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Climate Change and the European Water Dimension - Agri ...

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Atmospheric deposition to marine waters is driven primary by particle dry<br />

deposition <strong>and</strong> wet scavenging by precipitation mechanisms. Generally, <strong>the</strong> relative<br />

contribution of wet deposition accounts for about two thirds of <strong>the</strong> overall mercury<br />

budget entering to <strong>the</strong> marine system compared to particle dry deposition. However,<br />

in warm <strong>and</strong> dry region (i.e., Mediterranean) dry deposition was found to account for<br />

nearly 50% of <strong>the</strong> total flux. Gas exchange of gaseous mercury between <strong>the</strong> top<br />

water microlayer <strong>and</strong> <strong>the</strong> atmosphere is considered <strong>the</strong> major mechanisms driving<br />

gaseous mercury from <strong>the</strong> seawater to <strong>the</strong> air (e.g., Pirrone et al. 2001; Pirrone et al.<br />

2003).<br />

Once released to marine waters, it undergoes a number of chemical <strong>and</strong> physical<br />

transformations. Hg 0 is found in <strong>the</strong> mixed layer <strong>and</strong> in deeper waters of <strong>the</strong> ocean<br />

with concentrations generally ranging from 0.01 to 0.5 pM (e.g., Horvat et al. 2000).<br />

Gas exchange via Hg reduction <strong>and</strong> volatilization is <strong>the</strong> major loss term for marine<br />

Hg. Due to <strong>the</strong> low solubility of Hg 0 in water, almost all <strong>the</strong> aqueous mercury is<br />

present as Hg(II) in <strong>the</strong> inorganic form <strong>and</strong> organic methylmercury. Mercury levels in<br />

fish constitute a long-st<strong>and</strong>ing health hazard <strong>and</strong> this environmental problem relates<br />

predominantly to <strong>the</strong> conversion of inorganic Hg in neurotoxic monomethylmercury<br />

(MMHg) <strong>and</strong> dimethylmercury (DMHg) (e.g., IARC, 1994). MMHg is about 100 times<br />

more toxic than inorganic Hg <strong>and</strong> has been found to be mutagenic under<br />

experimental conditions. Anthropogenic activities presumably increased <strong>the</strong> surface<br />

water marine Hg concentration by a factor three, an increase which resulted amongst<br />

o<strong>the</strong>rs in elevated Hg concentrations in marine fishes (e.g., Amyot et al. 1997; Horvat<br />

et al. 2001). It is currently thought that most of <strong>the</strong> methylated Hg found in <strong>the</strong> water<br />

column <strong>and</strong> <strong>the</strong> biota of <strong>the</strong> marine waters is generated by in-situ production, though<br />

<strong>the</strong> reaction mechanisms are not yet clearly understood (e.g., Mason et al. 2002;<br />

Hintelman et al. 1997).<br />

Variations in <strong>the</strong> regional <strong>and</strong> global mercury cycle between atmospheric, marine<br />

<strong>and</strong> terrestrial ecosystems over time can occur due to changes in emissions of<br />

mercury <strong>and</strong> o<strong>the</strong>r atmospheric contaminants (e.g., NOx, SO2) as well as to climate<br />

change. The effects driven by climate change on <strong>the</strong> global mercury cycle can be<br />

classified as primary <strong>and</strong> secondary effects. Primary effects account for an increase<br />

in air <strong>and</strong> sea temperatures, wind speeds <strong>and</strong> variation in precipitation patterns,<br />

whereas secondary effects are related to an increase in O3 concentration <strong>and</strong><br />

aerosol loading, to a decrease of sea ice cover in <strong>the</strong> Arctic <strong>and</strong> changes in plant<br />

growth regimes. All <strong>the</strong>se primary <strong>and</strong> secondary effects may act with difference<br />

time scales <strong>and</strong> influence <strong>the</strong> atmospheric residence time of mercury <strong>and</strong> ultimately<br />

its dynamics from local to regional <strong>and</strong> global scale.<br />

VI.D.2. The Lifetime of Hg 0 (g) in <strong>the</strong> Planetary Boundary Layer<br />

The lifetime of elemental mercury is determined by <strong>the</strong> reactions which convert Hg 0 (g)<br />

to Hg(II)(g) which is much more readily scavenged <strong>and</strong> deposits much more rapidly<br />

than Hg 0 (g). The major atmospheric oxidants of Hg 0 (g) are O3 <strong>and</strong> OH in <strong>the</strong><br />

continental boundary layer <strong>and</strong> Br <strong>and</strong> o<strong>the</strong>r reactive halogen species in <strong>the</strong> Marine<br />

Boundary Layer (MBL). There are exceptions to <strong>the</strong>se generalisations however, it is<br />

known that in <strong>the</strong> Arctic halogens are important in so-called Mercury Depletion<br />

Events (MDEs), <strong>the</strong>se are none<strong>the</strong>less seen at coastal sites <strong>and</strong> thus not far<br />

removed from <strong>the</strong> MBL. The o<strong>the</strong>r known exception is <strong>the</strong> Mediterranean Sea region,<br />

where very high O3 concentrations are seen, particularly during <strong>the</strong> summertime<br />

(when air quality<br />

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