Controls on greenhouse gas concentrations in polymictic headwater lakes in Ireland.

Freshwater lakes are known to release carbon dioxide (CO(2)) and methane (CH(4)) to the atmosphere; however, the importance of lakes in global nitrous oxide (N(2)O) budgets is not yet known. Further, despite the abundance of small lakes on the landscape, neither emissions of these gases nor their drivers are well described. Dissolved concentrations of CO(2), CH(4) and N(2)O greenhouse gases were related to water chemistry, hydrology and catchment characteristics in order to identify factors controlling gas concentrations for 121 small Irish headwater lakes (median area: 2.0ha) in relatively undisturbed catchments; lake-atmosphere gas fluxes were also calculated. The majority of lakes were supersaturated (relative to the atmosphere) with CO(2) and N(2)O while CH(4) was above saturation in all lakes. Dissolved gas concentrations were correlated with land cover (rock, forest and grassland), deuterium excess (an indicator of hydrologic character) and lake organic carbon concentrations, although dissolved CO(2) exhibited few significant relationships. Principal components analysis indicated that higher levels of CH(4) and N(2)O supersaturation were exhibited under different conditions. Methane supersaturation was highest in low elevation catchments with an evaporative hydrologic character and high organic carbon concentrations. In contrast, lakes characteristic of N(2)O supersaturation were low in carbon and located in more rapidly flushed higher elevation catchments. Estimated fluxes of CO(2), CH(4) and N(2)O to the atmosphere averaged 14, 0.36 and 1.3×10(-3)mmolm(-2)d(-1), respectively.