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Controls on methylmercury concentrations in lakes and streams of peatland-rich catchments along a 1700 km permafrost gradient
Limnology and Oceanography
Abstract and Figures
Permafrost thaw may increase the production of neurotoxic methylmercury (MeHg) in northern peatlands, but the downstream delivery of MeHg is uncertain. We quantified total mercury (THg) and MeHg concentrations in lakes and streams along a 1700 km permafrost transect in boreal western Canada to determine the influence of regional permafrost extent compared to local lake and catchment characteristics. In lakes, we assessed sediment microbial communities and modeled potential rates of water column photodemethylation (PD). Regardless of permafrost conditions, peatlands were the primary sources of MeHg across the transect as MeHg concentrations in streams increased with aromatic dissolved organic carbon (DOC), iron, and lower pH. Higher DOC and greater catchment peatland extent were further associated with higher stream %MeHg (MeHg/THg). Peatland lakes were potential MeHg sinks, with lower MeHg concentrations than streams (mean±1SD: 0.19±0.23 and 0.47±0.77 ng MeHg L cm-1, respectively), and larger stream catchments had lower %MeHg where PD may occur in abundant small lakes. Microbial communities in lake sediments showed that abundance of Hg reducing genes (merA) predominated over Hg methylating (hgcA) and MeHg demethylating (merB) genes. The effects of permafrost extent on MeHg processes in lakes were secondary to the influence of local catchment characteristics, but lakes in regions with less permafrost had higher DOC concentrations, higher %MeHg, and lower potential rates of PD. Our study highlights a need to understand the impacts of climate change on MeHg source and sink processes, particularly as mediated through changes to peatland DOC, to improve projections of future MeHg concentrations in northern catchments.
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... This is important because paddy water is different from the natural water in lakes and rivers, and is characterized by relatively higher concentrations of DOC (15− 74 mg L − 1 ) and nitrate (10− 207 mg L − 1 ; Table S1) due to farming activities such as organic/inorganic fertilization. Furthermore, the complex of MeHg with different DOM components has been reported to result in difference in MeHg degradation in natural water (Li et al., 2024;Thompson et al., 2023;Zhang et al., 2022), while how DOM molecular properties and DOM contents impact MeHg degradation in paddy water warrants further study. Meanwhile, the contribution of dissolved iron (Fe), which is abundant in paddy soils and reported to be involved in MeHg photodegradation via the formation of hydroxyl radicals (Hammerschmidt and Fitzgerald, 2010), to MeHg photodegradation also needs future exploration. ...
Photodegradation is critical to reduce the potent neurotoxic methylmercury (MeHg) in water and its subsequent
accumulation along food chains. However, this process has been largely ignored in rice paddies, which are
hotspots of MeHg production and receive about a quarter of the world’s developed freshwater resources. Here,
we reported that significant MeHg photodegradation, primarily mediated by hydroxyl radicals, occurs in the
overlying water during rice growth. By incorporating field-measured light interception into a rice paddy
biogeochemistry model, as well as photodegradation rates obtained from 42 paddy soils stretching ~3500 km
across China, we estimated that photodegradation reduced MeHg concentrations in paddy water and rice by 82
% and 11 %, respectively. Without photodegradation, paddy water could be a significant MeHg source for
downstream ecosystems, with an annual export of 178 − 856 kg MeHg to downstream waters in China, the
largest rice producer. These findings suggest that photodegradation in paddy water is critical for preventing
greater quantities of MeHg entering human food webs.
... We also studied five peatland ponds ( Figure S2 in Supporting Information S1), three at Lutose (L1, L2, and L4) and two at Smith Creek (W1 and W2), all of which have been part of previous studies Thompson et al., 2023). All pond depths ranged from 0.5 to 2.5 m and were between 0.5 and 5 ha in area. ...
The greenhouse gas (GHG) balance of boreal peatlands in permafrost regions will be affected by climate change through disturbances such as permafrost thaw and wildfire. Although the future GHG balance of boreal peatlands including ponds is dominated by the exchange of both carbon dioxide (CO2) and methane (CH4), disturbance impacts on fluxes of the potent GHG nitrous oxide (N2O) could contribute to shifts in the net radiative balance. Here, we measured monthly (April to October) fluxes of N2O, CH4, and CO2 from three sites located across the sporadic and discontinuous permafrost zones of western Canada. Undisturbed permafrost peat plateaus acted as N2O sinks (−0.025 mg N2O m⁻² d⁻¹), but N2O uptake was lower from burned plateaus (−0.003 mg N2O m⁻² d⁻¹) and higher following permafrost thaw in the thermokarst bogs (−0.054 mg N2O m⁻² d⁻¹). The thermokarst bogs had below‐ambient N2O soil gas concentrations, suggesting that denitrification consumed atmospheric N2O during reduction to dinitrogen. Atmospheric uptake of N2O in peat plateaus and thermokarst bogs increased with soil temperature and soil moisture, suggesting sensitivity of N2O consumption to further climate change. Four of five peatland ponds acted as N2O sinks (−0.018 mg N2O m⁻² d⁻¹), with no influence of thermokarst expansion. One pond with high nitrate concentrations had high N2O emissions (0.30 mg N2O m⁻² d⁻¹). Overall, our study suggests that the future net radiative balance of boreal peatlands will be dominated by impacts of wildfire and permafrost thaw on CH4 and CO2 fluxes, while the influence from N2O is minor.
Climate change and permafrost thaw may impact the mobilization of terrestrial dissolved organic carbon (DOC), mercury (Hg), and neurotoxic methylmercury (MeHg) into aquatic ecosystems; thus, understanding processes that control analyte export in northern catchments is needed. We monitored water chemistry for 3 years (2019–2021) at a peatland catchment (Scotty Creek) and a mixed catchment (Smith Creek) in the Dehcho (Northwest Territories), within the discontinuous permafrost zone of boreal western Canada. The peatland catchment had higher DOC and dissolved MeHg, but lower total Hg concentrations (mean ± standard deviation; 19 ± 2.6 mg DOC L−1; 0.08 ± 0.04 ng DMeHg L−1; 1.1 ± 0.3 ng THg L−1) than the mixed catchment (12 ± 4.4 mg DOC L−1; 0.05 ± 0.01 ng DMeHg L−1; 3.1 ± 2.2 ng THg L−1). Analyte concentrations increased with discharge at the mixed catchment, suggesting transport limitation and the flushing of near-surface, organic-rich flow paths during wet periods. In contrast, analyte concentrations in the peatland catchment were not primarily associated with discharge. MeHg concentrations, MeHg:THg, and MeHg:DOC increased with water temperature, suggesting enhanced Hg methylation during warmer periods. Mean open water season DOC and total MeHg yields were greater and more variable from the peatland than the mixed catchment (1.1–6.6 vs. 1.4–2.4 g DOC m−2; 5.2–36 vs. 6.1–10 ng MeHg m−2). Crucial storage thresholds controlling runoff generation likely drove greater inter-annual variability in analyte yields from the peatland catchment. Our results suggest climate change may influence the production and transport of MeHg from boreal-Arctic catchments as temperatures increase, peatlands thaw, and runoff generation is altered.
Currently, little is available on how mercury (Hg) methylation couples with soil organic matter decomposition in degraded permafrost in high northern latitudes, where the climate is becoming warmer rapidly. Here, we revealed the complex interactions between soil organic matter (SOM) mineralization, dissolved organic matter (DOM) and methylmercury (MeHg) production based on an 87-day anoxic warming incubation experiment. Results supported remarkably promotion effects of warming on MeHg production, by 130%-205% on average. Total mercury (THg) loss under warming treatment depended on marsh types but showed an increasing trend on the whole. Warming yielded higher proportions of MeHg to THg (%MeHg), increased by 123%-569%. As expected, greenhouse gas emission was significantly enhanced by warming. Warming also strengthened fluorescence intensities of fulvic-like and protein-like DOM, with contributions to total fluorescence intensities of 49%-92% and 8%-51%, respectively. DOM and its spectral features explained 60% variation of MeHg, and the explanation increased to 82% in conjunction with greenhouse gas emissions. The structural equation model implied that warming, greenhouse gas emission, and humification of DOM had positive effects on Hg methylation potential, while microbial-derived DOM showed negative effects on MeHg. These results showed that accelerated Hg loss and increased methylation covaried with greenhouse gas emission and DOM formation under warming conditions in permafrost marsh.
Rising air temperatures, intensifying wildfire activity, and human disturbance are driving rapid permafrost thaw across the subarctic, particularly for thaw-sensitive discontinuous permafrost. The Taiga Plains and Taiga Shield ecozones of northwestern Canada have experienced rapid and widespread permafrost thaw over recent decades, creating significant community concerns and knowledge gaps. In direct response, this review: (1) outlines the observed thaw-induced changes in landcover, hydrology, and water quality; (2) discusses the underlying drivers and mechanisms of these changes; and (3) identifies knowledge gaps to guide future research in the discontinuous permafrost zone of the Taiga Plains and Shield (study region). In the Taiga Plains, permafrost is mainly associated with peatlands where its thaw increases the extent of thermokarst wetlands at the expense of treed peatlands underlain by permafrost. This thaw-induced landcover change enhances the hydrological connectivity of the landscape, which increases basin-scale runoff and annual streamflow, and enables wetland drainage such that permafrost-free treed wetlands develop. Thaw-induced landcover changes in the lake- and bedrock-dominated Taiga Shield are not well known but are expected to occur as limited or minor thermokarst pond development and changing lake extent due to the low (<5%) peatland coverage of this ecozone. Permafrost thaw also increases the connectivity between surface water and groundwater, leading to increasing winter baseflows and possibly icing (aufeis) development. Such increases in hydrologic connectivity can enhance the mobilization of parameters of concern for water quality, both in the Taiga Plains and Shield. The thawing of peatlands will likely increase the transport and concentrations of dissolved organic carbon and metals bound to organic compounds, including methylmercury. Further work is needed to fully understand the biogeochemical processes operating in these systems and the degree to which thawing peatlands will impact water quality and quantity at the larger basin scale. The greatest knowledge gaps across the study region surround the evolution of thaw-activated groundwater flow systems and the consequences for wetland biogeochemistry, the rates and patterns of permafrost thaw, contaminant transport, and streamflow of larger river systems. This synthesis not only informs future research directions in the study region but extends to similar subarctic peatland and Shield environments common throughout the circumpolar north.
Dramatic environmental shifts are occuring throughout the Arctic from climate change, with consequences for the cycling of mercury (Hg). This review summarizes the latest science on how climate change is influencing Hg transport and biogeochemical cycling in Arctic terrestrial, freshwater and marine ecosystems. As environmental changes in the Arctic continue to accelerate, a clearer picture is emerging of the profound shifts in the climate and cryosphere, and their connections to Hg cycling. Modeling results suggest climate influences seasonal and interannual variability of atmospheric Hg deposition. The clearest evidence of current climate change effects is for Hg transport from terrestrial catchments, where widespread permafrost thaw, glacier melt and coastal erosion are increasing the export of Hg to downstream environments. Recent estimates suggest Arctic permafrost is a large global reservoir of Hg, which is vulnerable to degradation with climate warming, although the fate of permafrost soil Hg is unclear. The increasing development of thermokarst features, the formation and expansion of thaw lakes, and increased soil erosion in terrestrial landscapes are increasing river transport of particulate-bound Hg and altering conditions for aquatic Hg transformations. Greater organic matter transport may also be influencing the downstream transport and fate of Hg. More severe and frequent wildfires within the Arctic and across boreal regions may be contributing to the atmospheric pool of Hg. Climate change influences on Hg biogeochemical cycling remain poorly understood. Seasonal evasion and retention of inorganic Hg may be altered by reduced sea-ice cover and higher chloride content in snow. Experimental evidence indicates warmer temperatures enhance methylmercury production in ocean and lake sediments as well as in tundra soils. Improved geographic coverage of measurements and modeling approaches are needed to better evaluate net effects of climate change and long-term implications for Hg contamination in the Arctic.
Small, organic‐rich lakes are important sources of methane (CH4) and carbon dioxide (CO2) to the atmosphere, yet the sensitivity of emissions to climate warming is poorly constrained and potentially influenced by permafrost thaw. Here, we monitored emissions from 20 peatland lakes across a 1,600 km permafrost transect in boreal western Canada. Contrary to expectations, we observed a shift from source to sink of CO2 for lakes warmer regions, driven by greater primary productivity associated with greater hydrological connectivity to lakes and nutrient availability in the absence of permafrost. Conversely, an 8‐fold increase in CH4 emissions in warmer regions was associated with water temperature and shifts in microbial communities and dominant anaerobic processes. Our results suggest that the net radiative forcing from altered greenhouse gas emissions of northern peatland lakes this century will be dominated by increasing CH4 emissions and only partially offset by reduced CO2 emissions.
Methane emissions from boreal and arctic wetlands, lakes, and rivers are expected to increase in response to warming and associated permafrost thaw. However, the lack of appropriate land cover datasets for scaling field-measured methane emissions to circumpolar scales has contributed to a large uncertainty for our understanding of present-day and future methane emissions. Here we present the Boreal–Arctic Wetland and Lake Dataset (BAWLD), a land cover dataset based on an expert assessment, extrapolated using random forest modelling from available spatial datasets of climate, topography, soils, permafrost conditions, vegetation, wetlands, and surface water extents and dynamics. In BAWLD, we estimate the fractional coverage of five wetland, seven lake, and three river classes within 0.5 × 0.5∘ grid cells that cover the northern boreal and tundra biomes (17 % of the global land surface). Land cover classes were defined using criteria that ensured distinct methane emissions among classes, as indicated by a co-developed comprehensive dataset of methane flux observations. In BAWLD, wetlands occupied 3.2 × 106 km2 (14 % of domain) with a 95 % confidence interval between 2.8 and 3.8 × 106 km2. Bog, fen, and permafrost bog were the most abundant wetland classes, covering ∼ 28 % each of the total wetland area, while the highest-methane-emitting marsh and tundra wetland classes occupied 5 % and 12 %, respectively. Lakes, defined to include all lentic open-water ecosystems regardless of size, covered 1.4 × 106 km2 (6 % of domain). Low-methane-emitting large lakes (>10 km2) and glacial lakes jointly represented 78 % of the total lake area, while high-emitting peatland and yedoma lakes covered 18 % and 4 %, respectively. Small (
The public and environmental health consequences of mercury (Hg) methylation have drawn much attention and considerable research to Hg methylation processes and their dynamics in diverse environments and under a multitude of conditions. However, the net methylmercury (MeHg) concentration that accumulates in the environment is equally determined by the rate of MeHg degradation, a complex process mediated by a variety of biotic and abiotic mechanisms, about which our knowledge is limited. Here we review the current knowledge on MeHg degradation and its potential pathways and mechanisms. We describe detoxification by resistant microorganisms that employ the Hg resistance (mer) system to reductively break the carbon–mercury (C–Hg) bond producing methane (CH4) and inorganic mercuric Hg(II), which is then reduced by the mercuric reductase to elemental Hg(0). Very recent research has begun to elucidate a mechanism for the long-recognized mer-independent oxidative demethylation, likely involving some strains of anaerobic bacteria as well as aerobic methane-oxidizing bacteria, i.e., methanotrophs. In addition, photochemical and chemical demethylation processes are described, including the roles of dissolved organic matter (DOM) and free radicals as well as dark abiotic demethylation in the natural environment about which little is currently known. We focus on mechanisms and processes of demethylation and highlight the uncertainties and known effects of environmental factors leading to MeHg degradation. Finally, we suggest future research directions to further elucidate the chemical and biochemical mechanisms of biotic and abiotic demethylation and their significance in controlling net MeHg production in natural ecosystems.
Mercury (Hg) is a highly toxic element due to its high affinity for protein sulfhydryl groups, which upon binding, can destabilize protein structure and decrease enzyme activity. Prokaryotes have evolved enzymatic mechanisms to detoxify inorganic Hg and organic Hg (e.g., MeHg) through the activities of mercuric reductase (MerA) and organomercury lyase (MerB), respectively. Here, the taxonomic distribution and evolution of MerAB was examined in 84,032 archaeal and bacterial genomes, metagenome assembled genomes, and single-cell genomes. Homologs of MerA and MerB were identified in 7.8 and 2.1% percent of genomes, respectively. MerA was identified in the genomes of 10 archaeal and 28 bacterial phyla previously unknown to code for this functionality. Likewise, MerB was identified in 2 archaeal and 11 bacterial phyla previously unknown to encode this functionality. Surprisingly, homologs of MerB were identified in a number of genomes (∼50% of all MerB-encoding genomes) that did not encode MerA, suggesting alternative mechanisms to detoxify Hg(II) once it is generated in the cytoplasm. Phylogenetic reconstruction of MerA place its origin in thermophilic Thermoprotei (Crenarchaeota), consistent with high levels of Hg(II) in geothermal environments, the natural habitat of this archaeal class. MerB appears to have been recruited to the mer operon relatively recently and likely among a mesophilic ancestor of Euryarchaeota and Thaumarchaeota. This is consistent with the functional dependence of MerB on MerA and the widespread distribution of mesophilic microorganisms that methylate Hg(II) at lower temperature. Collectively, these results expand the taxonomic and ecological distribution of mer -encoded functionalities, and suggest that selection for Hg(II) and MeHg detoxification is dependent not only on the availability and type of mercury compounds in the environment but also the physiological potential of the microbes who inhabit these environments. The expanded diversity and environmental distribution of MerAB identify new targets to prioritize for future research.
Methylmercury (MeHg) forms in anoxic environments and can bioaccumulate and biomagnify in aquatic food webs to concentrations of concern for human and wildlife health. Mercury (Hg) pollution in the Arctic environment may worsen as these areas warm and Hg, currently locked in permafrost soils, is remobilized. One of the main concerns is the development of Hg methylation hotspots in the terrestrial environment due to thermokarst formation. The extent to which net methylation of Hg is enhanced upon thaw is, however, largely unknown. Here, we have studied the formation of Hg methylation hotspots using existing thaw gradients at five Fennoscandian permafrost peatland sites. Total Hg (HgT) and MeHg concentrations were analyzed in 178 soil samples from 14 peat cores. We observed 10 times higher concentrations of MeHg and 13 times higher %MeHg in the collapse fen (representing thawed conditions) as compared to the peat plateau (representing frozen conditions). This suggests significantly greater net methylation of Hg when thermokarst wetlands are formed. In addition, we report HgT to soil organic carbon ratios representative of Fennoscandian permafrost peatlands (median and interquartile range of 0.09 ± 0.07 μg HgT g-1 C) that are of value for future estimates of circumpolar HgT stocks.
Developing spatially explicit permafrost datasets and climate assessments at scales relevant to northern communities is increasingly important as land users and decision makers incorporate changing permafrost conditions in community and adaptation planning. This need is particularly strong within the discontinuous permafrost zone of the Northwest Territories (NWT) Canada where permafrost peatlands are undergoing rapid thaw due to a warming climate. Current data products for predicting landscapes at risk of thaw are generally built at circumpolar scales and do not lend themselves well to fine-scale regional interpretations. Here, we present a new permafrost vulnerability dataset that assesses the degree of permafrost thaw within peatlands across a 750 km latitudinal gradient in the NWT. This updated dataset provides spatially explicit estimates of where peatland thermokarst potential exists, thus making it much more suitable for local, regional or community usage. Within southern peatland complexes, we show that permafrost thaw affects up to 70% of the peatland area and that thaw is strongly mediated by both latitude and elevation, with widespread thaw occuring particularly at low elevations. At the northern end of our latitudinal gradient, peatland permafrost remains climate-protected with relatively little thaw. Collectively these results demonstrate the importance of scale in permafrost analyses and mapping if research is to support northern communities and decision makers in a changing climate. This study offers a more scale-appropriate approach to support community adaptative planning under scenarios of continued warming and widespread permafrost thaw.
Abstract Dissolved organic matter (DOM) represents a mixture of organic molecules that vary due to different source materials and degree of processing. Characterizing how DOM composition evolves along the aquatic continuum can be difficult. Using a size‐exclusion chromatography technique (liquid chromatography‐organic carbon detection [LC‐OCD]), we assessed the variability in DOM composition from both surface and groundwaters across a number of Canadian ecozones (mean annual temperature spanning −10°C to +6°C). A wide range in DOM concentration was found from 0.2 to 120 mg C L−1. Proportions of different size‐based groupings across ecozones were variable, yet similarities between specific waterbody types, regardless of location, suggest commonality in the processes dictating DOM composition. A principal component analysis identified 70% of the variation in LC‐OCD derived DOM compositions could be explained by the waterbody type. We find that DOM composition within a specific waterbody type is similar regardless of the differences in climate or surrounding vegetation where the sample originated from.
The Pfam database is a widely used resource for classifying protein sequences into families and domains. Since Pfam was last described in this journal, over 350 new families have been added in Pfam 33.1 and numerous improvements have been made to existing entries. To facilitate research on COVID-19, we have revised the Pfam entries that cover the SARS-CoV-2 proteome, and built new entries for regions that were not covered by Pfam. We have reintroduced Pfam-B which provides an automatically generated supplement to Pfam and contains 136 730 novel clusters of sequences that are not yet matched by a Pfam family. The new Pfam-B is based on a clustering by the MMseqs2 software. We have compared all of the regions in the RepeatsDB to those in Pfam and have started to use the results to build and refine Pfam repeat families. Pfam is freely available for browsing and download at http://pfam.xfam.org/.
The gene pair hgcAB is essential for microbial mercury methylation. Our understanding of its abundance and diversity in nature is rapidly evolving. In this study we developed a new broad-range primer set for hgcAB, plus an expanded hgcAB reference library, and used these to characterize Hg-methylating communities from diverse environments. We applied this new Hg-methylator database to assign taxonomy to hgcA sequences from clone, amplicon, and metagenomic datasets. We evaluated potential biases introduced in primer design, sequence length, and classification, and suggest best practices for studying Hg-methylator diversity. Our study confirms the emerging picture of an expanded diversity of HgcAB-encoding microbes in many types of ecosystems, with abundant putative mercury methylators Nitrospirae and Chloroflexi in several new environments including salt marsh and peat soils. Other common microbes encoding HgcAB included Phycisphaerae, Aminicenantes, Spirochaetes, and Elusimicrobia. Combined with high-throughput amplicon specific sequencing, the new primer set also indentified novel hgcAB sequences similar to Lentisphaerae, Bacteroidetes, Atribacteria, and candidate phyla WOR-3 and KSB1 bacteria. Gene abundance data also corroborate the important role of two “classic” groups of methylators (Deltaproteobacteria and Methanomicrobia) in many environments, but generally show a scarcity of hgcAB+ Firmicutes. The new primer set was developed to specifically target hgcAB sequences found in nature, reducing degeneracy and providing increased sensitivity while maintaining broad diversity capture. We evaluated mock communities to confirm primer improvements, including culture spikes to environmental samples with variable DNA extraction and PCR amplification efficiencies. For select sites, this new workflow was combined with direct high-throughput hgcAB sequencing. The hgcAB diversity generated by direct amplicon sequencing confirmed the potential for novel Hg-methylators previously identified using metagenomic screens. A new phylogenetic analysis using sequences from freshwater, saline, and terrestrial environments showed Deltaproteobacteria HgcA sequences generally clustered among themselves, while metagenome-resolved HgcA sequences in other phyla tended to cluster by environment, suggesting horizontal gene transfer into many clades. HgcA from marine metagenomes often formed distinct subtrees from those sequenced from freshwater ecosystems. Overall the majority of HgcA sequences branch from a cluster of HgcAB fused proteins related to Thermococci, Atribacteria (candidate division OP9), Aminicenantes (OP8), and Chloroflexi. The improved primer set and library, combined with direct amplicon sequencing, provide a significantly improved assessment of the abundance and diversity of hgcAB+ microbes in nature.
Mercury (Hg) is a naturally occurring element that bonds with organic matter and, when converted to methylmercury, is a potent neurotoxicant. Here we estimate potential future releases of Hg from thawing permafrost for low and high greenhouse gas emissions scenarios using a mechanistic model. By 2200, the high emissions scenario shows annual permafrost Hg emissions to the atmosphere comparable to current global anthropogenic emissions. By 2100, simulated Hg concentrations in the Yukon River increase by 14% for the low emissions scenario, but double for the high emissions scenario. Fish Hg concentrations do not exceed United States Environmental Protection Agency guidelines for the low emissions scenario by 2300, but for the high emissions scenario, fish in the Yukon River exceed EPA guidelines by 2050. Our results indicate minimal impacts to Hg concentrations in water and fish for the low emissions scenario and high impacts for the high emissions scenario.
Accurately assessing the production of bioaccumulative neurotoxic methylmercury by characterizing the phylogenetic diversity, metabolic functions, and activity of methylators in the environment is crucial for understanding constraints on the mercury cycle. Much of our understanding of methylmercury production is based on cultured anaerobic microorganisms within the Deltaproteobacteria , Firmicutes , and Euryarchaeota. Advances in next-generation sequencing technologies have enabled large-scale cultivation-independent surveys of diverse and poorly characterized microorganisms from numerous ecosystems. We used genome-resolved metagenomics and metatranscriptomics to highlight the vast phylogenetic and metabolic diversity of putative mercury methylators and their depth-discrete activities in thawing permafrost. This work underscores the importance of using genome-resolved metagenomics to survey specific putative methylating populations of a given mercury-impacted ecosystem.
Significance
Over many millennia, northern peatlands have accumulated large amounts of carbon and nitrogen, thus cooling the global climate. Over shorter timescales, peatland disturbances can trigger losses of peat and release of greenhouses gases. Despite their importance to the global climate, peatlands remain poorly mapped, and the vulnerability of permafrost peatlands to warming is uncertain. This study compiles over 7,000 field observations to present a data-driven map of northern peatlands and their carbon and nitrogen stocks. We use these maps to model the impact of permafrost thaw on peatlands and find that warming will likely shift the greenhouse gas balance of northern peatlands. At present, peatlands cool the climate, but anthropogenic warming can shift them into a net source of warming.
Land-ocean linkages are strong across the circumpolar north, where the Arctic Ocean accounts for 1% of the global ocean volume and receives more than 10% of the global river discharge. Yet, estimates of Arctic riverine mercury (Hg) export constrained from direct Hg measurements remain sparse. Here, we report results from a coordinated, year-round sampling program that focused on the six major Arctic rivers to establish a contemporary (2012–2017) benchmark of riverine Hg export. We determine that the six major Arctic rivers exported an average of 20,000 kg y-1 of total Hg (THg, all forms of Hg). Upscaled to the pan-Arctic, we estimate THg flux of 37,000 kg y-1. More than 90% of THg flux occurred during peak river discharge in spring and summer. Normalizing fluxes to watershed area (yield) reveals higher THg yields in regions where greater denudation likely enhances Hg mobilization. River discharge, suspended sediment, and dissolved organic carbon predicted THg concentration with moderate fidelity, while suspended sediment and water yields predicted THg yield with high fidelity. These findings establish a benchmark in the face of rapid Arctic warming and an intensifying hydrologic cycle, which will likely accelerate Hg cycling in tandem with changing inputs from thawing permafrost and industrial activity.
Mercury (Hg) is a natural and widespread trace metal, but is considered a priority pollutant, particularly its organic form methylmercury (MMHg), because of human's exposure to MMHg through fish consumption. Pioneering studies showed the methylation of divalent Hg (HgII) to MMHg to occur under oxygen‐limited conditions and to depend on the activity of anaerobic microorganisms. Recent studies identified the hgcAB gene cluster in microorganisms with the capacity to methylate HgII and unveiled a much wider range of species and environmental conditions producing MMHg than previously expected. Here, we review the recent knowledge and approaches used to understand HgII‐methylation, microbial biodiversity and activity involved in these processes, and we highlight the current limits for predicting MMHg concentrations in the environment. The available data unveil the fact that HgII methylation is a bio‐physico‐chemical conundrum in which the efficiency of biological HgII methylation appears to depend chiefly on HgII and nutrients availability, the abundance of electron acceptors such as sulfate or iron, the abundance and composition of organic matter as well as the activity and structure of the microbial community. An increased knowledge of the relationship between microbial community composition, physico‐chemical conditions, MMHg production, and demethylation is necessary to predict variability in MMHg concentrations across environments.
Warming Arctic temperatures have led to permafrost thaw that threatens to release previously sequestered mercury (Hg) back into the environment. Mobilisation of Hg in permafrost waters is of concern, as Hg methylation produced under water-saturated conditions results in the neurotoxin, methyl Hg (MeHg). Thawing permafrost may enhance Hg export, but the magnitude and mechanisms of this mobilisation within Arctic ecosystems remain poorly understood. Such uncertainty limits prognostic modelling of Hg mobilisation and impedes a comprehensive assessment of its threat to Arctic ecosystems and peoples. Here, we address this knowledge gap through an assessment of Hg dynamics across a well-studied permafrost thaw sequence at the peak of the growing season in biologically active peat overlying permafrost, quantifying total gaseous mercury (TGM) fluxes, total mercury (HgTot) in the active layer peat, porewater MeHg concentrations, and identifying microbes with the potential to methylate Hg. During the initial thaw, TGM is liberated, likely by photoreduction from permafrost where it was previously stored for decades to centuries. As thawing proceeds, TGM is largely driven by hydrologic changes as evidenced by Hg accumulation in water-logged, organic-rich peat sediments in fen sites. MeHg in porewaters increase across the thaw gradient, a pattern coincident with increases in the relative abundance of microbes possibly containing genes allowing for methylation of ionic Hg. Findings suggest that under changing climate, frozen, well-drained habitats will thaw and collapse into saturated landscapes, increasing the production of MeHg and providing a significant source of the toxic, bioaccumulative contaminant.
In freshwater ecosystems, several studies have shown a strong linear relationship between total mercury (THg) or methylmercury (MeHg) and dissolved organic carbon (DOC) concentrations. Variations in this linear relationship have been reported, but the magnitude and causes of this variation are not well known. The objective of this study was to conduct a meta‐analysis to quantify and understand the global variation of this mercury (Hg)–DOC association. This meta‐analysis included 54 studies in lentic and lotic ecosystems for a total of 85 THg–DOC and 59 MeHg–DOC relationships. There was an increase in Hg with DOC concentrations in water with a global average slope of 0.25 (confidence interval (CI): 0.20–0.35) ng/mg for THg and 0.029 (CI: 0.014–0.044) ng/mg for MeHg. Relationships were stronger for (1) North American studies, (2) natural environments compared to those disturbed by anthropogenic activities, (3) spatial studies compared to temporal studies, (4) filtered samples (THg only), and (5) the aromatic fraction of DOC compared to the bulk DOC. Coupling with DOC was stronger for THg than for MeHg. Ecosystem type (lentic vs. lotic), geographical coordinates, and publication year did not influence the strength of relationships. Overall, we show that there is a strong but variable coupling between carbon and mercury cycles in freshwater ecosystems globally and that this link is modulated regionally by geographic location, temporal scale, and human activity, with implications for understanding these rapidly changing biogeochemical processes in response to global change.
The central aims of many host or environmental microbiome studies are to elucidate factors associated with microbial community compositions and to relate microbial features to outcomes. However, these aims are often complicated by difficulties stemming from high-dimensionality, non-normality, sparsity, and the compositional nature of microbiome data sets. A key tool in microbiome analysis is beta diversity, defined by the distances between microbial samples. Many different distance metrics have been proposed, all with varying discriminatory power on data with differing characteristics. Here, we propose a compositional beta diversity metric rooted in a centered log-ratio transformation and matrix completion called robust Aitchison PCA. We demonstrate the benefits of compositional transformations upstream of beta diversity calculations through simulations. Additionally, we demonstrate improved effect size, classification accuracy, and robustness to sequencing depth over the current methods on several decreased sample subsets of real microbiome data sets. Finally, we highlight the ability of this new beta diversity metric to retain the feature loadings linked to sample ordinations revealing salient intercommunity niche feature importance.
IMPORTANCE By accounting for the sparse compositional nature of microbiome data sets, robust Aitchison PCA can yield high discriminatory power and salient feature ranking between microbial niches. The software to perform this analysis is available under an open-source license and can be obtained at https://github.com/biocore/DEICODE ; additionally, a QIIME 2 plugin is provided to perform this analysis at https://library.qiime2.org/plugins/q2-deicode .
The formation of the potent neurotoxic methylmercury (MeHg) is a microbially mediated process that has raised much concern because MeHg poses threats to wildlife and human health. Since boreal forest soils can be a source of MeHg in aquatic networks, it is crucial to understand the biogeochemical processes involved in the formation of this pollutant. High-throughput sequencing of 16S rRNA and the mercury methyltransferase, hgcA, combined with geochemical characterisation of soils, were used to determine the microbial populations contributing to MeHg formation in forest soils across Sweden. The hgcA sequences obtained were distributed among diverse clades, including Proteobacteria, Firmicutes, and Methanomicrobia, with Deltaproteobacteria, particularly Geobacteraceae, dominating the libraries across all soils examined. Our results also suggest that MeHg formation is also linked to the composition of non-mercury methylating bacterial communities, likely providing growth substrate (e.g. acetate) for the hgcA-carrying microorganisms responsible for the actual methylation process. While previous research focused on mercury methylating microbial communities of wetlands, this study provides some first insights into the diversity of mercury methylating microorganisms in boreal forest soils.
Methylmercury is a potent human neurotoxin which biomagnifies in aquatic food webs. Although anaerobic microorganisms containing the hgcA gene potentially mediate the formation of methylmercury in natural environments, the diversity of these mercury methylating microbial communities remains largely unexplored. Previous studies have implicated sulphate-reducing bacteria as the main mercury methylators in aquatic ecosystems. In the present study, we characterized the diversity of mercury methylating microbial communities of boreal lake sediments using high-throughput sequencing of 16S rRNA and hgcA genes. Our results show that in the lake sediments also Methanomicrobiales and Geobacteraceae represent abundant members of the mercury methylating communities. In fact, incubation experiments with a mercury isotopic tracer and molybdate revealed that only between 38 % and 45 % of mercury methylation was attributed to sulphate-reduction. These results suggest that methanogens and iron-reducing bacteria may contribute to more than half of mercury methylation in boreal lakes.
Importance Despite global awareness that mercury, and methylmercury in particular, is a neurotoxin that millions of people continue to be exposed to, there are sizable gaps in the understanding of the processes and organisms involved in methylmercury formation in aquatic ecosystems. In the present study we shed light on the diversity of the microorganisms responsible for methylmercury formation in boreal lake sediments. All the microorganisms identified are associated with processing of organic matter in aquatic systems. Moreover, our results show that the well-known mercury methylating sulphate-reducing bacteria constituted only a minor portion of the potential mercury methylators. In contrast, methanogens and iron reducing bacteria were important contributors to methylmercury formation highlighting their role in mercury cycling in the environment.
Motivation
Quality control and preprocessing of FASTQ files are essential to providing clean data for downstream analysis. Traditionally, a different tool is used for each operation, such as quality control, adapter trimming and quality filtering. These tools are often insufficiently fast as most are developed using high-level programming languages (e.g. Python and Java) and provide limited multi-threading support. Reading and loading data multiple times also renders preprocessing slow and I/O inefficient.
Results
We developed fastp as an ultra-fast FASTQ preprocessor with useful quality control and data-filtering features. It can perform quality control, adapter trimming, quality filtering, per-read quality pruning and many other operations with a single scan of the FASTQ data. This tool is developed in C++ and has multi-threading support. Based on our evaluation, fastp is 2–5 times faster than other FASTQ preprocessing tools such as Trimmomatic or Cutadapt despite performing far more operations than similar tools.
Availability and implementation
The open-source code and corresponding instructions are available at https://github.com/OpenGene/fastp.
Large-scale metagenomic datasets enable the recovery of hundreds of population genomes from environmental samples. However, these genomes do not typically represent the full diversity of complex microbial communities. Gene-centric approaches can be used to gain a comprehensive view of diversity by examining each read independently, but traditional pairwise comparison approaches typically over-classify taxonomy and scale poorly with increasing metagenome and database sizes. Here we introduce GraftM, a tool that uses gene specific packages to rapidly identify gene families in metagenomic data using hidden Markov models (HMMs) or DIAMOND databases, and classifies these sequences using placement into pre-constructed gene trees. The speed and accuracy of GraftM was benchmarked with in silico and in vitro mock communities using taxonomic markers, and was found to have higher accuracy at the family level with a processing time 2.0-3.7× faster than currently available software. Exploration of a wetland metagenome using 16S rRNA- and methyl-coenzyme M reductase (McrA)-specific gpkgs revealed taxonomic and functional shifts across a depth gradient. Analysis of the NCBI nr database using the McrA gpkg allowed the detection of novel sequences belonging to phylum-level lineages. A growing collection of gpkgs is available online (https://github.com/geronimp/graftM_gpkgs), where curated packages can be uploaded and exchanged.
Mercury contamination is a growing concern for freshwater food webs in ecosystems without point sources of mercury. Methylmercury (MeHg) is of particular concern, as this is the form of mercury that crosses the blood–brain barrier and is neurotoxic to organisms. Wetlands and benthic sediments have high organic content and low oxygen availability. Anaerobic bacteria drive the metabolic function in these ecosystems and subsequently can methylate mercury. The bioavailability of MeHg is controlled by physicochemical characteristics such as pH, binding affinities, and dissolved organic matter (DOM). Similarly, photodemethylation is influenced by similar characteristics and thereby the two processes should be studied in tandem. The degradation of MeHg through photochemistry is an effective destruction mechanism in freshwater lakes. This review will highlight the uncertainties and known effects of DOM on subsequent photoreactions that lead to the occurrence of mercury photodemethylation and reduction in mercury bioavailability in freshwater ecosystems.
We created a new dataset of spatially interpolated monthly climate data for global land areas at a very high spatial resolution (approximately 1 km 2). We included monthly temperature (minimum, maximum and average), precipitation, solar radiation, vapour pressure and wind speed, aggregated across a target temporal range of 1970–2000, using data from between 9000 and 60 000 weather stations. Weather station data were interpolated using thin-plate splines with covariates including elevation, distance to the coast and three satellite-derived covariates: maximum and minimum land surface temperature as well as cloud cover, obtained with the MODIS satellite platform. Interpolation was done for 23 regions of varying size depending on station density. Satellite data improved prediction accuracy for temperature variables 5–15% (0.07–0.17 ∘ C), particularly for areas with a low station density, although prediction error remained high in such regions for all climate variables. Contributions of satellite covariates were mostly negligible for the other variables, although their importance varied by region. In contrast to the common approach to use a single model formulation for the entire world, we constructed the final product by selecting the best performing model for each region and variable. Global cross-validation correlations were ≥ 0.99 for temperature and humidity, 0.86 for precipitation and 0.76 for wind speed. The fact that most of our climate surface estimates were only marginally improved by use of satellite covariates highlights the importance having a dense, high-quality network of climate station data.
A detailed understanding of the formation of the potent neurotoxic methylmercury is needed to explain the large observed variability in methylmercury levels in aquatic systems. While it is known that organic matter interacts strongly with mercury, the role of organic matter composition in the formation of methylmercury in aquatic systems remains poorly understood. Here we show that phytoplankton-derived organic compounds enhance mercury methylation rates in boreal lake sediments through an overall increase of bacterial activity. Accordingly, in situ mercury methylation defines methylmercury levels in lake sediments strongly influenced by planktonic blooms. In contrast, sediments dominated by terrigenous organic matter inputs have far lower methylation rates but higher concentrations of methylmercury, suggesting that methylmercury was formed in the catchment and imported into lakes. Our findings demonstrate that the origin and molecular composition of organic matter are critical parameters to understand and predict methylmercury formation and accumulation in boreal lake sediments.
Mercury (Hg) methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). The highly conserved nature of the recently identified Hg methylation genes hgcAB provides a foundation for broadly evaluating spatial and niche-specific patterns of microbial Hg methylation potential in nature. We queried hgcAB diversity and distribution in >3500 publicly available microbial metagenomes, encompassing a broad range of environments and generating a new global view of Hg methylation potential. The hgcAB genes were found in nearly all anaerobic (but not aerobic) environments, including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human and mammalian microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate digestive tracts, thawing permafrost soils, coastal “dead zones,” soils, sediments, and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups capable of methylating Hg emerged, including lineages having no cultured representatives. Phylogenetic analysis points to an evolutionary relationship between hgcA and genes encoding corrinoid iron-sulfur proteins functioning in the ancient Wood-Ljungdahl carbon fixation pathway, suggesting that methanogenic Archaea may have been the first to perform these biotransformations.
The Canadian Arctic has vast freshwater resources, and fish are important in the diet of many Northerners. Mercury is a contaminant of concern because of its potential toxicity and elevated bioaccumulation in some fish populations. Over the last decade, significant advances have been made in characterizing the cycling and fate of mercury in these freshwater environments. Large amounts of new data on concentrations, speciation and fluxes of Hg are provided and summarized for water and sediment, which were virtually absent for the Canadian Arctic a decade ago. The biogeochemical processes that control the speciation of mercury remain poorly resolved, including the sites and controls of methylmercury production. Food web studies have examined the roles of Hg uptake, trophic transfer, and diet for Hg bioaccumulation in fish, and, in particular, advances have been made in identifying determinants of mercury levels in lake-dwelling and sea-run forms of Arctic char. In a comparison of common freshwater fish species that were sampled across the Canadian Arctic between 2002 and 2009, no geographic patterns or regional hotspots were evident. Over the last two to four decades, Hg concentrations have increased in some monitored populations of fish in the Mackenzie River Basin while other populations from the Yukon and Nunavut showed no change or a slight decline. The different Hg trends indicate that the drivers of temporal change may be regional or habitat-specific. The Canadian Arctic is undergoing profound environmental change, and preliminary evidence suggests that it may be impacting the cycling and bioaccumulation of mercury. Further research is needed to investigate climate change impacts on the Hg cycle as well as biogeochemical controls of methylmercury production and the processes leading to increasing Hg levels in some fish populations in the Canadian Arctic.
Catchment export of terrestrial dissolved organic matter (DOM) and its downstream degradation in aquatic ecosystems are important components of landscape scale carbon balances. In order to assess the influence of peatland permafrost on river DOM characteristics, we sampled 65 rivers along a 900 km transect crossing into the southern discontinuous permafrost zone on the Boreal and Tundra Plains of western Canada. Catchment peatland cover and catchment location north or south of the permafrost boundary were found together to have strong influences on dissolved organic carbon (DOC) concentrations and DOM chemical composition. River DOC concentrations increased with catchment peatland cover, but were consistently lower for catchments north of the permafrost boundary. In contrast, protein fluorescence (PARAFAC analysis), was unrelated to catchment peatland cover but increased significantly in rivers north of the permafrost boundary. Humic and
fulvic acid contribution to DOM fluorescence was lower in rivers draining catchments with large lakes than in other rivers, consistent with extensive photodegradation, but humic and fulvic acid fluorescence were also lower in rivers north of the permafrost boundary than in rivers to the south. We hypothesize that shifts in river DOM characteristics when crossing the permafrost boundary are related to the influence of permafrost on peatland hydrological connectivity to stream networks, peatland DOM characteristics and differences in DOM degradation within aquatic ecosystems.
Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts on route, with substantial water column losses by mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. Although DOM losses are significant at the global scale, little is known about how the reactivity of DOM varies across landscapes and climates. The reactivity of DOM is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden, and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment and climatic characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water residence time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red-shifted components, were most reactive. In contrast, protein-like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between -6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases to runoff in the boreal region may force lake DOM towards a higher overall amount and proportion of humic-like substances. This article is protected by copyright. All rights reserved.
Downstream mineralization and sedimentation of terrestrial dissolved organic carbon (DOC) render lakes important for landscape carbon cycling in the boreal region, with regulating processes potentially sensitive to perturbations associated with climate change including increased occurrence of wildfire. In this study we assessed chemical composition and reactivity (during both dark and UV incubations) of DOC from lakes and terrestrial sources within a peatland-rich western boreal plains region partially affected by a recent wildfire. While wildfire was found to increase aromaticity of DOC in peat pore-water above the water table, it had no effect on concentrations or composition of DOC from peatland wells and neither affected mineral well or lake DOC characteristics. Lake DOC composition reflected a mixing of peatland and mineral groundwater, with a greater influence of mineral sources to lakes in coarse- than fine-textured settings. Peatland DOC was less biodegradable than mineral DOC, but both mineralization and sedimentation of peatland DOC increased substantially during UV incubations through selective removal of aromatic humic and fulvic acids. DOC composition in lakes with longer residence times had characteristics consistent with increased UV-mediated processing. We estimate that about half of terrestrial DOC inputs had been lost within lakes, mostly due to UV-mediated processes. The importance of within-lake losses of aromatic DOC from peatland sources through UV-mediated processes indicate that terrestrial-aquatic C linkages in the study region are largely disconnected from recent terrestrial primary productivity. Together, our results suggest that characteristics of the study region (climate, surface geology and lake morphometry) render linkages between terrestrial and aquatic C cycling insensitive to the effects of wildfire by determining dominant terrestrial sources and within-lake processes of DOC removal.
Surface water mercury (Hg) and dissolved organic carbon (DOC) concentrations and their ratios, which play a critical role in food chain bioaccumulation of Hg, were examined in lakes from southern boreal, sub‐Arctic taiga, Arctic tundra and polar desert landscapes of eastern and northern Canada. The study sites investigated span a 30° latitudinal gradient representing differences in climate, ecosystem productivity, and atmospheric mercury deposition. Lakes were selected to obtain a range of simple morphometrics such as area, depth, volume and catchment area, with corresponding differences in water residence times (WRT), ranging from 0.1 to 7.5 years. Total mercury (THg) and mono‐methylmercury (MMHg) concentrations correlated positively but weakly with DOC in lake surface waters along the climate gradient, consistent with lower ecosystem and organic matter productivity at higher latitudes. Specific UV absorbance, an indicator of terrestrial organic matter sources, was found to explain some residual variability in THg not explained by DOC. Concentrations of THg and MMHg and their ratios with DOC, particularly the MMHg : DOC ratio as well as %MMHg, were best explained by inverse associations with WRT. These relationships were apparent both within and between regions along the latitudinal gradient, suggesting a net‐negative effect of in‐lake processing on THg and MMHg concentrations associated with longer WRTs. Since the water MMHg : DOC ratio was previously shown to explain foodweb MMHg in the same study lakes, our results suggest that smaller lakes with shorter residence times are more susceptible to MMHg exposure even at low levels of inorganic Hg loading or MMHg production.
The widely accepted conceptual model of mercury (Hg) cycling in freshwater lakes (atmospheric deposition and runoff of inorganic Hg, methylation in bottom sediments and subsequent bioaccumulation and biomagnification in biota) is practically accepted as common knowledge. There is mounting evidence that the dominant processes that regulate inputs, transformations, and bioavailability of Hg in many lakes may be missing from this picture, and the fixation on the temperate stratified lake archetype is impeding our exploration of understudied, but potentially important sources of methylmercury to freshwater lakes. In this review, the importance of understudied biogeochemical processes and sites of methylmercury production are highlighted, including the complexity of redox transformations of Hg within the lake system itself, the complex assemblage of microbes found in biofilms and periphyton (two vastly understudied important sources of methylmercury in many freshwater ecosystems), and the critical role of autochthonous and allochthonous dissolved organic matter which mediates the net supply of methylmercury from the cellular to catchment scale. A conceptual model of lake Hg in contrasting lakes and catchments is presented, highlighting the importance of the autochthonous and allochthonous supply of dissolved organic matter, bioavailable inorganic mercury and methylmercury and providing a framework for future convergent research at the lab and field scales to establish more mechanistic process-based relationships within and among critical compartments that regulate methylmercury concentrations in freshwater ecosystems.
Increasing evidences show that warming is driving Hg release from the cryosphere. However, Hg cycling in thawing permafrost is less understood to date. Here we show that permafrost thaw dominantly supplied no-running thermokarst ponds by permafrost melt waters (PMWs) with high concentration of photo-reducible Hg (PRHg) and subsequently controlled Hg(0) emissions in the Tibetan Plateau. This study was motivated by field survey suggesting that thermokarst ponds as recipient aquatic systems of PMWs could be an active converter of PRHg to Hg(0). Annual Hg mass balance in three seasonally ice-covered thermokarst ponds suggests that PMWs were the dominant input (81.2% to 91.2%) of PRHg in all three thermokarst ponds, and PRHg input would be constraint of Hg(0) emission owing to the fast photo-reduction of PRHg to Hg(0) in water column. Annual Hg(0) emission in the thermokarst ponds of study region was conservatively estimated to increase by 15% over the past half century. Our finding highlights that climate-induced landscape disturbances and changes in hydrogeochemical processes in climate-sensitive permafrost will quickly and in situ drive Hg stored in permafrost for a very long time into modern day Hg cycle, which potentially offsets the anthropogenic Hg mitigation policies.
Methane (CH4) is a potent greenhouse gas that is naturally produced and consumed in soil. The processes result in that soils may function as either a net sink or source of atmospheric methane. Although dry heath tundra ecosystems have recently been identified as important net sinks of atmospheric CH4, we understand little about how similar dry heath sites compare across both elevational gradients and wider geographical areas with regards to CH4 fluxes. To address this shortcoming, we measured CH4 fluxes and soil characteristics under ambient and experimental warming conditions at low and high elevation sites in South (61°N) and West (69°N) Greenland. We then used a structural equation model to explain CH4 fluxes in relation to air temperatures and soil moisture. Soils across all sites were almost universal net CH4 sinks (range for ambient plots: −1.2 to −3.9 μmol m⁻² h⁻¹). Observed soil CH4 fluxes across all sites were significantly positively correlated to soil temperatures at 5 cm depth and negatively correlated to soil moisture. Additional factors such as soil pH and disturbance could also help to explain the differences in CH4 fluxes between similar dry heath sites across greater spatial scales. Understanding the importance of these factors is likely critical to more accurately upscale plot-level measurements of CH4 fluxes in constraining the terrestrial high latitude CH4 sink.
Arctic permafrost soils contain large amounts of organic carbon and the pollutant mercury (Hg). Arctic warming and associated changes in hydrology, biogeochemistry and ecology risk mobilizing soil Hg to rivers and to the Arctic Ocean, yet little is known about the quantity, timing and mechanisms involved. Here we investigate seasonal particulate Hg (PHg) and organic carbon (POC) export in 32 small and medium rivers across a 1700 km latitudinal permafrost transect of the western Siberian Lowland. The PHg concentrations in suspended matter increased with decreasing watershed size. This underlines the significance of POC-rich small streams and wetlands in PHg export from watersheds. Maximum PHg concentrations and export fluxes were located in rivers at the beginning of permafrost zone (sporadic permafrost). We suggest this reflects enhanced Hg mobilization at the permafrost boundary, due to maximal depth of the thawed peat layer. Both the thickness of the active (unfrozen) peat layer and PHg run-off progressively move to the north during the summer and fall seasons, thus leading to maximal PHg export at the sporadic to discontinuous permafrost zone. The discharge-weighed PHg:POC ratio in western Siberian rivers (2.7 ± 0.5 μg Hg: g C) extrapolated to the whole Ob River basin yields a PHg flux of 1.5 ± 0.3 Mg y-1, consistent with previous estimates. For current climate warming and permafrost thaw scenarios in western Siberia, we predict that a northward shift of permafrost boundaries and increase of active layer depth may enhance the PHg export by small rivers to the Arctic Ocean by a factor of two over the next 10-50 years.
Methylmercury (MeHg) is a bioaccumulative toxic contaminant in many ecosystems, but factors governing its production are poorly understood. Recent work has shown that the anaerobic microbial conversion of mercury (Hg) to MeHg requires the Hg-methylation genes hgcAB and that these genes can be used as biomarkers in PCR-based estimators of Hg-methylator abundance. In an effort to determine reliable methods for assessing hgcAB abundance and diversity and linking them to MeHg concentrations, multiple approaches were compared including metagenomic shotgun sequencing, 16S rRNA gene pyrosequencing and cloning/sequencing hgcAB gene products. Hg-methylator abundance was also determined by quantitative hgcA qPCR amplification and metaproteomics for comparison to the above measurements. Samples from eight sites were examined covering a range of total Hg (HgT; 0.03–14 mg kg-1 dry wt. soil) and MeHg (0.05–27 µg kg-1 dry wt. soil) concentrations. In the metagenome and amplicon sequencing of hgcAB diversity, the Deltaproteobacteria were the dominant Hg-methylators while Firmicutes and methanogenic Archaea were typically ~50% less abundant. This was consistent with metaproteomics estimates where the Deltaproteobacteria were steadily higher. The 16S rRNA gene pyrosequencing did not have sufficient resolution to identify hgcAB+ species. Metagenomic and hgcAB results were similar for Hg-methylator diversity and clade-specific qPCR-based approaches for hgcA are only appropriate when comparing the abundance of a particular clade across various samples. Weak correlations between Hg-methylating bacteria and soil Hg concentrations were observed for similar environmental samples, but overall total Hg and MeHg concentrations poorly correlated with Hg-cycling genes.
The transformations of aqueous inorganic divalent mercury (Hg(II)i) to volatile dissolved gaseous mercury (Hg(0)(aq)) and toxic methylmercury (MeHg) govern mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)i, Hg(0)(aq), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)i reduction and Hg(II)i methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)i and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)(aq) to Hg(II)i exhibited an inverse relationship to Hg(II)i concentration. A ubiquitous pathway for Hg(0)(aq) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)i and decreasing the concentration of volatile Hg(0)(aq) relative to Hg(II)i. There was no evidence of Hg(0)(aq) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)i was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.
Large-scale studies are needed to identify the drivers of total mercury (THg) and monomethyl-mercury (MeHg) concentrations in aquatic ecosystems. Studies attempting to link dissolved organic matter (DOM) to levels of THg or MeHg are few and geographically constrained. Additionally, stream and river systems have been understudied as compared to lakes. Hence, the aim of this study was to examine the influence of DOM concentration and composition, morphological descriptors, land uses and water chemistry on THg and MeHg concentrations and the percentage of THg as MeHg (%MeHg) in 29 streams across Europe spanning from 41°N to 64 °N. THg concentrations (0.06-2.78 ng L-1) were highest in streams characterized by DOM with a high terrestrial soil signature and low nutrient content. MeHg concentrations (7.8-159 pg L-1) varied non-systematically across systems. Relationships between DOM bulk characteristics and THg and MeHg suggest that while soil derived DOM inputs control THg concentrations, autochthonous DOM (aquatically produced) and the availability of electron acceptors for Hg methylating microorganisms (e.g. sulfate) drive %MeHg and potentially MeHg concentration. Overall, these results highlight the large spatial variability in THg and MeHg concentrations at the European scale, and underscore the importance of DOM composition on mercury cycling in fluvial systems.
Changing climate in northern regions is causing permafrost to thaw with major implications for the global mercury (Hg) cycle. We estimated Hg in permafrost regions based on in situ measurements of sediment total mercury (STHg), soil organic carbon (SOC), and the Hg to carbon ratio (RHgC) combined with maps of soil carbon. We measured a median STHg of 43 ± 30 ng Hg g soil−1 and a median RHgC of 1.6 ± 0.9 μg Hg g C−1, consistent with published results of STHg for tundra soils and 11,000 measurements from 4,926 temperate, nonpermafrost sites in North America and Eurasia. We estimate that the Northern Hemisphere permafrost regions contain 1,656 ± 962 Gg Hg, of which 793 ± 461 Gg Hg is frozen in permafrost. Permafrost soils store nearly twice as much Hg as all other soils, the ocean, and the atmosphere combined, and this Hg is vulnerable to release as permafrost thaws over the next century. Existing estimates greatly underestimate Hg in permafrost soils, indicating a need to reevaluate the role of the Arctic regions in the global Hg cycle.
Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment in northern Minnesota. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations and we verified the complete breakdown of DOM through Hg spike addition analysis. We report a relatively large variation in mass-dependent fractionation (δ²⁰²Hg; from -2.12 to -1.32 ‰) and a smaller, but significant, variation of mass-independent fractionation (Δ¹⁹⁹Hg; from -0.35 to -0.12 ‰) during two years of sampling with streamflow varying from 0.003 to 7.8 L s⁻¹. Large variations in δ²⁰²Hg occurred only during low streamflow (< 0.6 L s⁻¹). These results suggest that under high streamflow conditions a peatland lagg zone between the bog (3.0 ha) and uplands (6.7 ha) becomes the dominant source of Hg and controls the isotopic signature of Hg in downstream waters. Further, we used a binary mixing model and showed that except for the spring snowmelt period, Hg in stream water from the catchment was mainly derived from dry deposition of gaseous elemental Hg (73-95 %). This study demonstrated the usefulness of Hg isotopes for tracing sources of Hg deposition, which can lead to a better understanding of the biogeochemical cycling and hydrological transport of Hg in headwater catchments.
Photodemethylation can be one of the primary processes for loss of neurotoxic methylmercury (MeHg) in freshwater lakes. Few studies have quantified seasonal variations in photodemethylation rate constants as a function of dissolved organic matter (DOM). We conducted 1-week irradiation experiments in two seasons to test for spatial and temporal differences in photodemethylation potential in temperate lake waters. Six study lakes in Kejimkujik National Park, Nova Scotia were sampled in summer and fall to include a range of naturally occurring DOM concentrations (4.4-13.4 and 3.9-16.4 mg C L(-1), respectively). A negative linear relationship (R(2) = 0.76, p = 0.01) was found between DOM concentration and photodemethylation rate constant across seasons, indicating that DOM is a strong predictor of MeHg photodemethylation independent of seasonal effects. The two highest carbon lakes (BDW and PEB) had significantly higher energy-normalized photodemethylation rate constants in summer compared to fall corresponding with lower DOM concentrations in summer relative to fall. Additionally, there were negative linear relationships between MeHg photodemethylation and DOM photomineralization (R(2)s = 0.58-0.72) and DOM photobleaching (R(2)s = 0.83-0.90). This key finding suggests that competition for photons within DOM structures may reduce the potential for MeHg photodemethylation in high carbon waters and that this relationship persists across seasons.
In arctic and sub-arctic environments, mercury (Hg), more specifically toxic methylmercury (MeHg), is of growing concern to local communities because of its accumulation in fish. In these regions, there is particular interest in the potential mobilization of atmospherically deposited Hg sequestered in permafrost that is thawing at unprecedented rates. Permafrost thaw and the resulting ground surface subsidence transforms forested peat plateaus into treeless and permafrost-free thermokarst wetlands where inorganic Hg released from the thawed permafrost and draining from the surrounding peat plateaus may be transformed to MeHg. This study begins to characterize the spatial distribution of MeHg in a peat plateau-thermokarst wetland complex, a feature that prevails throughout the wetland-dominated southern margin of thawing discontinuous permafrost in Canada's Northwest Territories. We measured pore water total Hg, MeHg, dissolved organic matter characteristics and general water chemistry parameters to evaluate the role of permafrost thaw on the pattern of water chemistry. A gradient in vegetation composition, water chemistry and dissolved organic matter characteristics followed a toposequence from the ombrotrophic bogs near the crest of the complex to poor fens at its downslope margins. We found that pore waters in poor fens contained elevated levels of MeHg, and the water draining from these features had dissolved MeHg concentrations 4.5 to 14.5 times higher than the water draining from the bogs. It was determined through analysis of historical aerial images that the poor fens in the toposequence had formed relatively recently (early 1970s) as a result of permafrost thaw. Differences between the fens and bogs are likely to be a result of their differences in groundwater function, and this suggests that permafrost thaw in this landscape can result in hotspots for Hg methylation that are hydrologically connected to downstream ecosystems.
Permafrost thaw ponds of the warming Eastern Canadian Arctic are major landscape constituents and often display high levels of methylmercury (MeHg). We examined photodegradation potentials in high-dissolved organic matter (DOC) thaw ponds on Bylot Island (BYL) and a low-DOC oligotrophic lake on Cornwallis Island (Char Lake). In BYL, the ambient MeHg photodemethylation (PD) rate over 48 h of solar exposure was 6.1 × 10-3 m2 E-1, and the rate in MeHg amended samples was 9.3 × 10-3 m2 E-1. In contrast, in low-DOC Char Lake, PD was only observed in the first 12 hours, which suggests that PD may not be an important loss process in polar desert lakes. Thioglycolic acid addition slowed PD, while glutathione and chlorides did not impact northern PD rates. During an ecosystem-wide experiment conducted in a covered BYL pond, there was neither net MeHg increase in the dark nor loss attributable to PD following re-exposure to sunlight. We propose that high-DOC Arctic thaw ponds are more prone to MeHg PD than nearby oligotrophic lakes, likely through photoproduction of reactive species rather than via thiol complexation. However, at the ecosystem level, these ponds, which are widespread through the Arctic, remain likely sources of MeHg for neighbouring systems.
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 also 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.
Ecologists and evolutionary biologists are relying on an increasingly
sophisticated set of statistical tools to describe complex natural systems. One
such tool that has gained increasing traction in the life sciences is
structural equation modeling (SEM), a variant of path analysis that resolves
complex multivariate relationships among a suite of interrelated variables. SEM
has historically relied on covariances among variables, rather than the values
of the data points themselves. While this approach permits a wide variety of
model forms, it limits the incorporation of detailed specifications. Here, I
present a fully-documented, open-source R package piecewiseSEM that builds on
the base R syntax for all current generalized linear, least-square, and mixed
effects models. I also provide two worked examples: one involving a
hierarchical dataset with non-normally distributed variables, and a second
involving phylogenetically-independent contrasts. My goal is to provide a
user-friendly and tractable implementation of SEM that also reflects the
ecological and methodological processes generating data.
Permafrost thaw ponds are ubiquitous in the eastern Canadian Arctic, yet little information exists on their potential as sources of methylmercury (MeHg) to freshwaters. They are microbially-active and conducive to methylation of inorganic mercury, and are also affected by Arctic warming. This multi-year study investigates thaw ponds in a discontinuous permafrost region in the Subarctic taiga (Kuujjuarapik-Whapmagoostui, QC) and a continuous permafrost region in the Arctic tundra (Bylot Island, NU). MeHg concentrations in thaw ponds were well above levels measured in most freshwater ecosystems in the Canadian Arctic (> 0.1 ng L-1). On Bylot, ice-wedge trough ponds showed significantly higher MeHg (0.3 - 2.2 ng L-1) than polygonal ponds (0.1 - 0.3 ng L-1) or lakes (< 0.1 ng L-1). High MeHg were measured in the bottom waters of Subarctic thaw ponds near Kuujjuarapik (0.1 - 3.1 ngL-1). High water MeHg concentrations in thaw ponds were strongly correlated with variables associated with high inputs of organic matter (DOC, a320, Fe), nutrients (TP, TN), and microbial activity (dissolved CO2 and CH4). Thawing permafrost due to Arctic warming will continue to release nutrients and organic carbon into these systems and increase ponding in some regions, likely stimulating higher water concentrations of MeHg. Greater hydrological connectivity from permafrost thawing may potentially increase transport of MeHg from thaw ponds to neighbouring aquatic ecosystems.
Whether intrinsic molecular properties or extrinsic factors such as environmental conditions control the decomposition of natural organic matter across soil, marine and freshwater systems has been subject to debate. Comprehensive evaluations of the controls that molecular structure exerts on organic matter’s persistence in the environment have been precluded by organic matter’s extreme complexity. Here we examine dissolved organic matter from 109 Swedish lakes using ultrahigh-resolution mass spectrometry and optical spectroscopy to investigate the constraints on its persistence in the environment. We find that degradation processes preferentially remove oxidized, aromatic compounds, whereas reduced, aliphatic and N-containing compounds are either resistant to degradation or tightly cycled and thus persist in aquatic systems. The patterns we observe for individual molecules are consistent with our measurements of emergent bulk characteristics of organic matter at wide geographic and temporal scales, as reflected by optical properties. We conclude that intrinsic molecular properties are an important control of overall organic matter reactivity.
Predicting the bioavailability of inorganic mercury (Hg) to bacteria that produce the potent bioaccumulative neurotoxin monomethylmercury remains one of the greatest challenges in predicting the environmental fate and transport of Hg. Dissolved organic matter (DOM) affects mercury methylation due to its influence on cell physiology (as a potential nutrient) and its influence on HgII speciation in solution (as a complexing agent), therefore controlling Hg bioavailability. We assessed the role of DOM on HgII bioavailability to a gram-negative bacterium bioreporter under oxic pseudo- and non-equilibrium conditions, using defined media and field samples spanning a wide range of DOM levels. Our results showed that HgII was considerably more bioavailable under non-equilibrium conditions than when DOM was absent or when HgII and DOM had reached pseudo-equilibrium (24h) prior to cell exposure. Under these enhanced uptake conditions, HgII bioavailability followed a bell shaped curve as DOM concentrations increased, both for defined media and natural water samples, consistent with bioaccumulation results in a companion paper (this issue) observed for amphipods. Experiments also suggest that DOM may not only provide shuttle molecules facilitating Hg uptake but also alter cell wall properties to facilitate the first steps towards HgII internalization. We propose the existence of a short-lived yet critical time window (<24h) during which DOM facilitates the entry of newly deposited HgII into aquatic food webs, suggesting that the bulk of mercury incorporation in aquatic food webs would occur within hours following its deposition from the atmosphere.
In the present review, key interactions between Hg and phytoplankton are described and discussed in order to highlight the role of phytoplankton in the biogeochemical cycle of Hg and to understand direct or indirect Hg effects on them. Phytoplankton are exposed to various Hg species in surface waters. By Hg uptake, phytoplankton affect the concentration, speciation and fate of mercury in aquatic systems. The mechanisms by which phytoplankton take up Hg are still not well known, but several studies have suggested that both facilitated transport and passive diffusion could be involved. Once internalized, Hg will impact several physiological processes, including photosynthesis. To counteract these negative effects, phytoplankton have developed several detoxification strategies, such as the reduction of Hg to elemental Hg(0) or its sequestration by intracellular ligands. Based on the toxicological studies performed so far in the laboratory, Hg is unlikely to be toxic to phytoplankton when they are exposed to environmentally relevant Hg concentrations. However, this statement should be taken with caution as questions remain as to which Hg species control Hg bioavailability and about Hg uptake mechanisms. Finally, phytoplankton are primary producers and accumulated Hg will be transferred to higher consumers. Phytoplankton are a key component in aquatic systems and their interactions with Hg still need to be further studied to fully comprehend the biogeochemical cycle of Hg and the impact of this ubiquitous metal on ecosystems. Environ Toxicol Chem © 2013 SETAC.