Atmospheric Concentrations and Wet/Dry Loadings of Mercury at the Remote Experimental Lakes Area, Northwestern Ontario, Canada.

Mercury (Hg) is a global pollutant released from both natural and human sources. Here we compare long-term records of wet deposition loadings of total Hg (THg) in the open to dry deposition loadings of THg in throughfall and litterfall under four boreal mixedwood canopy types at the remote Experimental Lakes Area (ELA) in Northwestern Ontario, Canada. We also present long-term records of atmospheric concentrations of gaseous elemental (GEM), gaseous oxidized (GOM), and particle bound (PBM) Hg measured at the ELA. We show that dry THg loadings in throughfall and litterfall are 2.7 to 6.1 times greater than wet THg loadings in the open. GEM concentrations showed distinct monthly and daily patterns, correlating positively in spring and summer with rates of gross ecosystem productivity and respiration. GOM and PBM concentrations were less variable throughout the year but were highest in the winter, when concentrations of anthropogenically sourced particles and gases were also high. Forest fires, Arctic air masses, and road salt also impacted GEM, GOM, and PBM concentrations at the ELA. A nested GEOS-Chem simulation for the ELA region produced a dry/wet deposition ratio of >5, suggesting that the importance of dry deposition in forested regions can be reasonably modeled by existing schemes for trace gases.

Observed decrease in atmospheric mercury explained by global decline in anthropogenic emissions.

Observations of elemental mercury (Hg(0)) at sites in North America and Europe show large decreases (∼ 1-2% y(-1)) from 1990 to present. Observations in background northern hemisphere air, including Mauna Loa Observatory (Hawaii) and CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) aircraft flights, show weaker decreases (<1% y(-1)). These decreases are inconsistent with current global emission inventories indicating flat or increasing emissions over that period. However, the inventories have three major flaws: (i) they do not account for the decline in atmospheric release of Hg from commercial products; (ii) they are biased in their estimate of artisanal and small-scale gold mining emissions; and (iii) they do not properly account for the change in Hg(0)/Hg(II) speciation of emissions from coal-fired utilities after implementation of emission controls targeted at SO2 and NOx. We construct an improved global emission inventory for the period 1990 to 2010 accounting for the above factors and find a 20% decrease in total Hg emissions and a 30% decrease in anthropogenic Hg(0) emissions, with much larger decreases in North America and Europe offsetting the effect of increasing emissions in Asia. Implementation of our inventory in a global 3D atmospheric Hg simulation [GEOS-Chem (Goddard Earth Observing System-Chemistry)] coupled to land and ocean reservoirs reproduces the observed large-scale trends in atmospheric Hg(0) concentrations and in Hg(II) wet deposition. The large trends observed in North America and Europe reflect the phase-out of Hg from commercial products as well as the cobenefit from SO2 and NOx emission controls on coal-fired utilities.

What Goes Up Must Come Down: Integrating Air and Water Quality Monitoring for Nutrients.

Excess nitrogen and phosphorus ("nutrients") loadings continue to affect ecosystem function and human health across the U.S. Our ability to connect atmospheric inputs of nutrients to aquatic end points remains limited due to uncoupled air and water quality monitoring. Where connections exist, the information provides insights about source apportionment, trends, risk to sensitive ecosystems, and efficacy of pollution reduction efforts. We examine several issues driving the need for better integrated monitoring, including: coastal eutrophication, urban hotspots of deposition, a shift from oxidized to reduced nitrogen deposition, and the disappearance of pristine lakes. Successful coordination requires consistent data reporting; collocating deposition and water quality monitoring; improving phosphorus deposition measurements; and filling coverage gaps in urban corridors, agricultural areas, undeveloped watersheds, and coastal zones.

Observational and modeling constraints on global anthropogenic enrichment of mercury.

Centuries of anthropogenic releases have resulted in a global legacy of mercury (Hg) contamination. Here we use a global model to quantify the impact of uncertainty in Hg atmospheric emissions and cycling on anthropogenic enrichment and discuss implications for future Hg levels. The plausibility of sensitivity simulations is evaluated against multiple independent lines of observation, including natural archives and direct measurements of present-day environmental Hg concentrations. It has been previously reported that pre-industrial enrichment recorded in sediment and peat disagree by more than a factor of 10. We find this difference is largely erroneous and caused by comparing peat and sediment against different reference time periods. After correcting this inconsistency, median enrichment in Hg accumulation since pre-industrial 1760 to 1880 is a factor of 4.3 for peat and 3.0 for sediment. Pre-industrial accumulation in peat and sediment is a factor of ∼ 5 greater than the precolonial era (3000 BC to 1550 AD). Model scenarios that omit atmospheric emissions of Hg from early mining are inconsistent with observational constraints on the present-day atmospheric, oceanic, and soil Hg reservoirs, as well as the magnitude of enrichment in archives. Future reductions in anthropogenic emissions will initiate a decline in atmospheric concentrations within 1 year, but stabilization of subsurface and deep ocean Hg levels requires aggressive controls. These findings are robust to the ranges of uncertainty in past emissions and Hg cycling.

Historical Mercury releases from commercial products: global environmental implications.

The intentional use of mercury (Hg) in products and processes ("commercial Hg") has contributed a large and previously unquantified anthropogenic source of Hg to the global environment over the industrial era, with major implications for Hg accumulation in environmental reservoirs. We present a global inventory of commercial Hg uses and releases to the atmosphere, water, soil, and landfills from 1850 to 2010. Previous inventories of anthropogenic Hg releases have focused almost exclusively on atmospheric emissions from "byproduct" sectors (e.g., fossil fuel combustion). Cumulative anthropogenic atmospheric Hg emissions since 1850 have recently been estimated at 215 Gg (only including commercial Hg releases from chlor-alkali production, waste incineration, and mining). We find that other commercial Hg uses and nonatmospheric releases from chlor-alkali and mining result in an additional 540 Gg of Hg released to the global environment since 1850 (air: 20%; water: 30%; soil: 30%; landfills: 20%). Some of this release has been sequestered in landfills and benthic sediments, but 310 Gg actively cycles among geochemical reservoirs and contributes to elevated present-day environmental Hg concentrations. Commercial Hg use peaked in 1970 and has declined sharply since. We use our inventory of historical environmental releases to force a global biogeochemical model that includes new estimates of the global burial in ocean margin sediments. Accounting for commercial Hg releases improves model consistency with observed atmospheric concentrations and associated historical trends.

Global biogeochemical implications of mercury discharges from rivers and sediment burial.

Rivers are an important source of mercury (Hg) to marine ecosystems. Based on an analysis of compiled observations, we estimate global present-day Hg discharges from rivers to ocean margins are 27 ± 13 Mmol a(-1) (5500 ± 2700 Mg a(-1)), of which 28% reaches the open ocean and the rest is deposited to ocean margin sediments. Globally, the source of Hg to the open ocean from rivers amounts to 30% of atmospheric inputs. This is larger than previously estimated due to accounting for elevated concentrations in Asian rivers and variability in offshore transport across different types of estuaries. Riverine inputs of Hg to the North Atlantic have decreased several-fold since the 1970s while inputs to the North Pacific have increased. These trends have large effects on Hg concentrations at ocean margins but are too small in the open ocean to explain observed declines of seawater concentrations in the North Atlantic or increases in the North Pacific. Burial of Hg in ocean margin sediments represents a major sink in the global Hg biogeochemical cycle that has not been previously considered. We find that including this sink in a fully coupled global biogeochemical box model helps to balance the large anthropogenic release of Hg from commercial products recently added to global inventories. It also implies that legacy anthropogenic Hg can be removed from active environmental cycling on a faster time scale (centuries instead of millennia). Natural environmental Hg levels are lower than previously estimated, implying a relatively larger impact from human activity.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

RATIONALE: Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. METHODS: Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. RESULTS: The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). CONCLUSIONS: Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data.

GLOBE Observer Data: 2016-2019.

This technical report summarizes the GLOBE Observer data set from 1 April 2016 to 1 December 2019. GLOBE Observer is an ongoing NASA-sponsored international citizen science project that is part of the larger Global Learning and Observations to Benefit the Environment (GLOBE) Program, which has been in operation since 1995. GLOBE Observer has the greatest number of participants and geographic coverage of the citizen science projects in the Earth Science Division at NASA. Participants use the GLOBE Observer mobile app (launched in 2016) to collect atmospheric, hydrologic, and terrestrial observations. The app connects participants to satellite observations from Aqua, Terra, CALIPSO, GOES, Himawari, and Meteosat. Thirty-eight thousand participants have contributed 320,000 observations worldwide, including 1,000,000 georeferenced photographs. It would take an individual more than 13 years to replicate this effort. The GLOBE Observer app has substantially increased the spatial extent and sampling density of GLOBE measurements and more than doubled the number of measurements collected through the GLOBE Program. GLOBE Observer data are publicly available (at observer.globe.gov).

Toward an Assessment of the Global Inventory of Present-Day Mercury Releases to Freshwater Environments.

Aquatic ecosystems are an essential component of the biogeochemical cycle of mercury (Hg), as inorganic Hg can be converted to toxic methylmercury (MeHg) in these environments and reemissions of elemental Hg rival anthropogenic Hg releases on a global scale. Quantification of effluent Hg releases to aquatic systems globally has focused on discharges to the global oceans, rather than contributions to freshwater systems that affect local exposures and risks associated with MeHg. Here we produce a first-estimate of sector-specific, spatially resolved global aquatic Hg discharges to freshwater systems. We compare our release estimates to atmospheric sources that have been quantified elsewhere. By analyzing available quantitative and qualitative information, we estimate that present-day global Hg releases to freshwater environments (rivers and lakes) associated with anthropogenic activities have a lower bound of ~1000 Mg· a-1. Artisanal and small-scale gold mining (ASGM) represents the single largest source, followed by disposal of mercury-containing products and domestic waste water, metal production, and releases from industrial installations such as chlor-alkali plants and oil refineries. In addition to these direct anthropogenic inputs, diffuse inputs from land management activities and remobilization of Hg previously accumulated in terrestrial ecosystems are likely comparable in magnitude. Aquatic discharges of Hg are greatly understudied and further constraining associated data gaps is crucial for reducing the uncertainties in the global biogeochemical Hg budget.