In situ experimental study of reed leaf decomposition along a full salinity gradient

An experimental study on Phragmites australis leaf litter decomposition was conducted in the estuarine environment, Ria de Aveiro, Western Portugal, using the leaf-bag technique, with fine- (1 mm) and coarse-mesh (5 mm) bags. The leaf bags were placed in the field sites at day 0, covering a complete salinity gradient, and replicates were collected over time, at days 3 (leaching), 7, 15, 30 and 60. The biomass loss through the leaching phase, about 20% of the initial leaf mass, was independent of both the salinity and the bag mesh size. The biomass decay pattern along the salinity gradient varied through time and presented strong similarities between the two mesh sizes, with the remaining biomass always lower in the 5 mm mesh-size bags. At days 7 and 15, the lowest remaining biomass was observed at the head of the estuary, the preferential distribution area of P. australis. At day 30, the remaining biomass was higher in the marine area and diminished under a direct relationship with salinity, reaching the lowest value in the freshwater environment, with values ranging from 66% to 44% of the initial weight in 5 mm bags, and from 79% to 51% in 1 mm bags. The largest heterogeneity in the remaining biomass among the study areas positioned along the salinity gradient was found close to days 30 (5 mm) and 40 (1 mm). The overall results indicate that the relationship between leaf decay rate and salinity depends on the decay time considered (k₁₅, k₃₀ or k₆₀) and, for the later stages (k₆₀), also on the leaf-bag mesh size. This implies that the use of leaf litter decay rates as a functional indicator in transitional waters will need to take into consideration the factor location in the salinity gradient and leaf litter stage at which the decay rate is determined. The differences between the decay rates with the mesh size acted mainly at the level of the absolute k value and not at the level of the pattern along the salinity gradient. Even so, the data obtained at the mouth of the estuary, in the area closest to a fully marine environment, indicated that after the initial biomass loss through leaching, P. australis decayed either very slowly, in the 5 mm, or not at all, in the 1 mm mesh bags.     

The heterogeneous formation of N2O over bulk condensed phases in the presence of SO2 at high humidities

In view of the uncertainty of the origin of the secular increase of N₂O, we studied heterogeneous processes that contribute to formation of N₂O in an environment that comes as close as possible to exhaust conditions containing NO and SO₂, among other constituents. The N₂O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO₂, NO, NO₂ and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N ₂ O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO₂, O₂ in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N₂O. The stoichiometry of the overall reaction is: 2 NO+SO₂+H₂O N₂O+H₂SO₄. The maximum rate of N₂O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N₂O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN₂O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N₂O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.