the Iberian Peninsula, suggests regional‐scale Hg transport and deposition and shows earlier marine Hg pollution than elsewhere in Europe. Moreover, the mat also records a higher number of historic contamination phases, in comparison with other natural archives, probably due to the fact that the bioaccumulating capacity of P. oceanica magnify environmental changes in Hg concentrations. In this study, we demonstrate the uniqueness of P. oceanica meadows as a long‐term archive recording trends in Hg abundance in the marine coastal environment, as well as its potential role in the Mediterranean as a long‐term Hg sink.