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

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POPs exist in <strong>the</strong> atmosphere in <strong>the</strong> gas phase <strong>and</strong> associated with particles. Their<br />

partitioning is controlled by temperature (Bidleman, 1988; Falconer <strong>and</strong> Bidleman,<br />

1994) <strong>and</strong> can be quite different in different environments – <strong>the</strong> tropics compared to<br />

<strong>the</strong> Arctic, for example.<br />

4. Reaction rates:<br />

POPs are degraded in <strong>the</strong> environment, in <strong>the</strong> atmosphere by reactions with <strong>the</strong><br />

hydroxyl radical, <strong>and</strong> in soils/sediments by microbially mediated processes (e.g.,<br />

Anderson <strong>and</strong> Hites, 1996; Totten <strong>and</strong> Eisenreich 2000, M<strong>and</strong>alakis et al., 2003).<br />

Despite all <strong>the</strong>se obvious examples of <strong>the</strong> influence of temperature on <strong>the</strong> emissions<br />

<strong>and</strong> environmental distributions of POPs, it must be remembered that regional or<br />

global increases in ambient temperatures attributed to underlying changes in climate<br />

are ‘small’ – averaging only 1-2 0 C over time frames of decades or longer. These are<br />

unlikely to be sufficient – by <strong>the</strong>mselves – to substantially impact global POPs cycles.<br />

After all, timeframes of decades are sufficient to see <strong>the</strong> ‘rise <strong>and</strong> fall’ of POP<br />

compound production/use/restrictions/bans, while reaction rates <strong>and</strong> environmental<br />

partitioning phenomena generally only increase by a factor of 2-3 for a 10 0 C<br />

increase in temperature.<br />

The role of air-surface exchange<br />

As noted above, <strong>the</strong>re is evidence that gas phase POPs can ‘hop’ between<br />

environmental surfaces <strong>and</strong> <strong>the</strong> atmosphere (Gouin et al., 2004). The clearest<br />

evidence for this comes from measurements of <strong>the</strong> diurnal cycling of atmospheric<br />

concentrations (highest in <strong>the</strong> day, lowest at night) that are positively correlated with<br />

temperature. However, such cycling is not observed in all studies, <strong>and</strong> appears to be<br />

a strong function of <strong>the</strong> underlying surface. The clearest evidence for such T-driven<br />

cycling comes from studies over vegetated surfaces - a peat bog in Minnesota <strong>and</strong><br />

grassl<strong>and</strong> in <strong>the</strong> UK, for example (Hornbuckle <strong>and</strong> Eisenreich, 1996; Lee et al., 1998)<br />

as well as urban areas (Brunciak et al., 2002; Dachs et al., 2002). In contrast, studies<br />

over <strong>the</strong> open ocean suggest that o<strong>the</strong>r factors control atmospheric concentrations<br />

over a typical 24-hour cycle (Jaward et al., 2004c). When diurnal cycling has been<br />

observed, it is clearest where ambient temperatures show <strong>the</strong> largest diurnal<br />

amplitude <strong>and</strong> where <strong>the</strong> surface compartment undergoes large diurnal shifts in<br />

temperature. These observations are potentially important with respect to possible<br />

influences of climate change, because underlying changes that affect <strong>the</strong> nature <strong>and</strong><br />

partitioning properties of environmental surfaces may impact <strong>the</strong> rate <strong>and</strong> magnitude<br />

of <strong>the</strong> air-surface exchange of POPs. Hence – it is hypo<strong>the</strong>sised - increased<br />

desertification, changes in l<strong>and</strong> use <strong>and</strong> vegetative cover, changes in <strong>the</strong> extent of<br />

<strong>the</strong> ice sheets, <strong>and</strong> changes in <strong>the</strong> rates of primary productivity in <strong>the</strong> oceans may all<br />

exert an influence on global POP cycling.<br />

Vegetation:<br />

Vegetation is a compartment that actively participates in air-surface exchange of<br />

POPs. The waxy surfaces of leaves can provide an important storage compartment<br />

for <strong>the</strong>se compounds (Barber et al., 2004), are in intimate contact with <strong>the</strong><br />

atmosphere, <strong>and</strong> can undergo substantial diurnal <strong>and</strong> seasonal changes in<br />

temperature. It is not a compartment with a particularly large capacity to store POPs,<br />

compared to soils or sediments for example, but it can:<br />

• scavenge POPs from <strong>the</strong> atmosphere;<br />

• enhance <strong>the</strong> rates of deposition to forested areas relative to adjacent<br />

clearings, <strong>and</strong> on vegetated areas relative to adjacent bare soil;<br />

• store POPs in quantities which vary as a function of <strong>the</strong> plants lipid content;<br />

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