Two decades of changing anthropogenic mercury emissions in Australia: inventory development, trends, and atmospheric implications.

Mercury is a toxic environmental pollutant emitted into the atmosphere by both natural and anthropogenic sources. In Australia, previous estimates of anthropogenic mercury emissions differ by up to a factor of three, with existing inventories either outdated or inaccurate and several lacking Australia-specific input data. Here, we develop a twenty-year inventory of Australian anthropogenic mercury emissions spanning 2000-2019 with annual resolution. Our inventory uses Australia-specific data where possible and incorporates processes not included in other Australian inventories, such as delayed release effects from waste emissions. We show that Australian anthropogenic mercury emissions have decreased by more than a factor of two over the past twenty years, with the largest decrease from the gold production sector followed by brown coal-fired power plants and commercial product waste. Only the aluminium sector has shown a notable increase in mercury emissions. Using a global 3-D chemical transport model (GEOS-Chem), we show that the reduction in emissions has led to a small decrease in mercury deposition to the Australian continent, with annual oxidised mercury deposition ∼3-4% lower with present day emissions than with emissions from the year 2000. We also find that Australian emissions are not accurately represented in recent global emissions inventories and that differences between inventories have a larger impact than emissions trends on simulated mercury deposition. Overall, this work suggests a significant benefit to Australia from the Minamata Convention, with further reductions to Australian mercury deposition expected from decreases in both Australian and global anthropogenic emissions.

Effects of Sea Salt Aerosol Emissions for Marine Cloud Brightening on Atmospheric Chemistry: Implications for Radiative Forcing.

Marine cloud brightening (MCB) is proposed to offset global warming by emitting sea salt aerosols to the tropical marine boundary layer, which increases aerosol and cloud albedo. Sea salt aerosol is the main source of tropospheric reactive chlorine (Cl y ) and bromine (Br y ). The effects of additional sea salt on atmospheric chemistry have not been explored. We simulate sea salt aerosol injections for MCB under two scenarios (212-569 Tg/a) in the GEOS-Chem global chemical transport model, only considering their impacts as a halogen source. Globally, tropospheric Cl y and Br y increase (20-40%), leading to decreased ozone (-3 to -6%). Consequently, OH decreases (-3 to -5%), which increases the methane lifetime (3-6%). Our results suggest that the chemistry of the additional sea salt leads to minor total radiative forcing compared to that of the sea salt aerosol itself (~2%) but may have potential implications for surface ozone pollution in tropical coastal regions.

Total Mercury Released to the Environment by Human Activities.

We estimate that a cumulative total of 1540 (1060-2800) Gg (gigagrams, 109 grams or thousand tonnes) of mercury (Hg) have been released by human activities up to 2010, 73% of which was released after 1850. Of this liberated Hg, 470 Gg were emitted directly into the atmosphere, and 74% of the air emissions were elemental Hg. Cumulatively, about 1070 Gg were released to land and water bodies. Though annual releases of Hg have been relatively stable since 1880 at 8 ± 2 Gg, except for wartime, the distributions of those releases among source types, world regions, and environmental media have changed dramatically. Production of Hg accounts for 27% of cumulative Hg releases to the environment, followed by silver production (24%) and chemicals manufacturing (12%). North America (30%), Europe (27%), and Asia (16%) have experienced the largest releases. Biogeochemical modeling shows a 3.2-fold increase in the atmospheric burden relative to 1850 and a contemporary atmospheric reservoir of 4.57 Gg, both of which agree well with observational constraints. We find that approximately 40% (390 Gg) of the Hg discarded to land and water must be sequestered at contaminated sites to maintain consistency with recent declines in atmospheric Hg concentrations.

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.

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.