Global mercury concentrations in biota: their use as a basis for a global biomonitoring framework.

An important provision of the Minamata Convention on Mercury is to monitor and evaluate the effectiveness of the adopted measures and its implementation. Here, we describe for the first time currently available biotic mercury (Hg) data on a global scale to improve the understanding of global efforts to reduce the impact of Hg pollution on people and the environment. Data from the peer-reviewed literature were compiled in the Global Biotic Mercury Synthesis (GBMS) database (>550,000 data points). These data provide a foundation for establishing a biomonitoring framework needed to track Hg concentrations in biota globally. We describe Hg exposure in the taxa identified by the Minamata Convention: fish, sea turtles, birds, and marine mammals. Based on the GBMS database, Hg concentrations are presented at relevant geographic scales for continents and oceanic basins. We identify some effective regional templates for monitoring methylmercury (MeHg) availability in the environment, but overall illustrate that there is a general lack of regional biomonitoring initiatives around the world, especially in Africa, Australia, Indo-Pacific, Middle East, and South Atlantic and Pacific Oceans. Temporal trend data for Hg in biota are generally limited. Ecologically sensitive sites (where biota have above average MeHg tissue concentrations) have been identified throughout the world. Efforts to model and quantify ecosystem sensitivity locally, regionally, and globally could help establish effective and efficient biomonitoring programs. We present a framework for a global Hg biomonitoring network that includes a three-step continental and oceanic approach to integrate existing biomonitoring efforts and prioritize filling regional data gaps linked with key Hg sources. We describe a standardized approach that builds on an evidence-based evaluation to assess the Minamata Convention's progress to reduce the impact of global Hg pollution on people and the environment.

Measuring riverine macroplastic: Methods, harmonisation, and quality control.

River systems are a key environmental recipient of macroplastic pollution. Understanding the sources of macroplastic to rivers and the mechanisms controlling fate and transport is essential to identify and tailor measures that can effectively reduce global plastic pollution. Several guidelines exist for monitoring macroplastic in rivers; yet, no single method has emerged representing the standard approach. This reflects the substantial variability in river systems globally and the need to adapt methods to the local environmental context and monitoring goals. Here we present a critical review of methods used to measure macroplastic flows in rivers, with a specific focus on opportunities for methods testing, harmonisation, and quality assurance and quality control (QA/QC). Several studies have already revealed important findings; however, there is significant disparity in the reporting of methodologies and data. There is a need to converge methods, and their adaptations, towards greater comparability. This can be achieved through: i) methods testing to better understand what each method effectively measures and how it can be applied in different contexts; ii) incorporating QA/QC procedures during sampling and analysis; and iii) reporting methodological details and data in a more harmonised way to facilitate comparability and the utilisation of data by several end users, including policy makers. Setting this as a priority now will facilitate the collection of rigorous and comparable monitoring data to help frame solutions to limit plastic pollution, including the forthcoming global treaty on plastic pollution.

Five decades of declining methylmercury concentrations in boreal foodwebs suggest pivotal role for sulphate deposition.

Widespread declines in mercury (Hg) in fish in pristine lakes in Fennoscandia since the 1970s are unexplained. Interactions between climate, atmospheric deposition, and elemental cycling of carbon (C), sulphur (S) and Hg are complex and affect Hg bioaccumulation. A parallel significant decline in methyl-Hg (MeHg) concentrations in aquatic macroinvertebrates (Chironomidae) was found between 1976-78 and 2004-15 in an intensely studied, pristine boreal lake (Langtjern, boreal Fennoscandia). Monitoring at Langtjern demonstrated a four-fold decrease in aqueous sulphate concentrations (SO4, 50-year record), significant lake browning (30-year records), increasing sediment Hg concentrations (50-year record), warming (45-year record) and increased runoff (40-year record). Contrasting Hg trends in biota (downward) and sediment (upward) indicated a disconnect between lake Hg loading and foodweb Hg bioaccumulation. We suggest that reduced SO4-deposition has 1) constrained substrate availability for SO4-reducing methylating bacteria (causing reduced foodweb MeHg exposure despite increased Hg loading to the lake), and 2), increased the binding affinity between aqueous organic matter and Hg species (leading to reduced MeHg bioavailability). The downward MeHg trend at the base of the foodweb at Langtjern is mirrored at higher trophic levels by strong declines in perch (Perca fluviatilis) and pike (Esox lucius) Hg concentrations in boreal Fennoscandia. A plausible explanation is that declining SO4-deposition, rather than climate change or reduced atmospheric Hg, is currently driving reduced MeHg contamination in northern freshwater foodwebs.

Mercury-Organic Matter Interactions in Soils and Sediments: Angel or Devil?

Many studies have suggested that organic matter (OM) substantially reduces the bioavailability and risks of mercury (Hg) in soils and sediments; however, recent reports have supported that OM greatly accelerates Hg methylation and increases the risks of Hg exposure. This study aims to summarize the interactions between Hg and OM in soils and sediments and improve our understanding of the effects of OM on Hg methylation. The results show that OM characteristics, promotion of the activity of Hg-methylating microbial communities, and the microbial availability of Hg accounted for the acceleration of Hg methylation which increases the risk of Hg exposure. These three key aspects were driven by multiple factors, including the types and content of OM, Hg speciation, desorption and dissolution kinetics and environmental conditions.

Improved Environmental Status: 50 Years of Declining Fish Mercury Levels in Boreal and Subarctic Fennoscandia.

Temporally (1965-2015) and spatially (55°-70°N) extensive records of total mercury (Hg) in freshwater fish showed consistent declines in boreal and subarctic Fennoscandia. The database contains 54 560 fish entries ( n: pike > perch ≫ brown trout > roach ≈ Arctic charr) from 3132 lakes across Sweden, Finland, Norway, and Russian Murmansk area. 74% of the lakes did not meet the 0.5 ppm limit to protect human health. However, after 2000 only 25% of the lakes exceeded this level, indicating improved environmental status. In lakes where local pollution sources were identified, pike and perch Hg concentrations were significantly higher between 1965 and 1990 compared to values after 1995, likely an effect of implemented reduction measures. In lakes where Hg originated from long-range transboundary air pollution (LRTAP), consistent Hg declines (3-7‰ per year) were found for perch and pike in both boreal and subarctic Fennoscandia, suggesting common environmental controls. Hg in perch and pike in LRTAP lakes showed minimal declines with latitude, suggesting that drivers affected by temperature, such as growth dilution, counteracted Hg loading and food web exposure. We recommend that future fish Hg monitoring sampling design should include repeated sampling and collection of pollution history, water chemistry, fish age, and stable isotopes to enable evaluation of emission reduction policies.

The organic pollutant status of rivers in Bosnia and Herzegovina as determined by a combination of active and passive sampling methods.

There is an overall lack of data concerning the pollution status of Bosnia Herzegovina, which is confounded by fragmented national environmental management. The present study aimed to provide some initial data for concentrations of priority substances in two major Bosnian Rivers, using two types of passive sampler (PS) as well as by using high volume water sampling (HVWS). Overall, concentrations of most persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and legacy pesticides, were shown to be low. However, around the town of Doboj on the Bosna River, concentrations of polycyclic aromatic hydrocarbons (PAH) breached European standards for several compounds and reached 67 ng L-1 for freely dissolved concentrations and 250 ng L-1 for total concentrations. In general, contamination was lower in the Neretva River compared to the Bosna, although for brominated diphenyl ethers (PBDEs), results suggested an active source of PBDEs at one location based on the ratio of congeners 47 and 99. Direct comparisons between the different sampling techniques used are not straightforward, but similar patterns of PAH contamination were shown by HVWS and PS in the Bosna River. There are both scientific and practical considerations when choosing which type of sampling technique to apply, and this should be decided based on the goals of each individual study.

Mercury in fish from Norwegian lakes: The complex influence of aqueous organic carbon.

Mercury (Hg) concentrations in water and biota are often positively correlated to organic matter (OM), typically measured as total or dissolved organic carbon (TOC/DOC). However, recent evidence suggests that higher OM concentrations inhibit bioaccumulation of Hg. Here, we test how TOC impacts the Hg accumulation in fish in a synoptic study of Methyl-Hg (MeHg) in water and total Hg (THg) in perch (Perca fluviatilis) in 34 boreal lakes in southern Norway. We found that aqueous MeHg (r2 = 0.49, p < 0.0001) and THg (r2 = 0.69, p < 0.0001), and fish THg (r2 = 0.26, p < 0.01) were all positively related with TOC. However, we found declining MeHg bioaccumulation factors (BAFMeHg) for fish with increasing TOC concentrations. The significant correlation between fish THg concentrations and aqueous TOC suggests that elevated fish Hg levels in boreal regions are associated with humic lakes. The declining BAFMeHg with increasing TOC suggest that increased OM promotes increased aqueous Hg concentrations, but lowers relative MeHg bioaccumulation. A mechanistic understanding of the response from OM on BAFMeHg might be found in the metal-complexation properties of OM, where OM complexation of metals reduces their bioavailability. Hence, suggesting that MeHg bioaccumulation becomes less effective at higher TOC, which is particularly relevant when assessing potential responses of fish Hg to predicted future changes in OM inputs to boreal ecosystems. Increased browning of waters may affect fish Hg in opposite directions: an increase of food web exposure to aqueous Hg, and reduced bioavailability of Hg species. However, the negative relationship between BAFMeHg and TOC is challenging to interpret, and carries a great deal of uncertainty, since this relationship may be driven by the underlying correlation between TOC and MeHg (i.e. spurious correlations). Our results suggest that the trade-off between Hg exposure and accumulation will have important implications for the effects of lake browning on Hg transport, bioavailability, and trophodynamics.

Past and present mercury accumulation in the Lake Baikal seal: Temporal trends, effects of life history, and toxicological implications.

Despite global efforts to reduce anthropogenic mercury (Hg) emissions, the timescale and degree to which Hg concentrations in the environment and biota respond to decreased emissions remain challenging to assess or predict. In the present study we characterize long-term trends and life-history patterns in Hg accumulation and toxicological implications of Hg contamination for a freshwater seal from one of the world's largest lakes (Lake Baikal, Siberia, Russia) using contemporary tissues and archival teeth. Stable isotope analysis and Hg analyses of soft tissues (muscle, liver, kidney, blood, brain, heart) and teeth from 22 contemporary seals revealed rapid changes in diet and Hg accumulation in the first year of life with a stable diet and increase in tissue Hg throughout the rest of life. Although maternal transfer of Hg was an important source of Hg to seal pups, reproduction and lactation by female seals did not appear to result in sex-related differences in Hg concentrations or age-related accumulation in adult seals. Based on Hg analysis of archival teeth (n = 114) and reconstructed values for soft tissues, we also assessed temporal trends in seal Hg between the years 1960 and 2013. Seal Hg concentrations in hard (teeth) and soft (e.g., muscle, liver) tissues were highest in the 1960s and 1970s, followed by a decrease. The decline in seal Hg concentrations in recent decades was most likely driven by a reduction in Hg inputs to the lake, suggesting that global and regional efforts to reduce Hg emissions have been successful at reducing ecosystem and human health risks posed by Hg in Lake Baikal. Environ Toxicol Chem 2018;37:1476-1486. © 2018 SETAC.

The influence of permanently submerged macrophytes on sediment mercury distribution, mobility and methylation potential in a brackish Norwegian fjord.

Macrophytes are shown to affect the microbial activity in different aqueous environments, with an altering of the sediment cycling of mercury (Hg) as a potential effect. Here, we investigated how a meadow with permanently submerged macrophytes in a contaminated brackish fjord in southern Norway influenced the conditions for sulfate reducing microbial activity, the methyl-Hg (MeHg) production and the availability of MeHg. Historically discharged Hg from a chlor-alkali plant (60-80tons, 1947-1987) was evident through high Hg concentrations (491mgTot-Hgkg-1, 268µgMeHgkg-1) in intermediate sediment depths (10-20cm) outside of the meadow, with reduced concentrations within the meadow. Natural recovery of the fjord was revealed by lower sediment surface concentrations (1.9-15.5mgTot-Hgkg-1, 1.3-3.2µgMeHgkg-1). Within the meadow, vertical gradients of sediment hydrogen sulfide (H2S) Eh and pH suggested microbial sulfate reduction in 2-5cm depths, coinciding with peak values of relative MeHg levels (0.5% MeHg). We assume that MeHg production rates was stimulated by the supply and availability of organic carbon, microbial activity and a sulfide oxidizing agent (e.g. O2) within the rhizosphere. Following this, % MeHg in sediment (0-5cm) within the meadow was approximately 10× higher compared to outside the meadow. Further, enhanced availability of MeHg within the meadow was demonstrated by significantly higher fluxes (p<0.01) from sediment to overlying water (0.1-0.6ngm-2d-1) compared to sediment without macrophytes (0.02-0.2ngm-2d-1). Considering the productivity and species richness typical for such habitats, submerged macrophyte meadows located within legacy Hg contaminated sediment sites may constitute important entry points for MeHg into food webs.

Petroleum oil and mercury pollution from shipwrecks in Norwegian coastal waters.

Worldwide there are tens of thousands of sunken shipwrecks lying on the coastal seabed. These potentially polluting wrecks (PPW) are estimated to hold 3-25milliont of oil. Other hazardous cargo in PPW includes ordnance, chemicals and radioactive waste. Here, we present and discuss studies on mercury (Hg) and oil pollution in coastal marine sediment caused by two of the >2100 documented PPW in Norwegian marine waters. The German World War II (WWII) submarine (U-864) lies at about 150m below the sea surface, near the Norwegian North Sea island of Fedje. The submarine is estimated to have been carrying 67t of elemental Hg, some of which has leaked on to surrounding sediment. The total Hg concentration in bottom surface sediment within a 200m radius of the wreckage decreases from 100g/kgd.w. at the wreckage hotspot to about 1mg/kgd.w. at 100m from the hotspot. The second wreck is a German WWII cargo ship (Nordvard), that lies at a depth of ca. 30m near the Norwegian harbor of Moss. Oil leakage from Nordvard has contaminated the bottom coastal sediment with polycyclic aromatic hydrocarbons (PAH). The findings from this study provide useful insight to coastal administration authorities involved in assessing and remediating wreck-borne pollution from any of the tens of thousands of sunken shipwrecks.

Effects of disturbance and vegetation type on total and methylmercury in boreal peatland and forest soils.

Mercury (Hg) concentrations in freshwater fish relates to aquatic Hg concentrations, which largely derives from soil stores of accumulated atmospheric deposition. Hg in catchment soils as a source for aquatic Hg is poorly studied. Here we test if i) peatland soils produce more methylmercury (MeHg) than forest soils; ii) total Hg (THg) concentrations in top soils are determined by atmospheric inputs, while MeHg is produced in the soils; and iii) soil disturbance promotes MeHg production. In two small boreal catchments, previously used in a paired-catchment forest harvest manipulation study, forest soils and peatlands were sampled and analysed for Hg species and additional soil chemistry. In the undisturbed reference catchment, soils were sampled in different vegetation types, of varying productivity as reflected in tree density, where historical data on precipitation and throughfall Hg and MeHg fluxes were available. Upper soil THg contents were significantly correlated to throughfall inputs of Hg, i.e. lowest in the tree-less peatland and highest in the dense spruce forest. For MeHg, top layer concentrations were similar in forest soils and peatlands, likely related to atmospheric input and local production, respectively. The local peatland MeHg production was documented through significantly higher MeHg-to-THg ratios in the deeper soil layer samples. In the disturbed catchment, soils were sampled in and just outside wheeltracks in an area impacted by forest machinery. Here, MeHg concentrations and the MeHg-to-THg ratios in the upper 5 cm were weakly significantly (p = 0.07) and significantly (p = 0.04) different in and outside of the wheeltracks, respectively, suggesting that soil disturbance promotes methylation. Differences in catchment Hg and MeHg streamwater concentrations were not explained by soil Hg and MeHg information, perhaps because hydrological pathways are a stronger determinant of streamwater chemistry than small variations in soil chemistry driven by disturbance and atmospheric inputs of Hg.

Effects of organic matter addition on methylmercury formation in capped and uncapped marine sediments.

In situ subaqueous capping (ISC) of contaminated marine sediments is frequently proposed as a feasible and effective mitigation option. However, though effective in isolating mercury species migration into overlying water, capping can also alter the location and extent of biogeochemical zones and potentially enhance methylmercury (MeHg) formation in Hg-contaminated marine sediments. We carried out a boxcosm study to investigate whether the addition of organic carbon (OC) to Hg-contaminated marine sediments beneath an in situ cap would initiate and/or enhance MeHg formation of the inorganic Hg present. The study was motivated by ongoing efforts to remediate ca. 30,000 m(2) of Hg-contaminated seabed sediments from a Hg spill from the U864 WWII submarine wreck. By the time of sinking, the submarine is assumed to have been holding a cargo of ca. 65 tons of liquid Hg. Natural organic matter and petroleum hydrocarbons from fuels and lubricants in the wreck are potential sources of organic carbon that could potentially fuel MeHg formation beneath a future cap. The results of our study clearly demonstrated that introduction of algae OC to Hg-contaminated sediments, triggered high rates of MeHg production as long a there was sufficient OC. Thus, MeHg production was limited by the amount of organic carbon available. The study results also confirmed that, within the six-month duration of the study and in the absence of bioturbating fauna, a 3-cm sediment clay cap could effectively reduce fluxes of Hg species to the overlying water and isolate the Hg-contaminated sediments from direct surficial deposition of organic matter that could potentially fuel methylation.

Effects of photodemethylation on the methylmercury budget of boreal Norwegian lakes.

Methylmercury (MeHg) concentrations in freshwater fish from southeastern Norway continue to increase, highlighting the need for a comprehensive understanding of MeHg sources, cycling, and degradation in the aquatic environment. The authors assessed the importance of photodemethylation in the MeHg budget of 4 Norwegian lakes. Photodemethylation rates were determined using incubation experiments with MeHg-spiked natural lake water. The authors determined full-spectrum exposure rates at all study sites and waveband-specific rates (photosynthetically active radiation, ultraviolet-A radiation, and ultraviolet-B radiation) at 1 clear-water (Sognsvann) and 1 humic (Langtjern) site. No significant differences in photodemethylation rates between the sites were found, and the authors' observed rates agreed with available literature for lake and wetland waters. The authors paired experimentally derived photodemethylation rates with lake-specific incident irradiation, light attenuation, and MeHg concentrations to estimate MeHg loss through photodemethylation for the study sites. For Langtjern, losses through photodemethylation equalled 27% of total annual inputs, highlighting the importance of photodemethylation in the MeHg budget. Furthermore, the authors assessed how changes in terrestrial dissolved organic carbon (DOC) exported to freshwaters and climate-driven reductions in ice cover duration may affect MeHg losses through photodemethylation. Results suggest that future increases in DOC may lead to higher aqueous MeHg concentrations in boreal lakes due to increased DOC-associated MeHg inputs paired with significant decreases in the loss of MeHg through photodemethylation due to increased light attenuation.

Seasonal and year-to-year variation of mercury concentration in perch (Perca fluviatilis) in boreal lakes.

The authors examined the seasonal and year-to-year variations of mercury (Hg) concentrations in populations of perch (Perca fluviatilis) from 2 boreal freshwater lakes in southeast Norway. Fish Hg concentrations were determined seasonally (spring, summer, and autumn) over 3 yr (2010, 2011, and 2012) to test the hypothesis that there are substantial changes in fish Hg concentrations during the year (seasonal variation) as well as annually. Concentrations were significantly (p < 0.0001) different in the 2 study lakes, with mean seasonal concentrations varying from 0.24 mg/kg to 0.36 mg/kg and from 0.29 mg/kg to 0.37 mg/kg, respectively. The Hg concentrations of both perch populations showed significant year-to-year (p < 0.0001) and seasonal variation (p < 0.01). The changing fish Hg concentrations were 25% and 28% (2010-2011) and 17% and 0% (2011-2012) in the 2 lakes over the 3 yr, respectively. The results demonstrate how the significant year-to-year increase is, among other variables, related to changes in trophic position, shown through stable nitrogen (δ(15)N) isotope data. The seasonal variation is related to summer growth dilution. The results highlight the clear need for yearly studies of fish Hg concentrations, rather than the 3-yr cycle suggested by current European policy through the Water Framework Directive. The lack of yearly sampling may result in erroneous conclusions regarding fish Hg concentration time trends.

Biogeochemical consequences of an oxygenated intrusion into an anoxic fjord.

BACKGROUND: This paper is based on the studies of the biogeochemical structure of the water column in the anoxic Fjord Hunnbunn (south-eastern Norway) performed in 2009, 2011 and 2012. This Fjord is an enclosed basin of brackish water separated by a narrow and shallow outlet to the sea with a permanently anoxic layer. We show how an oxygenated intrusion could lead to both positive and negative effects on the ecosystem state in Hunnbunn due to a change in the biogeochemical structure. RESULTS: During the stratified periods in 2009 and 2012 the anoxic layer amounted to approximately 10% of the total water volume in the Fjord, while dissolved oxygen (DO) was present in 80-90% of the water. In the autumn of 2011 the water chemistry structure observed in Fjord Hunnbunn was clearly affected by a recent oxygenated intrusion defined by abnormal salinity patterns. This led to a shift of the DO boundary position to shallower depths, resulting in a thicker anoxic layer comprising approximately 40% of the total water volume, with DO present only in approximately 60% of the water. The oxygenated water intrusions led to a twofold decrease of the concentrations of hydrogen sulphide, ammonia, phosphate and silicate in the deep layers with a simultaneous increase of these nutrients and a decrease of the pH level in the surface layers. The concentrations of manganese, iron, and mercury species changed dramatically and in particular revealed a significant supply of iron and methylmercury to the water column. CONCLUSIONS: Oxic water intrusions into anoxic fjords could lead not only to the flushing of the bottom anoxia, but to a dispersal of sulphidic and low oxygen conditions to the larger bottom area. The elevation of the hydrogen sulphide to the shallower layers (that can be rapidly oxidized) is accompanied by the appearance in the subsurface water of methylmercury, which is easily accumulated by organisms and can be transported to the surrounding waters, affecting the ecosystem over a larger area.