Patterns and trends of atmospheric mercury in the GMOS network: Insights based on a decade of measurements.

The Global Mercury Observation System (GMOS) network, initially a five-year project (2010-2015) funded by the European Commission, continued as a GEO Flagship program to support the Global Observation System for Mercury (GOS4M). GMOS was envisioned as a coordinated global observing system to monitor atmospheric mercury (Hg) on a global scale, to support and evaluate the effective implementation of the Minamata Convention on Mercury (MCM). Twenty-eight ground-based stations have participated in monitoring activities, following GMOS sampling protocols and related data quality control management. The GMOS network provides representative coverage of all latitudes, from the Northern Hemisphere to the Southern Hemisphere including the Arctic Circle, Antarctica, and the Tropical Zone. This work presents atmospheric Hg data, available as Total Gaseous Mercury (TGM) or Gaseous Elemental Mercury (GEM) concentrations, recorded within the GMOS network from 2011 to 2020. TGM/GEM concentrations were analysed in terms of their variability along latitudinal areas, considering their comparability, temporal trends and patterns. The main results confirmed a clear gradient of TGM/GEM concentrations between the northern (1.58 ± 0.31 ng/m3) and southern (0.97 ± 0.14 ng/m3) hemispheres. Decreasing trends in TGM/GEM levels were found to be strongly significant only for selected remote stations with at least 5 years of data coverage. Seasonality in atmospheric TGM/GEM concentrations was observed to increase with latitude and is greater at inland sites than at coastal sites.

Over a decade of atmospheric mercury monitoring at Amsterdam Island in the French Southern and Antarctic Lands.

The Minamata Convention, a global and legally binding treaty that entered into force in 2017, aims to protect human health and the environment from harmful mercury (Hg) effects by reducing anthropogenic Hg emissions and environmental levels. The Conference of the Parties is to periodically evaluate the Convention's effectiveness, starting in 2023, using existing monitoring data and observed trends. Monitoring atmospheric Hg levels has been proposed as a key indicator. However, data gaps exist, especially in the Southern Hemisphere. Here, we present over a decade of atmospheric Hg monitoring data at Amsterdam Island (37.80°S, 77.55°E), in the remote southern Indian Ocean. Datasets include gaseous elemental and oxidised Hg species ambient air concentrations from either active/continuous or passive/discrete acquisition methods, and annual total Hg wet deposition fluxes. These datasets are made available to the community to support policy-making and further scientific advancements.

Seven-year monitoring of mercury in wet precipitation and atmosphere at the Amsterdam Island GMOS station.

Mercury (Hg) fate and transport research requires more effort to obtain a deep knowledge of its biogeochemical cycle, particularly in the Southern Hemisphere and Tropics that are still missing of distributed monitoring sites. Continuous monitoring of atmospheric Hg concentrations and trend worldwide is relevant for the effectiveness evaluation of the Minamata Convention on Mercury (MCM) actions. In this context, Gaseous Elemental Mercury (GEM) and total mercury (THg) in precipitations were monitored from 2013 to 2019 at the Amsterdam Island Observatory (AMS - 37°48'S, 77°34'E) to provide insights into the Hg pathway in the remote southern Indian Ocean, also considering ancillary dataset of Rn-222, CO2, CO, and CH4. GEM average concentration was 1.06 ± 0.07 ng m-3, with a slight increase during the austral winter due to both higher wind speed over the surface ocean and contributions from southern Africa. In wet depositions, THg average concentration was 2.39 ± 1.17 ng L-1, whereas the annual flux averaged 2.04 ± 0.80 µg m-2 year-1. In general, both GEM and Volume-Weighted Mean Concentration (VWMC) of THg did not show an increasing/decreasing trend over the seven-year period, suggesting a substantial lack of evolution about emission of Hg reaching AMS. Air masses Cluster Analysis and Potential Source Contribution Function showed that oceanic evasion was the main Hg contributor at AMS, while further contributions were attributable to long-range transport events from southern Africa, particularly when the occurrence of El Niño increased the frequency of wildfires.

Observations of the chemistry and concentrations of reactive Hg at locations with different ambient air chemistry.

The Hg research community needs methods to more accurately measure atmospheric Hg concentrations and chemistry. The Reactive Mercury Active System (RMAS) uses cation exchange, nylon, and PTFE membranes to determine reactive mercury (RM), gaseous oxidized mercury, and particulate-bound mercury (PBM) concentrations and chemistry. New data for Atlanta, Georgia (NRGT) demonstrated that particulate-bound Hg was dominant and the chemistry was primarily N and S HgII compounds. At Great Salt Lake, Utah (GSL), RM was predominately PBM, with NS > organics > halogen > O HgII compounds. At Guadalupe Mountains National Park, Texas (GUMO), halogenated compound concentrations were lowest when air interacting with the site was primarily derived from the Midwest, and highest when the air was sourced from Mexico. At Amsterdam Island, Southern Indian Ocean, compounds were primarily halogenated with some N, S, and organic HgII compounds potentially associated with biological activity. The GEOS-Chem model was applied to see if it predicted measurements at five field sites. Model values were higher than observations at GSL, slightly lower at NRGT, and observations were an order of magnitude higher than modeled values for GUMO and Reno, Nevada. In general, data collected from 13 locations indicated that N, S, and organic RM compounds were associated with city and forest locations, halogenated compounds were sourced from the marine boundary layer, and O compounds were associated with long-range transport. Data being developed currently, and in the past, suggest there are multiple forms of RM that modelers must consider, and PBM is an important component of RM.

Sunlight-driven nitrate loss records Antarctic surface mass balance.

Standard proxies for reconstructing surface mass balance (SMB) in Antarctic ice cores are often inaccurate or coarsely resolved when applied to more complicated environments away from dome summits. Here, we propose an alternative SMB proxy based on photolytic fractionation of nitrogen isotopes in nitrate observed at 114 sites throughout East Antarctica. Applying this proxy approach to nitrate in a shallow core drilled at a moderate SMB site (Aurora Basin North), we reconstruct 700 years of SMB changes that agree well with changes estimated from ice core density and upstream surface topography. For the under-sampled transition zones between dome summits and the coast, we show that this proxy can provide past and present SMB values that reflect the immediate local environment and are derived independently from existing techniques.

Mercury isotope evidence for Arctic summertime re-emission of mercury from the cryosphere.

During Arctic springtime, halogen radicals oxidize atmospheric elemental mercury (Hg0), which deposits to the cryosphere. This is followed by a summertime atmospheric Hg0 peak that is thought to result mostly from terrestrial Hg inputs to the Arctic Ocean, followed by photoreduction and emission to air. The large terrestrial Hg contribution to the Arctic Ocean and global atmosphere has raised concern over the potential release of permafrost Hg, via rivers and coastal erosion, with Arctic warming. Here we investigate Hg isotope variability of Arctic atmospheric, marine, and terrestrial Hg. We observe highly characteristic Hg isotope signatures during the summertime peak that reflect re-emission of Hg deposited to the cryosphere during spring. Air mass back trajectories support a cryospheric Hg emission source but no major terrestrial source. This implies that terrestrial Hg inputs to the Arctic Ocean remain in the marine ecosystem, without substantial loss to the global atmosphere, but with possible effects on food webs.

Occurrence of legacy and emerging organic contaminants in snow at Dome C in the Antarctic.

Concentrations of 9 organophosphate esters (OPEs), 16 perfluoroalkylated substances (PFASs) and 17 polycyclic aromatic hydrocarbons (PAHs) were investigated in surface snow samples collected at Dome C on the Antarctic Plateau in summer 2016. Tris(1-chloro-2-propyl) phosphate (TCPP), tris-(2-chloroethyl) phosphate (TCEP) and tri-n-butylphosphate (TnBP) were the dominant compounds of OPEs, with mean concentrations of 8157 ± 4860, 1128 ± 928 and 1232 ± 1147 pg/L. Perfluorooctanoic acid (PFOA, mean: 358 ± 71 pg/L) was the dominant compound of PFASs, and following by perfluoro-n-hexanoic acid (PFHxA, mean: 222 ± 97 pg/L), perfluoro-n-heptanoic acid (PFHpA, 183 ± 60 pg/L) and perfluoro-n-pentanoic acid (PFPeA, 175 ± 105 pg/L). 2-(Heptafluoropropoxy)propanoic acid (HFPO-DA, mean: 9.2 ± 2.6 pg/L) was determined in the Antarctic for the first time. Significantly positive correlations were observed between HFPO-DA and the short-chain PFASs, implying they have similar emission sources and long-range transport potential. High levels of 2-methylnaphthalene and 1-methylnaphthalene, as well as the ratios of PAH congeners indicated PAHs were attributable mostly to combustion origin. Occurrence and profiles of the indicators of OPEs, PFASs and PAHs, as well as air mass back-trajectory analysis provided direct evidences of human activities on Concordia station and posed obvious impacts on local environments in the Antarctic. Nevertheless, the exchange processes among different environmental matrices may drive the long-range transport and redistribution of the legacy and emerging Organic contaminants from coast to inland in the Antarctic.

Seasonal shift in airborne microbial communities.

Microorganisms are ubiquitous in the atmosphere. Global investigations on the geographical and temporal distribution of airborne microbial communities are critical for identifying the sources and the factors shaping airborne communities. At mid-latitude sites, a seasonal shift in both the concentration and diversity of airborne microbial communities has been systematically observed in the planetary boundary layer. While the factors suspected of affecting this seasonal change were hypothesized (e.g., changes in the surface conditions, meteorological parameters and global air circulation), our understanding on how these factors influence the temporal variation of airborne microbial communities, especially at the microbial taxon level, remains limited. Here, we investigated the distribution of both airborne bacterial and fungal communities on a weekly basis over more than one year at the mid-latitude and continental site of puy de Dôme (France; +1465 m altitude above sea level). The seasonal shift in microbial community structure was likely correlated to the seasonal changes in the characteristics of puy de Dôme's landscape (croplands and natural vegetation). The airborne microbial taxa that were the most affected by seasonal changes trended differently throughout the seasons in relation with their trophic mode. In addition, the windy and variable local meteorological conditions found at puy de Dôme were likely responsible for the intraseasonal variability observed in the composition of airborne microbial communities.

Author Correction: Global airborne microbial communities controlled by surrounding landscapes and wind conditions.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Global airborne microbial communities controlled by surrounding landscapes and wind conditions.

The atmosphere is an important route for transporting and disseminating microorganisms over short and long distances. Understanding how microorganisms are distributed in the atmosphere is critical due to their role in public health, meteorology and atmospheric chemistry. In order to determine the dominant processes that structure airborne microbial communities, we investigated the diversity and abundance of both bacteria and fungi from the PM10 particle size (particulate matter of 10 micrometers or less in diameter) as well as particulate matter chemistry and local meteorological characteristics over time at nine different meteorological stations around the world. The bacterial genera Bacillus and Sphingomonas as well as the fungal species Pseudotaeniolina globaosa and Cladophialophora proteae were the most abundant taxa of the dataset, although their relative abundances varied greatly based on sampling site. Bacterial and fungal concentration was the highest at the high-altitude and semi-arid plateau of Namco (China; 3.56 × 106 ± 3.01 × 106 cells/m3) and at the high-altitude and vegetated mountain peak Storm-Peak (Colorado, USA; 8.78 × 104 ± 6.49 × 104 cells/m3), respectively. Surrounding ecosystems, especially within a 50 km perimeter of our sampling stations, were the main contributors to the composition of airborne microbial communities. Temporal stability in the composition of airborne microbial communities was mainly explained by the diversity and evenness of the surrounding landscapes and the wind direction variability over time. Airborne microbial communities appear to be the result of large inputs from nearby sources with possible low and diluted inputs from distant sources.

Methods to Investigate the Global Atmospheric Microbiome.

The interplay between microbes and atmospheric physical and chemical conditions is an open field of research that can only be fully addressed using multidisciplinary approaches. The lack of coordinated efforts to gather data at representative temporal and spatial scales limits aerobiology to help understand large scale patterns of global microbial biodiversity and its causal relationships with the environmental context. This paper presents the sampling strategy and analytical protocols developed in order to integrate different fields of research such as microbiology, -omics biology, atmospheric chemistry, physics and meteorology to characterize atmospheric microbial life. These include control of chemical and microbial contaminations from sampling to analysis and identification of experimental procedures for characterizing airborne microbial biodiversity and its functioning from the atmospheric samples collected at remote sites from low cell density environments. We used high-volume sampling strategy to address both chemical and microbial composition of the atmosphere, because it can help overcome low aerosol and microbial cell concentrations. To account for contaminations, exposed and unexposed control filters were processed along with the samples. We present a method that allows for the extraction of chemical and biological data from the same quartz filters. We tested different sampling times, extraction kits and methods to optimize DNA yield from filters. Based on our results, we recommend supplementary sterilization steps to reduce filter contamination induced by handling and transport. These include manipulation under laminar flow hoods and UV sterilization. In terms of DNA extraction, we recommend a vortex step and a heating step to reduce binding to the quartz fibers of the filters. These steps have led to a 10-fold increase in DNA yield, allowing for downstream omics analysis of air samples. Based on our results, our method can be integrated into pre-existing long-term monitoring field protocols for the atmosphere both in terms of atmospheric chemistry and biology. We recommend using standardized air volumes and to develop standard operating protocols for field users to better control the operational quality.

Feedback mechanisms between snow and atmospheric mercury: Results and observations from field campaigns on the Antarctic plateau.

The Antarctic Plateau snowpack is an important environment for the mercury geochemical cycle. We have extensively characterized and compared the changes in surface snow and atmospheric mercury concentrations that occur at Dome C. Three summer sampling campaigns were conducted between 2013 and 2016. The three campaigns had different meteorological conditions that significantly affected mercury deposition processes and its abundance in surface snow. In the absence of snow deposition events, the surface mercury concentration remained stable with narrow oscillations, while an increase in precipitation results in a higher mercury variability. The Hg concentrations detected confirm that snowfall can act as a mercury atmospheric scavenger. A high temporal resolution sampling experiment showed that surface concentration changes are connected with the diurnal solar radiation cycle. Mercury in surface snow is highly dynamic and it could decrease by up to 90% within 4/6 h. A negative relationship between surface snow mercury and atmospheric concentrations has been detected suggesting a mutual dynamic exchange between these two environments. Mercury concentrations were also compared with the Br concentrations in surface and deeper snow, results suggest that Br could have an active role in Hg deposition, particularly when air masses are from coastal areas. This research presents new information on the presence of Hg in surface and deeper snow layers, improving our understanding of atmospheric Hg deposition to the snow surface and the possible role of re-emission on the atmospheric Hg concentration.

Bacterial characterization of the snow cover at Spitzberg, Svalbard.

A sampling campaign was organized during spring 2004 in Spitzberg, Svalbard, in the area around the scientific base of Ny-Alesund, to characterize the snow pack bacterial population. Total bacteria counts were established by 4',6-diamino-2-phenylindole (DAPI) in the seasonal snow pack bordering the sea. On the sea shore, bacterial concentration was about 6 x 10(4) cells mL(-1), without any significant variation according to depth. In the accumulation snow layer of the glacier, concentrations were about 2 x 10(4 )cells mL(-1), except in the 2003 summer layer, where it reached 2 x 10(5) cells mL(-1), as the result of cell multiplication allowed by higher temperature and snow melting. Strains isolated from the seasonal snow pack were identified from their 16S rRNA gene sequences, and lodged in GenBank. They belong to the Alphaproteobacteria, Betaproteobacteria and Gammaproteobacteria, Firmicutes and Actinobacteria. They are closely related to cold environment bacteria, as revealed by phylogenetic tree constructions, and two appear to be of unknown affiliation. Using 1H nuclear magnetic resonance, it was shown that these isolates have the capacity to degrade organic compounds found in Arctic snow (propionate, acetate and formate), and this can allow them to develop when snow melts, and thus to be actively involved in snow chemistry.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network.

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.