Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Relative kinetic studies have been performed on the reactions of Cl atoms with a series of methyl alkyl esters in a 405-liter borosilicate glass chamber at (298 ± 3) K and one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. Rate coefficients (in units of cm³ molecule^?1 s^?1) were determined for the following compounds: methyl acetate (2.48 ± 0.58) × 10^?12; methyl propanoate (1.68 ± 0.36) × 10^?11; methyl butanoate (4.77 ± 0.87) × 10^?11; methyl pentanoate (7.84 ± 1.15) × 10^?11; methyl hexanoate (1.09 ± 0.31) × 10^?10; methyl heptanoate (1.56 ± 0.37) × 10^?10; methyl cyclohexane carboxylate (3.32 ± 0.76) × 10^?10; methyl-2-methyl butanoate (9.41 ± 1.39) × 10^?11.In addition rate coefficients (in units of 10^?11 cm³ molecule^?1 s^?1) have been obtained for the reactions of OH radicals with the following compounds: methyl butanoate (3.55 ± 0.71), methyl pentanoate (5.41 ± 1.08), and methyl-2-methyl butanoate (4.08 ± 0.82).Using the kinetic rate data tropospheric lifetimes for the methyl alkyl esters with respect to their reactions with OH, and Cl have been estimated for typical ambient air concentrations of these oxidants.     

Infiltration of acetochlor and two of its metabolites in two contrasting soils

To obtain data concerning the risk of leaching of acetochlor (2-chloro-2'-methyl-6'-ethyl-N-ethoxymethyl-acetanilide) and its major metabolites, ethanesulfonic acid (ESA) and oxanilic acid (OA), to ground water, we studied the fate of these products in two different soil types (luvisol and calcisol) under the same weather conditions. The metabolites were detected in the soils as early as 7 d after application, indicating a rapid onset of acetochlor degradation. Ethanesulfonic acid was predominant over OA in the calcisol, regardless of time or depth, whereas the ESA to OA ratio varied with both time and depth in the luvisol. The maximum depths at which they were detected were 60 to 70 and 10 to 20 cm for ESA and OA, respectively, in the luvisol, and 60 to 70 cm (maximum depth sampled) and 30 to 40 cm for ESA and OA, respectively, in the calcisol. Acetochlor was still detected in the surface layer of the two soils 344 d after its application, although the molecule was partially leached. The maximum depths at which acetochlor was detected (60-70 cm in the luvisol and 50-60 cm [maximum depth sampled] in the calcisol) were recorded during the first sampling 7 d after application. Acetochlor was not detected on later dates below the 30- to 40-cm layer in the calcisol or the 5- to 10-cm layer in the luvisol. The greater preferential flow in the luvisol, which would have favored leaching, might partially explain why the mass balances done 7 d after application were lower in the luvisol (approximately 26%) than in the calcisol (approximately 45%).     

Stable isotope ratios indicate differential omnivory among syntopic rocky shore suspension-feeders

We utilised stable isotope ratios to assess differences in diet among three indigenous and syntopic rocky shore suspension-feeders (mussels Perna perna, barnacles Tetraclita serrata, and polychaetes Gunnarea gaimardi). We also determined the spatial and temporal variability in the suspension-feeder diets by collecting specimens on two occasions from two regions adjacent to hydrologically distinct river mouths (i.e. one with larger annual freshwater throughput than the other). The results showed that the isotopic niches (used as proxies for trophic niches) of the three species did not overlap and that the barnacles occupied a trophic position (3.4) well above those of the mussels (2) and polychaetes (2.6). We ascribed the interspecific differences primarily to the disparate feeding mechanisms used by the species. Large-scale regional (~50 km) differences in suspension-feeder diets were apparent, but not small-scale (up to a few km north and south of each estuary mouth). The regional differences in diet resulted from the increased availability of estuarine-origin suspended particulate matter (SPM) and zooplankton in the region adjacent to the river with relatively larger freshwater output, although overall incorporation of zooplankton versus mixed SPM into consumer diets was relatively consistent between regions and through time. Temporal shifts in suspension-feeder diets were apparent from stable carbon isotope ratios in the consumers. Our results showcase the measurable effects of regional-scale processes that can alter the food sources for dominant primary consumers in the rocky intertidal, thus potentially affecting entire food webs through bottom-up processes. The clear evidence for trophic niche partitioning offers valuable insights into how potentially strong competitors can coexist.