Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

Sediment contamination in floodplains and alluvial terraces as an historical record of gold exploitation in the Carmo River basin,Southeast Quadrilátero Ferrífero,Minas Gerais,Brazil

This paper describes the geochemistry of sediment samples placed in floodplains and alluvial terraces downstream from gold mines in the Carmo River basin, Quadrilátero Ferrífero, Minas Gerais, Brazil. The geochemistry signature Na₂O, K₂O, SiO₂, CaO, MgO, Al₂O₃, Fe₂O₃, TiO₂, P₂O₅, Mn, As, Cu, Zn, Ba, Ni, Cr, S, Co were analyzed in different facies from stratigraphic profiles. As, Cu, Zn, and Mn anomalies are mainly associated with the clayed facies deposited in floodplains and oxbow lakes, and with coarse‐sediment facies deposited in the channel. The facies were accumulated by the gold exploitation activity in the region. The contamination of As, Cu, and Zn was controlled by minerals such as iron oxides and hydroxides (hematite, magnetite, and mainly goethite), manganese oxides, and sulfide‐rich minerals. The As‐bearing sediments of the region characterize one of the most As contaminated area of Brazil. Their main source is associated with gold exploration in the last three centuries.     

Tracer measurements in groyne fields for the quantification of mean hydraulic residence times and of the exchange with the stream

Tracer experiments were carried out in groyne fields (GF) of the river Elbe near Havelberg (Germany) in order to estimate the hydraulic connectivity with the river channel. The characteristic times of the five groyne fields, which were estimated from the exponentially declining tracer curves in 43 runs, ranged between 15 min and 69 min and did not correlate with the water level. Methodological investigations show that single point injection and two measurements (in the outflowing water and in the dominant region) are sufficient to provide robust in‐situ tracer curves. Using simplified mathematical simulations with connected stirred tanks, the conditions are investigated for the development of breaks in tracer curves and for the occurrence of significant errors in the estimation of intrinsic residence times. It was shown that an initial uniform dye distribution is not mandatory for the estimation during steady states. In special cases, point injections are more advisable. Moreover, the mean hydraulic residence time was found to be not equivalent to the estimated characteristic time. In fact, it is mostly overestimated by tracer experiments. The degree of overestimation depends on mixing and the volumetric proportions between the different parts of the GF and can be calculated from measured dye concentration differences. For example, an overestimation of 32% was calculated for a groyne field with a commonly found circulation flow pattern.     

Pre‐ and post‐test mathematical modelling of a plan‐asymmetric reinforced concrete frame building

Pre‐ and post‐test analyses of the structural response of a three‐storey asymmetric reinforced concrete frame building were performed, aimed at supporting test preparation and performance as well as studying mathematical modelling. The building was designed for gravity loads only. Full‐scale pseudo‐dynamic tests were performed in the ELSA laboratory in Ispra. In the paper the results of initial parametric studies, of the blind pre‐test predictions, and of the post‐test analysis are summarized. In all studies a simple mathematical model, with one‐component member models with concentrated plasticity was employed. The pre‐test analyses were performed using the CANNY program. After the test results became available, the mathematical model was improved using an approach based on a displacement‐controlled analysis. Basically, the same mathematical model was used as in pre‐test analyses, except that the values of some of the parameters were changed. The OpenSees program was employed. Fair agreement between the test and numerical results was obtained. The results prove that relatively simple mathematical models are able to adequately simulate the detailed seismic response of reinforced concrete frame structures to a known ground motion, provided that the input parameters are properly determined. Copyright © 2006 John Wiley & Sons, Ltd.     

DEVEX-disdrometer evaluation experiment: Basic results and implications for hydrologic studies

Increasing our understanding of the small scale variability of drop size distributions (DSD), and therefore of several bulk characteristics of rainfall processes, has major implications for our interpretation of the remote sensing based estimates of precipitation and its uncertainty. During the spring and summer of 2002 the authors conducted the DEVEX experiment (disdrometer evaluation experiment) to compare measurements of natural rain made with three different types of disdrometers collocated at the Iowa City Municipal Airport in Iowa City, Iowa in the Midwestern United States. This paper focuses on the evaluation of the instruments rather than analysis of the hydrometeorological aspects of the observed events. The comparison demonstrates discrepancies between instruments. The authors discuss the systematic and random effects in terms of rainfall quantities, drop size distribution properties, and the observed drop size vs. velocity relationships. Since the instruments were collocated, the effects of the natural variability of rain are reduced some with time integration, isolating the instrumental differences. The authors discuss the status of DSD measurement technologies and the implications for a range of hydrologic applications from remote sensing of rainfall to atmospheric deposition to soil erosion and sediment transport in the environment. The data set collected during the DEVEX experiment is made available to the research community.     

Precise orbit determination for the GRACE mission using only GPS data

The GRACE (gravity recovery and climate experiment) satellites, launched in March 2002, are each equipped with a BlackJack GPS onboard receiver for precise orbit determination and gravity field recovery. Since launch, there have been significant improvements in the background force models used for satellite orbit determination, most notably the model for the geopotential. This has resulted in significant improvements to orbit accuracy for very low altitude satellites. The purpose of this paper is to investigate how well the orbits of the GRACE satellites (about 470 km in altitude) can currently be determined using only GPS data and based on the current models and methods. The orbit accuracy is assessed using a number of tests, which include analysis of orbit fits, orbit overlaps, orbit connecting points, satellite Laser ranging residuals and K-band ranging (KBR) residuals. We show that 1-cm radial orbit accuracy for the GRACE satellites has probably been achieved. These precise GRACE orbits can be used for such purposes as improving gravity recovery from the GRACE KBR data and for atmospheric profiling, and they demonstrate the quality of the background force models being used.     

Modeling the length of day and extrapolating the rotation of the Earth

The stochastic behavior of the length of day (LOD) process is analyzed and is modeled within statistical accuracy on a time-scale ranging from weeks to millennia by a three-component model comprising a global Brownian motion process, decadal fluctuations, and a 50-day Madden–Julian oscillation. While the model is intended to be phenomenological, some possible physical models underlying the three components are speculated upon. The model is applied to estimate long-range extrapolation errors. For example, it predicts a standard error of 1 h in the clock-time correction ΔT for extrapolation by 1,500 years from 500 to 2000 BC.     

Comparison between earthquake magni-tudes determined by China seismograph network and US seismograph network (II): Surface wave magnitude

Introduction Earthquake magnitude is the most common measure of an earthquake′s size,and is one of the basic parameters of an earthquake.There are three most familiar scales of earthquake magnitude:ML(local earthquake magnitude),MS(surface wave magnitude)and mB/mb(body wave magni-tude).Richter(1935)introduced ML when studying earthquakes in Southern California.In1945,Gutenberg(1945a)put forward surface wave magnitude scale to determine earthquake magnitude(MS)using surface waves(20s)of s…     

Fitting a Vital Linkage Piece into the Multidimensional Emissions-reduction Puzzle: Nongovernmental Pathways to Consumption Changes in the PRC and the USA

The United States and China are responsible for nearly 40 per cent of total annual greenhouse gas emissions. Global climatic stabilization cannot succeed without the participation of people and organizations in the PRC and the USA. Given the likelihood of continued political paralysis at the national level in both countries, it is important to assess the strengths, weaknesses, and potential of nongovernmental actors in bringing about durable reductions in GHG emissions. Consumption trajectories present one of the most intractable barriers to anthropogenic GHG-emissions reductions and to long-term climatic stabilization. Nordlund and Garvill's (2003) model is adapted and applied in assessing prospects for value change, specific problem awareness, and sustainable-consumption behavior in the PRC and USA. The contributions of nonstate actors are elucidated when issue bundling (specifically links with stress reduction and healthy futures) and principle bundling are incorporated into the explanatory framework. The involvement of transnationally competent activists in emissions-mitigation projects, value change, and durable sustainable-consumption practices provides a beacon for future possibilities. Chinese transnationals are a key overlooked and underestimated piece in the current emissions-reduction puzzle because of their critical position at the intersection of values, behavior change, and nongovernmental institutions directly and indirectly involved in climatic-change mitigation. Given their special U.S./P.R.C. leverage, other actors concerned with building a sustainable-consumption movement and with climatic stabilization are likely to benefit from devoting increased attention and responsibilities to this group.