Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

全球贸易自由化对中国和世界经济的影响

全球贸易自由化是当前和未来世界经济发展不可避免的趋势,2001年开始的多哈回合贸易自由化多边谈判和最近刚刚取消的“多种纤维协定”（MFA）将在全球贸易自由化进程中发挥重要的作用。本研究的目的是通过一些案例分析,揭示贸易自由化对中国和世界经济的影响。采用全球贸易模型,我们分析了MFA和在多哈回合初期欧盟、美国和凯恩斯集团分别提出的贸易自由化提案。研究结果表明,虽然取消MFA对一些国家纺织部门带来冲击,但它极大地促进了大多数国家经济的发展,改善了全球福利;多哈谈判过程中提出的各种贸易自由化提案都在不同程度上促进世界经济的发展,但其影响大小依次为凯恩斯提案、美国提案和欧盟提案;贸易自由化对经济的影响在不同部门和不同国家间存在显著差别;更大程度的贸易自由化不但符合全球共同利益,也符合中国国家利益;中国在推动全球贸易自由化过程中应发挥更积极和更大的作用。     

Palaeolimnological studies of the eutrophication of volcanic Lake Albano (Central Italy)

We use palaeolimnological techniques to reconstruct the eutrophication history of a volcanic lake (Lake Albano, central Italy) over the past three centuries. The presence of annual varves down to the bottom of the core (c. 1700 A.D.) indicated the lack of bioturbation and likely long-term meromixis. Sedimentation rates were estimated by varve counts (calcite/diatom couplets), indicating a mean rate of 0.15 cm yr^–1. The reconstruction of eutrophication was traced using past populations of algal and photosynthetic bacteria (through their fossil pigment), and geochemistry, as well as fossil remains of chironomids. Phaeophorbidea and the red carotenoid astaxanthin were used to detect past zooplankton development.The first sign of trophic change related to human activities is datedc. 1870 A.D. From that period onward a sharp increase of authigenic CaCO₃, nitrogen, N:P ratio, and dinoxanthin, a characteristic carotenoid of Chrysophyceae and Dinophyceae, is observed.Chironomid analyses showed the near absence of a deep water fauna throughout the core length. The populations of chironomid larvae are restricted to oxygenated littoral zones. In fact, the few fossil remains found are primarily of littoral origin, representing shallow water midges that were transported to profundal waters. The reduction of total chironomid in the uppermost layers of the core is to be related to human land uses.     

Statistical analysis of time-dependent earthquake occurrence and its impact on hazard in the low seismicity region Lower Rhine Embayment

The time-dependence of earthquake occurrence is mostly ignored in standard seismic hazard assessment even though earthquake clustering is well known. In this work, we attempt to quantify the impact of more realistic dynamics on the seismic hazard estimations. We include the time and space dependences between earthquakes into the hazard analysis via Monte Carlo simulations. Our target region is the Lower Rhine Embayment, a low seismicity area in Germany. Including aftershock sequences by using the epidemic type aftershock-sequence (ETAS) model, we find that on average the hypothesis of uncorrelated random earthquake activity underestimates the hazard by 5–10 per cent. Furthermore, we show that aftershock activity of past large earthquakes can locally increase the hazard even centuries later. We also analyse the impact of the so-called long-term behaviour, assuming a quasi-periodic occurrence of main events on a major fault in that region. We found that a significant impact on hazard is only expected for the special case of a very regular recurrence of the main shocks.     

The American Crocodile in Florida Bay

The American crocodile was declared endangered in the United States in 1975. At that time 75% of the remaining crocodile nests were in Everglades National Park, in Florida Bay. In 1980, the National Park Service established a crocodile sanctuary in northeastern Florida Bay to protect nesting and nursery habitat. In 1985, a monitoring program, focused on nesting, growth, and survival, was established to evaluate the effects of modified water deliveries on crocodiles in Florida Bay. The number and range of crocodile nests increased between 1970 and 1995, but nesting success decreased slightly. Nests on artificial substrates in the Greater Flamingo-Cape Sable area accounted for most of the increase in nests. Nests on artificial substrates were more prone to predation by raccoons. At least 1.5% of marked hatchlings survived for more than 12 mo, and growth rates were variable. Detailed information on growth and survival of crocodiles is still lacking. It is no longer a question of whether crocodiles with survive in Florida Bay, but how ecosystem restoration and management can be applied to improve conditions for crocodiles.     

Surveying the Townscape of Roman Ammaia in Portugal: An Integrated Geoarchaeological Investigation of the Forum Area

Geoarchaeological research, integrating traditional excavations, and ground truthing with intensive geophysical surveys, aerial photography, and GIS‐based data processing, has revealed the full intramural plan of the abandoned Roman city of Ammaia in central Portugal. Although this multidisciplinary effort also focussed on understanding the town/territory relationships and the system of resource exploitation, this paper presents the most important results from fieldwork in the central monumental area of the town, the Roman Forum. Here, excavations, geomorphological survey, and an array of geophysical methods illuminate the long history of the site, from the first settlement and monument‐building phases in early Imperial times, to the ongoing post‐abandonment processes. This paper discusses some of the benefits of compiling these complementary data sets and proposes the use of a wide array of approaches in order to achieve full understanding of the complex topography and evolution of a classical urban site. It further demonstrates the need for effective stratigraphical control and geomorphological analysis of crucial areas revealed by high‐quality geophysics.     

Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.