Chemical pathway analysis of the Martian atmosphere: CO2-formation pathways

The chemical composition of a planetary atmosphere plays an important role for atmospheric structure, stability, and evolution. Potentially complex interactions between chemical species do not often allow for an easy understanding of the underlying chemical mechanisms governing the atmospheric composition. In particular, trace species can affect the abundance of major species by acting in catalytic cycles. On Mars, such cycles even control the abundance of its main atmospheric constituent CO₂. The identification of catalytic cycles (or more generally chemical pathways) by hand is quite demanding. Hence, the application of computer algorithms is beneficial in order to analyze complex chemical reaction networks. Here, we have performed the first automated quantified chemical pathways analysis of the Martian atmosphere with respect to CO₂-production in a given reaction system. For this, we applied the Pathway Analysis Program (PAP) to output data from the Caltech/JPL photochemical Mars model. All dominant chemical pathways directly related to the global CO₂-production have been quantified as a function of height up to 86 km. We quantitatively show that CO₂-production is dominated by chemical pathways involving HO_x and O_x. In addition, we find that NO_x in combination with HO_x and O_x exhibits a non-negligible contribution to CO₂-production, especially in Mars’ lower atmosphere. This study reveals that only a small number of chemical pathways contribute significantly to the atmospheric abundance of CO₂ on Mars; their contributions to CO₂-production vary considerably with altitude. This analysis also endorses the importance of transport processes in governing CO₂-stability in the Martian atmosphere. Lastly, we identify a previously unknown chemical pathway involving HO_x, O_x, and HO₂-photodissociation, contributing 8% towards global CO₂-production by chemical pathways using recommended up-to-date values for reaction rate coefficients.     

Cold-season soil respiration in response to grazing and warming in High-Arctic Svalbard

The influence of goose grazing intensity and open-topped chambers (OTCs) on near-surface quantities and qualities of soil organic carbon (SOC) was evaluated in wet and mesic ecosystems in Svalbard. This study followed up a field experiment carried out in 2003–05 (part of the project Fragility of Arctic Goose Habitat: Impacts of Land Use, Conservation and Elevated Temperatures). New measurements of soil CO₂ effluxes, temperatures and water contents were regularly made from July to November 2007. SOC stocks were quantified, and the reactivity and composition measured by basal soil respiration (BSR) and solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Results reveal variations in soil carbon cycling, with significant seasonal trends controlled by temperature, water content and snow. Experimental warming (OTCs) increased near-surface temperatures in the growing season, resulting in significantly higher CO₂ effluxes. Different grazing intensities had no significant effects on observed soil respiration, but BSR rates at the mesic site (13–23 µg CO₂ g soil-C⁻¹ h⁻¹) were highest with moderate grazing and lowest in the absence of grazing. A limited effect of grazing on microbial respiration is consistent with a lack of significant differences in SOC quantity and quality. NMR data show that the composition of A-horizon SOC is dominated by O-N-alkyl C and alkyl C groups, and less by carboxyl C and aromatic C groups: but again no marked variation in response to grazing was evident. It can be concluded that two years after a goose grazing experiment, SOC cycling was less than the natural variation within contrasting vegetation types.     

Mineralisation and structural changes during the initial phase of microbial degradation of pyrogenic plant residues in soil

The microbial recalcitrance of char accumulated after vegetation fires was studied using pyrogenic organic material (PyOM) with increasing degrees of charring, produced from rye grass (Lolium perenne) and pine wood (Pinus sylvestris) at 350 °C under oxic conditions. Solid state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy confirmed increasing aromaticity and the formation of heterocyclic N with prolonged charring. After mixing with a mineral soil, the PyOM was aerobically incubated for 48 days at 30 °C. To account for the input of fresh litter after a fire event, unburnt rye grass residue was added as a co-substrate. The grass-derived PyOM showed the greatest extent of C mineralisation. After 48 days incubation, up to 3.2% of the organic C (OC) was converted to CO₂. More severe thermal alteration resulted in a decrease in the total C mineralisation to 2.5% of OC. In the pine-derived PyOM, only 0.7% and 0.5% of the initial C were mineralised. The co-substrate additions did not enhance PyOM mineralisation during initial degradation. ¹³C NMR spectroscopic analysis indicated structural changes during microbial degradation of the PyOM. Concomitant with a decrease in O-alkyl/alkyl-C, carboxyl/carbonyl C content increased, pointing to oxidation. Only the strongly thermally altered pine PyOM showed a reduction in aromaticity. The small C losses during the experiment indicated conversion of aryl C into other C groups. As revealed by the increase in carboxyl/carbonyl C, this conversion must have included the opening and partial oxidation of aromatic ring structures. Our study demonstrates that plant PyOM can be microbially attacked and mineralised at rates comparable to those for soil organic matter (SOM), so its role as a highly refractory SOM constituent may need re-evaluation.     

Anatomical variation of five plant species along an elevation gradient in Mexico City basin within the Trans-Mexican Volcanic Belt,Mexico

Change in environmental conditions with altitudinal gradients induces morpho-anatomical variations in plants that have been poorly documented in intertropical regions. Five species with three life forms, cryptophyte (Alchemilla procumbens, Geranium seemannii), hemicryptophyte (Acaena elongata, Lupinus montanus), and phanerophyte (Symphoricarpos microphyllus), distributed along an altitudinal gradient in the Sierra Nevada of central Mexico, were studied. The aims were to identify and evaluate their morpho-anatomical modifications under the hypothesis that the sizes of individuals and of their wood and leaf cell types decrease as elevation increases. Three individuals per species per site were collected at seven locations along the altitudinal gradient (2949-3952 m). Their morpho-anatomical characters were analyzed through multiple regression analyses. Elevation was the variable that best explained anatomical changes in the leaf and wood of the five species. Canopy density and potassium content in the soil also contributed to explain the variation in anatomical variables along the gradient. As elevation increased a bimodal pattern was observed in various anatomical characters as in the leaf width of A. elongata, A. procumbens and G. seemannii and in the vessel diameter of A. procumbens, G. seemannii, and L. montanus. Other features as the vessel diameter of A. elongata, the fiber length of S. microphyllus, and the ray width of A. elongata increased as the elevation increased. Anatomical traits have a tendency to decrease in size but just toward the end of the gradient, which is probably related to changes in canopy density. The plant response to the altitudinal gradient is more focused on anatomical adaptations than morphological variation; it is also species dependent.     

Reference Minerals for the Microanalysis of Light Elements

The quantitative determination of light element concentrations in geological specimens represents a major analytical challenge as the electron probe is generally not suited to this task. With the development of new in situ analytical techniques, and in particular the increasing use of secondary ion mass spectrometry, the routine determination of Li, Be and B contents has become a realistic goal. However, a major obstacle to the development of this research field is the critical dependence of SIMS on the availability of well characterized, homogeneous reference materials that are closely matched in matrix (composition and structure) to the sample being studied. Here we report the first results from a suite of large, gem crystals which cover a broad spectrum of minerals in which light elements are major constituents. We have characterized these materials using both in situ and wet chemical techniques. The samples described here are intended for distribution to geochemical laboratories active in the study of light elements. Further work is needed before reference values for these materials can be finalized, but the availability of this suite of materials represents a major step toward the routine analysis of the light element contents of geological specimens.     

Fate of Benzalkonium Chloride in a Sewage Sludge Low Temperature Conversion Process Investigated by LC‐LC/ESI‐MS/MS

Thermocatalytic low temperature conversion (LTC) is a new method for the disposal of sewage sludge. Using this method, sludge is converted into a residual solid (coal) along with reaction water, oil, and non‐condensable gases. The oil can be used as an energy source and the coal as a substitute for charcoal. To this end, it is important to determine whether there are any easily available contaminants present in the coal generated by the process. Contaminants that can be strongly sorbed by sewage sludge solids are, e. g., pharmaceuticals and disinfectants. As an example the fate of the persistent and strong adsorbing disinfectant benzalkonium chloride (BAC) has been investigated within the LTC process. The sewage sludge was spiked with BAC and then subjected to the LTC process. The resulting coal was extracted and analyzed using LC‐LC/ESI‐MS/MS (ion trap). BAC could not be detected in the LTC coal, although it could be extracted from the spiked sludge before the LTC treatment. It can thus be concluded that the investigated compound is not easily available in the coal, and hence that its use does not present a risk.     

Beyond the headlines: changing patterns in international student enrollment in the United States

In the aftermath of the terrorist attacks of September 11, 2001, newspapers and magazines reported a dramatic decline in the enrollment of international students at US universities. Many of these articles blamed this decrease on the difficulties of getting a visa to the US and expressed concern about the potential impact on the US education system and economy. A look beyond the headlines, however, reveals that this decline cannot be attributed exclusively to the heightened security measures, as student numbers from some countries had already begun to decline before 2001 or continue to increase despite the changed regulations. Therefore, other factors also play a role in explaining the diverse migration patterns—most notably increasing competition from other host countries and changing economic and educational conditions in sending countries. Since international students often stay in their host countries after the completion of their degrees, the United States has a strong interest in continuing to attract international students as potential highly skilled immigrants. In order to achieve this, changes need to be implemented at the government level as well as at individual universities.     

A bridge over troubled waters? Systems theory and dialogue in geography

In physical geography, systems are seen as a unity of parts and relationships, whereas human geographers using a second-order sociological systems approach define systems in terms of the difference between system and environment. Starting from this, dialogue between physical and human geographers using terms derived from systems theory is mostly in vain. This article explores some of the consequences that follow for dialogue in geography: the differences in defining systems, in the understanding of processes, the problem of system borders, the inconsistent understanding of the 'environment' itself as well as the different epistemology that comes with it (or leads to it). The article tries to bring systems theory back into geography with the decisive aim of enhancing the potentials for interaction between human and physical geographers and, therefore, to explore the possibility of connecting the social with the physical world – deviating from systems theory.