Study of methyl halide fluxes in temperate and tropical ecosystems
CH3Br and CH3Cl (methyl halides) are the most abundant natural vectors of bromine and chlorine into the stratosphere and play an important role in stratospheric ozone destruction. The current knowledge of their respective natural sources is incomplete leading to large uncertainties in their global budgets. Beside the issue of quantification, characterisation of possible sources is needed to assist modelling of future environmental change impacts on these sources and hence the stratosphere. This study describes measurements conducted at two temperate salt marsh and three temperate forest sites in Scotland, and one tropical rainforest site in Malaysian Borneo to quantify and characterise natural methyl halide producing processes in these respective ecosystems. Measurements were conducted with static enclosure techniques, and methyl halide fluxes were calculated from the concentration difference between blank/background and afterenclosure samples. Methyl halide concentrations were determined via oxygen-doped GCECD with a custom-built pre-concentration unit. External factors such as photosyntheticallyactive radiation (PAR), total solar radiation, air temperature, soil temperature, internal chamber temperature and soil moisture were recorded in parallel to the enclosures to determine possible dependencies. Salt marsh studies were carried out at Heckie’s Hole in East Lothian, and Hollands Farmin East Dumfriesshire for 2 years. The study subjects were salt marsh plants that were enclosed during daylight hours in transparent enclosures for 10min each at 2–4 week intervals throughout the year. Parallel to this monitoring programme, systematic manipulation experiments and diurnal studies were carried out to learn more about the possible influence of potential drivers such as sunlight and temperature. Mean annual net fluxes ( standard deviation (sd)) were 300 44 ngm-2 h-1 for CH3Br and 660 270 ngm-2 h-1 for CH3Cl, with fluxes of both gases following a diurnal as well as an annual cycle, being lowest during winter nights and highest during summer days. A possible link between variations of daytime fluxes over the course of a year and changes in temperature was found. CH3Cl and CH3Br fluxes were positively correlated to each other and average fluxes of CH3Cl were linked to dry mass of certain species such as Puccinellia maritima, Aster tripolium, Juncus gerardi and Plantago maritima as found at the different measurement locations. No link between methyl halide fluxes and total halogen content or halogen concentration of the enclosed vegetation was found. Work in temperate forests was carried out for over one year at Fir Links, a mixed beech/ sycamore forest in East Lothian, and on one occasion each in Griffin Forest, a sitka spruce plantation in Perthshire, and finally the Hermitage of Braid, a mixed woodland park in Edinburgh. The study subject was leaf and needle litter which was enclosed in opaque 12 L containers for 10min–24h. During enclosure, internal chamber temperature was recorded, and leaf/needle litter water content was determined after enclosure. Combined average CH3Br and CH3Cl fluxes from temperate forest litter were 4.3 10-3 ngg-1 h-1 and 0.91 ngg-1 h-1, respectively. Average fluxes measured from leaf and needle litter were comparable in magnitude and CH3Br and CH3Cl were positively correlated. However no correlation of methyl halide fluxes to either temperature or litter water content was observed. Work at Danum Valley inMalaysian Borneo focused on flux measurements from both trees and leaf litter in a tropical dipterocarp forest. Fluxes from tropical trees were measured with transparent branch chambers at 20min enclosure times whilst methyl halide fluxes from leaf litter were measured with opaque 12 L containers at 24h enclosure times. Mean CH3Br and CH3Cl fluxes from branch enclosures were 0.53 ngg-1 h-1 and 27 ngg-1 h-1, respectively, and CH3Br and CH3Cl fluxes from tropical leaf litter were 1.4 10-3 ngg-1 h-1 and 2.3 ngg-1 h-1 respectively. Again fluxes of CH3Br and CH3Cl were positively correlated but no direct environmental driver for flux variations was found. The magnitude of methyl halide fluxes was species specific with individuals of the genus Shorea generally producing large amounts of methyl halide. Tropical rainforests were confirmed to be potentially the largest single natural source of CH3Cl. Global estimates were derived from extrapolating measured fluxes from the respective global land cover areas. These estimates suggest that the ecosystems examined in this study could account for over 1/3 of global CH3Cl production and up to 13%of global CH3Br production in nature. The ratio of CH3Br to CH3Cl emissions for these ecosystems is likely to be dependent on the abundance of bromine in the plant material with higher bromine content boosting CH3Br production and suppressing CH3Cl production. For this reason salt marshes are only a very minor source of CH3Cl.