Chemical cycling and deposition of atmospheric mercury in Polar Regions: review of recent measurements and comparison with models

Mercury (Hg) is a worldwide contaminant that can cause adverse health effects to wildlife and humans. While atmospheric modeling traces the link from emissions to deposition of Hg onto environmental surfaces, large uncertainties arise from our incomplete understanding of atmospheric processes (oxidation pathways, deposition, and re-emission). Atmospheric Hg reactivity is exacerbated in high latitudes and there is still much to be learned from polar regions in terms of atmospheric processes. This paper provides a synthesis of the atmospheric Hg monitoring data available in recent years (2011–2015) in the Arctic and in Antarctica along with a comparison of these observations with numerical simulations using four cutting-edge global models. The cycle of atmospheric Hg in the Arctic and in Antarctica presents both similarities and differences. Coastal sites in the two regions are both influenced by springtime atmospheric Hg depletion events and by summertime snowpack re-emission and oceanic evasion of Hg. The cycle of atmospheric Hg differs between the two regions primarily because of their different geography. While Arctic sites are significantly influenced by northern hemispheric Hg emissions especially in winter, coastal Antarctic sites are significantly influenced by the reactivity observed on the East Antarctic ice sheet due to katabatic winds. Based on the comparison of multi-model simulations with observations, this paper discusses whether the processes that affect atmospheric Hg seasonality and interannual variability are appropriately represented in the models and identifies research gaps in our understanding of the atmospheric Hg cycling in high latitudes

Thickness variation of sediment lamination in Puyehue Lake (Lake District, Southern Chile) during the last millennium: a regional southern hemisphere record of El Niño?

Lake District (Southern Chile) is investigated as a new regional record of past climate changes in Southern Hemisphere, in particular in order to evidence any regional impact of ENSO in South-America. We analyzed three short cores (60 cm) from the key-site of Puyehue Lake (40°S) which has been selected for multiproxy analyses (Bertrand et al., this session). Sedimentation model is related by a laminated mud increment mainly controlled by the biogenic activity and by the annual thermal lake cycles (turn-over of the nutrients during autumn and winter-time). We analysed lamination occurrence and thickness from enlarged images of thin-sections preparation (magnitude 5x) in order to increase sediment resolution. The age-model of the cores is based on counting laminations, assuming that sedimentation is varved. Indeed, this varve sedimentation model is in accordance with chronology based on the decrease of 210Pb rates and peaks of 137Cs. Variation of the lamination thickness shows four different phases of sedimentation. (1) Since c.a. 1350 A.D. (base of the cores) to 1460 A.D., varve-thickness ranges around 400 µm and sedimentation rates are 0,5 mm/yr. (2) From 1460 A.D. to 1890 A.D., varve-thickness is about 600 µm with a minimum at 1730 A.D., and sedimentation rates increases from 0,7 to 1,2 mm/yr. (3) From 1890 A.D. to c.a 1930 A.D., varve-thickness increases up to 2000 µm, and sedimentation rates vary between 1,2 to 2,3 mm/yr. (4) From c.a. 1930 A.D. to Actual, varves are about 500 µm with a destratified layer coincident with the 1960 seismic event of Valdivia; sedimentation rates are between 0,6 to 1,2 mm/yr. The four phases are discussed according to variations of the lake palaeoproductivity by respect with river run-off detrital supplies; the influence of the westerlies on the variations of the lamination thickness is discussed in term of possible regional impact of ENSO

Photolytic modification of seasonal nitrate isotope cycles in East Antarctica

Nitrate in Antarctic snow has seasonal cycles in nitrogen and oxygen isotopic ratios that reflect its sources and atmospheric formation processes, and as a result, nitrate archived in Antarctic ice should have great potential to record atmospheric chemistry changes over thousands of years. However, sunlight that strikes the snow surface results in photolytic nitrate loss and isotopic fractionation that can completely obscure the nitrate's original isotopic values. To gain insight into how photolysis overwrites the seasonal atmospheric cycles, we collected 244 snow samples along an 850 km transect of East Antarctica during the 2013–2014 CHICTABA traverse. The CHICTABA route's limited elevation change, consistent distance between the coast and the high interior plateau, and intermediate accumulation rates offered a gentle environmental gradient ideal for studying the competing pre- and post-depositional influences on archived nitrate isotopes. We find that nitrate isotopes in snow along the transect are indeed notably modified by photolysis after deposition, and drier sites have more intense photolytic impacts. Still, an imprint of the original seasonal cycles of atmospheric nitrate isotopes is present in the top 1–2 m of the snowpack and likely preserved through archiving in glacial ice at these sites. Despite this preservation, reconstructing past atmospheric values from archived nitrate in similar transitional regions will remain a difficult challenge without having an independent proxy for photolytic loss to correct for post-depositional isotopic changes. Nevertheless, nitrate isotopes should function as a proxy for snow accumulation rate in such regions if multiple years of deposition are aggregated to remove the seasonal cycles, and this application can prove highly valuable in its own right.</p

Understanding mercury oxidation and air–snow exchange on the East Antarctic Plateau: a modeling study

Distinct diurnal and seasonal variations of mercury (Hg) have been observed in near-surface air at Concordia Station on the East Antarctic Plateau, but the processes controlling these characteristics are not well understood. Here, we use a box model to interpret the Hg0 (gaseous elemental mercury) measurements in thes year 2013. The model includes atmospheric Hg0 oxidation (by OH, O3, or bromine), surface snow HgII (oxidized mercury) reduction, and air–snow exchange, and is driven by meteorological fields from a regional climate model. The simulations suggest that a photochemically driven mercury diurnal cycle occurs at the air–snow interface in austral summer. The fast oxidation of Hg0 in summer may be provided by a two-step bromine-initiated scheme, which is favored by low temperature and high nitrogen oxides at Concordia. The summertime diurnal variations of Hg0 (peaking during daytime) may be confined within several tens of meters above the snow surface and affected by changing mixed layer depths. Snow re-emission of Hg0 is mainly driven by photoreduction of snow HgII in summer. Intermittent warming events and a hypothesized reduction of HgII occurring in snow in the dark may be important processes controlling the mercury variations in the non-summer period, although their relative importance is uncertain. The Br-initiated oxidation of Hg0 is expected to be slower at Summit Station in Greenland than at Concordia (due to their difference in temperature and levels of nitrogen oxides and ozone), which may contribute to the observed differences in the summertime diurnal variations of Hg0 between these two polar inland stations.</p

Science and Management of Intermittent Rivers and Ephemeral Streams (SMIRES)

More than half of the global river network is composed of intermittent rivers and ephemeral streams (IRES), which are expanding in response to climate change and increasing water demands. After years of obscurity, the science of IRES has bloomed recently and it is being recognised that IRES support a unique and high biodiversity, provide essential ecosystem services and are functionally part of river networks and groundwater systems. However, they still lack protective and adequate management, thereby jeopardizing water resources at the global scale. This Action brings together hydrologists, biogeochemists, ecologists, modellers, environmental economists, social researchers and stakeholders from 14 different countries to develop a research network for synthesising the fragmented, recent knowledge on IRES, improving our understanding of IRES and translating this into a science-based, sustainable management of river networks. Deliverables will be provided through i) research workshops synthesising and addressing key challenges in IRES science, supporting research exchange and educating young researchers, and ii) researcher-stakeholder workshops translating improved knowledge into tangible tools and guidelines for protecting IRES and raising awareness of their importance and value in societal and decision-maker spheres. This Action is organized within six Working Groups to address: (i) the occurrence, distribution and hydrological trends of IRES; (ii) the effects of flow alterations on IRES functions and services; (iii) the interaction of aquatic and terrestrial biogeochemical processes at catchment scale; (iv) the biomonitoring of the ecological status of IRES; (v) synergies in IRES research at the European scale, data assemblage and sharing; (vi) IRES management and advocacy training

Multi-model study of mercury dispersion in the atmosphere : Atmospheric processes and model evaluation

Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air-surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM=GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM=GEM ratios from spring to summer. O3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere

State of the Antarctic and Southern Ocean Climate System

This paper reviews developments in our understanding of the state of the Antarctic and Southern Ocean climate and its relation to the global climate system over the last few millennia. Climate over this and earlier periods has not been stable, as evidenced by the occurrence of abrupt changes in atmospheric circulation and temperature recorded in Antarctic ice core proxies for past climate. Two of the most prominent abrupt climate change events are characterized by intensification of the circumpolar westerlies (also known as the Southern Annular Mode) between ∼6000 and 5000 years ago and since 1200–1000 years ago. Following the last of these is a period of major trans-Antarctic reorganization of atmospheric circulation and temperature between A.D. 1700 and 1850. The two earlier Antarctic abrupt climate change events appear linked to but predate by several centuries even more abrupt climate change in the North Atlantic, and the end of the more recent event is coincident with reorganization of atmospheric circulation in the North Pacific. Improved understanding of such events and of the associations between abrupt climate change events recorded in both hemispheres is critical to predicting the impact and timing of future abrupt climate change events potentially forced by anthropogenic changes in greenhouse gases and aerosols. Special attention is given to the climate of the past 200 years, which was recorded by a network of recently available shallow firn cores, and to that of the past 50 years, which was monitored by the continuous instrumental record. Significant regional climate changes have taken place in the Antarctic during the past 50 years. Atmospheric temperatures have increased markedly over the Antarctic Peninsula, linked to nearby ocean warming and intensification of the circumpolar westerlies. Glaciers are retreating on the peninsula, in Patagonia, on the sub-Antarctic islands, and in West Antarctica adjacent to the peninsula. The penetration of marine air masses has become more pronounced over parts of West Antarctica. Above the surface, the Antarctic troposphere has warmed during winter while the stratosphere has cooled year-round. The upper kilometer of the circumpolar Southern Ocean has warmed, Antarctic Bottom Water across a wide sector off East Antarctica has freshened, and the densest bottom water in the Weddell Sea has warmed. In contrast to these regional climate changes, over most of Antarctica, near-surface temperature and snowfall have not increased significantly during at least the past 50 years, and proxy data suggest that the atmospheric circulation over the interior has remained in a similar state for at least the past 200 years. Furthermore, the total sea ice cover around Antarctica has exhibited no significant overall change since reliable satellite monitoring began in the late 1970s, despite large but compensating regional changes. The inhomogeneity of Antarctic climate in space and time implies that recent Antarctic climate changes are due on the one hand to a combination of strong multidecadal variability and anthropogenic effects and, as demonstrated by the paleoclimate record, on the other hand to multidecadal to millennial scale and longer natural variability forced through changes in orbital insolation, greenhouse gases, solar variability, ice dynamics, and aerosols. Model projections suggest that over the 21st century the Antarctic interior will warm by 3.4° ± 1°C, and sea ice extent will decrease by ∼30%. Ice sheet models are not yet adequate enough to answer pressing questions about the effect of projected warming on mass balance and sea level. Considering the potentially major impacts of a warming climate on Antarctica, vigorous efforts are needed to better understand all aspects of the highly coupled Antarctic climate system as well as its influence on the Earth\u27s climate and oceans

Multi-year record of atmospheric mercury at Dumont d'Urville, East Antarctic coast: continental outflow and oceanic influences

Under the framework of the Global Mercury Observation System (GMOS) project, a 3.5-year record of atmospheric gaseous elemental mercury (Hg(0)) has been gathered at Dumont d'Urville (DDU, 66°40′ S, 140°01′ E, 43 m above sea level) on the East Antarctic coast. Additionally, surface snow samples were collected in February 2009 during a traverse between Concordia Station located on the East Antarctic plateau and DDU. The record of atmospheric Hg(0) at DDU reveals particularities that are not seen at other coastal sites: a gradual decrease of concentrations over the course of winter, and a daily maximum concentration around midday in summer. Additionally, total mercury concentrations in surface snow samples were particularly elevated near DDU (up to 194.4 ng L⁻¹) as compared to measurements at other coastal Antarctic sites. These differences can be explained by the more frequent arrival of inland air masses at DDU than at other coastal sites. This confirms the influence of processes observed on the Antarctic plateau on the cycle of atmospheric mercury at a continental scale, especially in areas subject to recurrent katabatic winds. DDU is also influenced by oceanic air masses and our data suggest that the ocean plays a dual role on Hg(0) concentrations. The open ocean may represent a source of atmospheric Hg(0) in summer whereas the sea-ice surface may provide reactive halogens in spring that can oxidize Hg(0). This paper also discusses implications for coastal Antarctic ecosystems and for the cycle of atmospheric mercury in high southern latitudes

Preliminary results from a continuous record of atmospheric gaseous mercury at the coastal station Dumont d’Urville in Antarctica

While the tropospheric reactivity of mercury (Hg) in the Arctic is more and more documented only a few attempts were made to study the Hg cycle in the Southern Polar Regions. The role of the Antarctic continent and its influence on the global geochemical cycle of mercury is unclear today, and is certainly under evaluated by current models. Here, we present the first continuous high-time-resolution measurements of atmospheric gaseous elemental mercury (GEM) in East Antarctica from February 2010 to March 2011 at the coastal research station Dumont d’Urville (DDU) (66°40’S, 140°01’E, 43 m asl). We report an annual mean level of 1.062 ± 0.321 ng/m3 with well-marked daily fluctuations from October to January. An intense reactivity originated from the atmospheric boundary layer of the Antarctic plateau under sunlight conditions is observed at DDU. Partly GEM-depleted air masses are exported from the continent and dramatically influence the GEM record at DDU. From November to January, surface waters of the Southern Ocean are an important source of GEM

Preliminary results from a continuous record of atmospheric gaseous mercury at the coastal station Dumont d’Urville in Antarctica

While the tropospheric reactivity of mercury (Hg) in the Arctic is more and more documented only a few attempts were made to study the Hg cycle in the Southern Polar Regions. The role of the Antarctic continent and its influence on the global geochemical cycle of mercury is unclear today, and is certainly under evaluated by current models. Here, we present the first continuous high-time-resolution measurements of atmospheric gaseous elemental mercury (GEM) in East Antarctica from February 2010 to March 2011 at the coastal research station Dumont d’Urville (DDU) (66°40’S, 140°01’E, 43 m asl). We report an annual mean level of 1.062 ± 0.321 ng/m3 with well-marked daily fluctuations from October to January. An intense reactivity originated from the atmospheric boundary layer of the Antarctic plateau under sunlight conditions is observed at DDU. Partly GEM-depleted air masses are exported from the continent and dramatically influence the GEM record at DDU. From November to January, surface waters of the Southern Ocean are an important source of GEM