Humic acid in ice: Photo-enhanced conversion of nitrogen dioxide into nitrous acid

Laboratory studies on the heterogeneous conversion of nitrogen dioxide into nitrous acid on irradiated ice films containing humic acid are described. It was found that the presence of light in the visible range of the solar spectrum significantly enhances the rate of nitrous acid release from a humic acid doped ice film. This process might contribute to observed HONO production in snow, where the NO₂ is thought to originate from nitrate photolysis. Analysis of the experimental data based on the Langmuir Hinshelwood model framework allowed quantification of the observed dependencies of the nitrous acid production rate on nitrogen dioxide concentration. The observed dependencies on the humic acid concentration as well as on the irradiation intensity were used to estimate light-driven HONO fluxes for environmental snow covers.     

Sample intake position and loading rates from nonpoint source pollution

Paired water samples were simultaneously activated from two different vertical positions within the approach section of a flow-control structure to determine the effect of sample intake position on nonpoint runoff parameter concentrations and subsequent event loads. Suspended solids (SS), total phosphorus (TP) and organic plus exchangeable nitrogen [(Or+Ex)-N] were consistently higher throughout each runoff event when sampled from the floor of the approach section as opposed to those samples taken at midstage. Dissolved molybdate reactive phosphorus (DMRP) and ammonium (NH₄-N) concentrations did not appear to be significantly affected by the vertical difference in intake position. However, the nitrate plus nitrite nitrogen [(NO₃+NO₂)-N] concentrations were much higher when sampled from the midstage position.Although the concentration differences between the two methods were not appreciable, when evaluated in terms of event loads, discrepancies were evident for all parameters. Midstage sampling produced event loads for SS, TP, (Or + Ex)–N, DMRP, NH₄-N, and (NO₃+NO₂)-N that were 44,39,35,80,71, and 181%, respectively, of floor sampling loads. Differences in loads between the two methods are attributed to the midstage position, sampling less of the bed load. The correct position will depend on the objective; however, such differences should be recognized during the design phase of the monitoring program.This work was supported by the Soil Science Department, College of Agriculture and Life Sciences, University of Wisconsin-Madison, and by the U.S. Environmental Protection Agency, Region V., Chicago, Illinois (Grant No. G005139-01).     

High acidity tolerance in lichens with fumarprotocetraric, perlatolic or thamnolic acids is correlated with low pKa1 values of these lichen substances

The depsidone fumarprotocetraric acid as well as the depsides perlatolic and thamnolic acids are lichen secondary metabolites. Their first dissociation constants (pK_a1) in methanol were determined to be 2.7 for perlatolic acid and 2.8 for fumarprotocetraric and thamnolic acids by UV spectroscopy. Lower pK_a1 values are, so far, not known from lichen substances. Several lichens producing at least one of these compounds are known for their outstanding tolerance to acidic air pollution. This is demonstrated by evaluating published pH preferences for central European lichens. The low pK_a1 values suggest that strong dissociation of the studied lichen substances is a prerequisite for the occurrence of lichens with these compounds on very acidic substrata, as protonated lichen substances of different chemical groups, but not their conjugated bases, are known to shuttle protons into the cytoplasm and thereby apparently damage lichens.     

Neanderthal medics? Evidence for food, cooking, and medicinal plants entrapped in dental calculus

Neanderthals disappeared sometime between 30,000 and 24,000?years ago. Until recently, Neanderthals were understood to have been predominantly meat-eaters; however, a growing body of evidence suggests their diet also included plants. We present the results of a study, in which sequential thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) were combined with morphological analysis of plant microfossils, to identify material entrapped in dental calculus from five Neanderthal individuals from the north Spanish site of El Sidrón. Our results provide the first molecular evidence for inhalation of wood-fire smoke and bitumen or oil shale and ingestion of a range of cooked plant foods. We also offer the first evidence for the use of medicinal plants by a Neanderthal individual. The varied use of plants that we have identified suggests that the Neanderthal occupants of El Sidrón had a sophisticated knowledge of their natural surroundings which included the ability to select and use certain plants.