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.     

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.     

Komsomolskaya diamondiferous eclogites: evidence for oceanic crustal protoliths

The Komsomolskaya kimberlite is one of numerous (>1,000) kimberlite pipes that host eclogite xenoliths on the Siberian craton. Eclogite xenoliths from the adjacent Udachnaya kimberlite pipe have previously been geochemically well characterized; however, data from surrounding diamond-bearing kimberlite pipes from the center of the craton are relatively sparse. Here, we report major- and trace-element data, as well as oxygen isotope systematics, for mineral separates of diamondiferous eclogite xenoliths from the Komsomolskaya kimberlite, suggesting two distinct subgroups of a metamorphosed, subducted oceanic crustal protolith. Using almandine contents, this suite can be divided into two subgroups: group B1, with a high almandine component (>20 mol%) and group B2, with a low almandine component (<20 mol%). Reconstructed REE profiles for B1 eclogites overlap with typical oceanic basalts and lack distinct Eu anomalies. In addition, elevated oxygen isotope values, which are interpreted to reflect isotopic exchange with seawater at low temperatures (<350 °C), are consistent with an upper-oceanic crustal protolith. Reconstructed REE profiles for B2 eclogites are consistent with oceanic gabbros and display distinct Eu anomalies, suggesting a plagioclase-rich cumulate protolith. In contrast to B1, B2 eclogites do not display elevated oxygen isotope values, suggesting an origin deep within the crustal pile, where little-to-no interaction with hydrothermal fluids has occurred. Major-element systematics were reconstructed based on mineral modes; group B1 eclogites have higher MgO wt% and lower SiO₂ wt%, with respect to typical oceanic basalts, reflecting a partial melting event during slab subduction. Calculated residues from batch partial melt modeling of a range of Precambrian basalts overlap with group B1 trace-element chemistry. When taken together with the respective partial melt trajectories, these melting events are clearly linked to the formation of Tonalite–Trondhjemite–Granodiorite (TTG) complexes. As a result, we propose that many, if not all, diamondiferous eclogite xenoliths from Komsomolskaya represent mantle ‘restites’ that preserve chemical signatures of Precambrian oceanic crust.     

Conventional and combined pump-and-treat systems under nonuniform background flow

We investigate the performance of vertical hydraulic barriers in combination with extraction wells for the partial hydraulic isolation of contaminated aquifer areas. The potential advantage of such combinations compared to a conventional pump-and-treat system has already been demonstrated in a previous study. Here we extend the scope of the performance analysis to the impact of uncertainty in the regional flow direction as well as to highly heterogeneous aquifer transmissivity distributions. In addition, two new well-barrier scenarios are proposed and analyzed. The hydraulic efficiency of the scenarios is rated based on the expected (mean) reduction of the pumping rate that is required to achieve downgradient contaminant capture. The uncertain spatial distribution of aquifer transmissivity is considered by means of unconditioned Monte Carlo simulations. The significance of uncertain background flow conditions is incorporated by computing minimized pumping rates for deviations of the regional flow direction up to 30 degrees from a normative base case. The results give an answer on how pumping rates have to be changed for each barrier-well combination in order to achieve robust systems. It is exposed that in comparison to installing exclusively wells, the barrier-supported approach generally yields savings in the (average) pumping rate. The particular efficiency is shown to be highly dependent on the interaction of variance and integral scale of transmissivity distribution, well and barrier position, as well as direction of background flow.     

中国土地利用/土地覆盖的多尺度空间分布特征分析

研究了我国土地利用影响因素及其空间规模相关性,采用数理统计与ＧＩＳ手段从多个规模尺度上探讨了我国土地利用的空间分布特征。其结果对全国以及各级政府进行土地利用规划、制定相应的土地开发与利用政策等具有一定的参考意义。     

Coupled ‘storm‐flood’ depositional model: Application to the Miocene–Modern Baram Delta Province,north‐west Borneo

The Miocene to Modern Baram Delta Province is a highly efficient source to sink system that has accumulated 9 to 12 km of coastal–deltaic to shelf sediments over the past 15 Myr. Facies analysis based on ca 1 km of total vertical outcrop stratigraphy, combined with subsurface geology and sedimentary processes in the present‐day Baram Delta Province, suggests a ‘storm‐flood’ depositional model comprising two distinct periods: (i) fair‐weather periods are dominated by alongshore sediment reworking and coastal sand accumulation; and (ii) monsoon‐driven storm periods are characterized by increased wave‐energy and offshore‐directed downwelling storm flow that occur simultaneously with peak fluvial discharge caused by storm precipitation (‘storm‐floods’). The modern equivalent environment has the following characteristics: (i) humid‐tropical monsoonal climate; (ii) narrow (ca <100 km) and steep (ca 1°), densely vegetated, coastal plain; (iii) deep tropical weathering of a mudstone‐dominated hinterland; (iv) multiple independent, small to moderate‐sized (10² to 10⁵ km²) drainage basins; (v) predominance of river‐mouth bypassing; and (vi) supply‐dominated shelf. The ancient, proximal part of this system (the onshore Belait Formation) is dominated by strongly cyclical sandier‐upward successions (metre to decametre‐scale) comprising (from bottom to top): (i) finely laminated mudstone with millimetre‐scale silty laminae; (ii) heterolithic sandstone–mudstone alternations (centimetre to metre‐scale); and (iii) sharp‐based, swaley cross‐stratified sandstone beds and bedsets (metre to decimetre‐scale). Gutter casts (decimetre to metre‐scale) are widespread, they are filled with swaley cross‐stratified sandstone and their long axes are oriented perpendicular to the palaeo‐shoreline. The gutter casts and other associated waning‐flow event beds suggest that erosion and deposition was controlled by high‐energy, offshore‐directed, oscillatory‐dominated, sediment‐laden combined flows within a shoreface to delta front setting. The presence of multiple river mouths and exceptionally high rates of accommodation creation (characteristic of the Neogene to Recent Baram Delta Province; up to 3000 m Ma⁻¹), in a ‘storm‐flood’‐dominated environment, resulted in a highly efficient and effective offshore‐directed sediment transport system.     

The application of GPR to barrier-lagoon sedimentation study in Boao of Hainan Island

Sedimentary successions and internal structure of the coastal barrier-lagoon system of Boao, eastern Hainan Island were studied through utilizing data from test holes and trenches and ground-penetrating-radar (GPR) profiles. During late Pleistocene, fluvial and delta plains developed over an unevenly eroded bedrock during low sea level stand, followed by the formation of littoral and lagoon facies and defined coastal barrier-lagoon-estuary system during the post-glacial uppermost Pleistocene-lower Holocene eustatic rise of the sea level, and the upper Holocene high stand. GPR results show that Yudaitan, a sandy coastal bar backed by a low-laying land (shoal) just east of the active lagoon, is a continuous, parallel and slightly-wavy reflectors indicating homogeneous sandy or sandy gravel sediments, and inclined reflectors partly caused by progradation and accumulation of beach sand and gravel. Quasi-continuous, hummocky and chaotic reflectors from the shoal of Nangang village correspond to mixed accumula     

The effects of climate and landscape position on chemical denudation and mineral transformation in the Santa Catalina mountain critical zone observatory

Understanding the interactions of climate, physical erosion, chemical weathering and pedogenic processes is essential when considering the evolution of critical zone systems. Interactions among these components are particularly important to predicting how semiarid landscapes will respond to forecasted changes in precipitation and temperature under future climate change. The primary goal of this study was to understand how climate and landscape structure interact to control chemical denudation and mineral transformation across a range of semiarid ecosystems in southern Arizona. The research was conducted along the steep environmental gradient encompassed by the Santa Catalina Mountains Critical Zone Observatory (SCM-CZO). The gradient is dominated by granitic parent materials and spans significant range in both mean annual temperature (>10 °C) and precipitation (>50 cm a^?1), with concomitant shift in vegetation communities from desert scrub to mixed conifer forest. Regolith profiles were sampled from divergent and convergent landscape positions in five different ecosystems to quantify how climate-landscape position interactions control regolith development. Regolith development was quantified as depth to paralithic contact and degree of chemical weathering and mineral transformation using a combination of quantitative and semi-quantitative X-ray diffraction (XRD) analyses of bulk soils and specific particle size classes. Depth to paralithic contact was found to increase systematically with elevation for divergent positions at approximately 28 cm per 1000 m elevation, but varied inconsistently for convergent positions. The relative differences in depth between convergent and divergent landscape positions was greatest at the low and high elevation sites and is hypothesized to be a product of changes in physical erosion rates across the gradient. Quartz/Plagioclase (Q/P) ratios were used as a general proxy for bulk regolith chemical denudation. Q/P was generally higher in divergent landscape positions compared to the adjacent convergent hollows. Convergent landscape positions appear to be collecting solute-rich soil–waters from divergent positions thereby inhibiting chemical denudation. Clay mineral assemblage of the low elevation sites was dominated by smectite and partially dehydrated halloysite whereas vermiculite and kaolinite were predominant in the high elevation sites. The increased depth to paralithic contact, chemical denudation and mineral transformation are likely functions of greater water availability and increased primary productivity. Landscape position within a given ecosystem exerts strong control on chemical denudation as a result of the redistribution of water and solutes across the landscape surface. The combined data from this research demonstrates a strong interactive control of climate, landscape position and erosion on the development of soil and regolith.     

Comparing palaeolimnological and instrumental evidence of climate change for remote mountain lakes over the last 200 years

This paper compares the palaeolimnological evidence for climate change over the last 200 years with instrumental climate data for the same period at seven European remote mountain lakes. The sites are Øvre Neådalsvatn (Norway), Saanajärvi (Finland), Gossenköllesee (Austria), Hagelseewli (Switzerland), Jezero v Ledvici (Slovenia), Estany Redó (Spain, Pyrenees), and Niné Terianske Pleso (Slovakia). We used multiple regression analysis to transfer homogenised lowland air temperature records to each of the sites, and these reconstructions were validated using data from on-site automatic weather stations. These data showed that mean annual temperature has varied over the last 200 years at each site by between 1 and 2 °C, typical of the high frequency variability found throughout the Holocene, and appropriate, therefore, to test the sensitivity of the various proxy methods used. Sediment cores from each site were radiometrically dated using ²¹⁰Pb, ¹³⁷Cs and ²⁴¹Am and analysed for loss-on-ignition, C, N, S, pigments, diatoms, chrysophytes, Cladocera and chironomids. Comparisons between the proxy data and the instrumental data were based on linear regression analysis with the proxy data treated as response variables and the instrumental data (after smoothing using LOESS regressions) as predictor variables. The results showed few clear or consistent patterns with generally low or very low r² values. Highest values were found when the data were compared after smoothing using a broad span, indicating that some of the proxy data were capturing climate variability but only at a relatively coarse time resolution. Probable reasons for the weak performance of the methods used include inaccurate dating, especially for earlier time periods, the influence of confounding forcing factors at some sites e.g., air pollution, earthquakes, and the insensitivity of some methods to low amplitude climate forcing. Nevertheless, there were trends in some proxy records at a number of sites that had a relatively unambiguous correspondence with the instrumental climate records. These included organic matter and associated variables (C and N) and planktonic diatom assemblages at the majority of sites and chrysophytes and chironomids at a few sites. Overall for longer term studies of the Holocene, these results indicate the need to be cautious in the interpretation of proxy records, the importance of proxy method validation, the continuing need to use reinforcing multi-proxy approaches, and the need for careful site and method selection.     

A variance-ratio test for supporting a variable mean in kriging

This article discusses the issue of whether to use a variable mean and describes a test that can be used to evaluate whether it is justified to add terms to the drift (deterministic part) of a geostatistical model. The basic model could be the intrinsic one, where the deterministic part is a constant, and the alternate model could be any model that includes a constant term in the expression for the drift. Also, differences between constant- and variable-mean models are discussed.