Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products

Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSⁿ and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC₁₀-keto-aldehydes, C₁₀-keto-carboxylicacids, C₁₀-hydroxy-keto-carboxylic acids, andC₁₀-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from -pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC₉-ketones, C₉-dicarboxylic acids, andC₁₀-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers from-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC₉-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C₈-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C₁₀-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC₁₀-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC₁₀-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC₉-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.     

The last glaciation of the Arctic volcanic island Jan Mayen

The volcanic island of Jan Mayen, remotely located in the Norwegian-Greenland Sea, was covered by a contiguous ice cap during the Late Weichselian. Until now, it has been disputed whether parts of the island south of the presently glaciated Mount Beerenberg area were ever glaciated. Based on extensive field mapping we demonstrate that an ice cap covered all land areas and likely also extended onto the shallow shelf areas southeast and east of the island. Chronological interpretations are based on K-Ar and ⁴⁰Ar/³⁹Ar dating of volcanic rocks, cosmogenic nuclide (³⁶Cl) surface exposure dating of bedrock and glacial erratics, and radiocarbon dating. We argue that ice growth started after 34 ka and that an initial deglaciation started some 21.5–19.5 ka in the southern and middle parts of the island. In the northern parts, closer to the present glaciers, the deglaciation might have started later, as evidenced by the establishment of vegetation 17–16 cal. ka BP. During full glaciation, the ice cap was likely thickest over the southern part of the island. This may explain a seemingly delayed deglaciation compared with the northern parts despite earlier initial deglaciation. In a broader context, the new knowledge of the Late Weichselian of the island contributes to the understanding of glaciations surrounding the North Atlantic and its climate history.     

Geochemical and isotopic evidence for upward flow of saline fluid to the Mississippi River Valley alluvial aquifer,southeastern Arkansas,USA

Hydrogeology Journal - Groundwater from the Quaternary Mississippi River Valley Alluvial (MRVA) aquifer in southeastern Arkansas (SE AR), USA, has higher salinity compared to other MRVA...     

Origin and extent of fresh groundwater, salty paleowaters and recent saltwater intrusions in Red River flood plain aquifers, Vietnam

A model has been established on the origin and extent of fresh groundwater, salty paleowaters and saltwater from recent seawater intrusions in the Red River flood plain in Vietnam. This was done with geological observations, geophysical borehole logging and transient electromagnetic methods. Salt paleowater is present up to 50–75?km from the coastline, with occurrence controlled by the Holocene transgression. A density-driven leaching of salty porewater has occurred from high-permeability Holocene sediments into underlying Pleistocene deposits, whereas diffusion has dominated in low-permeability layers. In the Pleistocene aquifer, the highest content of dissolved solids is found below two intrinsic valleys with Holocene marine sediments and along the coastline. Recent intrusion of saltwater from the South China Sea is observed in shallow groundwater 35?km inland, probably a result of transport of salty water inland in rivers or leaching of paleowaters from very young near-coast marine sediments. The observed inverted salinity profile, with high saline water overlying fresher groundwater, has been formed due to the global eustatic sea-level changes during the last 8,000–9,000?years. The proposed model may therefore be applicable to other coastal aquifers, with a proper incorporation of the local geological environments.     

A 10Be‐based reconstruction of the last deglaciation in southern Sweden

We present 23 cosmogenic surface exposure ages from 10 localities in southern Sweden. The new ¹⁰Be ages allow a direct correlation between the east and west coasts of southern Sweden, based on the same dating technique, and provide new information about the deglaciation of the Fennoscandian Ice Sheet in the circum‐Baltic area. In western Skåne, southernmost Sweden, a single cosmogenic surface exposure sample gave an age of 16.8±1.0 ka, whereas two samples from the central part of Skåne gave ages of 17.0±0.9 and 14.1±0.8 ka. Further northeast, in southern Småland, two localities gave ages ranging from 15.2±0.8 to 16.9±0.9 ka (n=5) indicating a somewhat earlier deglaciation of the area than has previously been suggested. Our third locality, in S Småland, gave ages ranging from 10.2±0.5 to 18.4±1.6 ka (n=3), which are probably not representative of the timing of deglaciation. In central Småland one locality was dated to 14.5±0.8 ka (n=3), whereas our northernmost locality, situated in northern Småland, was dated to 13.8±0.8 ka (n=3). Samples from the island of Gotland suggest deglaciation before 13 ka ago. We combined the new ¹⁰Be ages with previously published deglaciation ages to constrain the deglaciation chronology of southern Sweden. The combined deglaciation chronology suggests a rather steady deglaciation in southern Sweden starting at c. 17.9 cal. ka BP in NW Skåne and reaching northern Småland, ～200 km further north, c. 13.8 ka ago. Overall the new deglaciation ages agree reasonably well with existing deglaciation chronologies, but suggest a somewhat earlier deglaciation in Småland.     

Origin of high manganese concentrations in coal mine drainage, eastern Tennessee

The origin of high dissolved manganese concentrations in slightly acidic mine runoff from a surface mine operated by the Cumberland Coal Company in eastern Tennessee was investigated. Mineralogical and chemical analyses were performed on 31 samples of sandstone, shale, coal, and mudstone from the mine to identify the sources and stratigraphic distribution of high extractable manganese contents in the spoil materials. The samples were analyzed for their bulk mineral content by X-ray diffraction, net acid-base potential, and reaction to 2 or 4 chemical extraction procedures. A limited number of samples were analyzed for petrographic characteristics, clay mineral composition by X-ray diffraction, and mineral compositions by electron microprobe. Analysis of the data and consideration of the geochemical conditions at the mine were used to identify probable sources for the high extractable manganese contents.The results indicate 2 prominent, independent sources of extractable manganese. The first source is exchangeable manganese on clay minerals (mainly illite + muscovite and chlorite) and is concentrated in shale and mudstone rock types. The second and more significant source is manganese in siderite concretions and cement, mainly in shale and mudstone. Comparison to other coal-bearing strata indicates that manganese-rich siderite is common in fresh- to brackish-water subaqueous sediments that overlie coal. This is especially the case for coals formed in wet, tropical environments.Ratios of manganese to calcium and magnesium in mine runoff suggest that manganese from siderite is the major cause of the high dissolved manganese contents. A conceptual model is developed to explain the high manganese contents of the mine runoff. Oxidation of pyrite creates mildly acidic waters that are subsequently partially neutralized by reaction with impure siderite. Solubilized manganese remains dissolved in the slightly acidic runoff water, whereas dissolved iron precipitates as ferric hydroxide or goethite. Consideration of data from other coal mining regions suggests that similar reactions involving impure siderite may be responsible for high manganese concentrations in acidic to slightly acidic mine runoff. Geochemical reaction path modeling of pyrite and impure siderite with rainwater illustrate how resulting water compositions may vary depending on pyrite to siderite ratios in spoil materials. Spoil water compositions from the Cumberland mine are largely consistent with reaction of pyrite and impure siderite in proportions observed in the sediments; however, deviations may be explained by minor mixing with waters that reacted only with impure siderite or clay mineral exchange reactions.     

Aspects Of The Atmospheric Surface Layers On Mars And Earth

The structures of mean flow and turbulence in the atmospheric surface boundary layer have been extensively studied on Earth, and to a far less extent on Mars, where only the Viking missions and the Pathfinder mission have delivered in-situ data. Largely the behaviour of surface-layer turbulence and mean flow on Mars is found to obey the same scaling laws as on Earth. The largest micrometeorological differences between the two atmospheres are associated with the low air density of the Martian atmosphere. Together with the virtual absence of water vapour, it reduces the importance of the atmospheric heat flux in the surface energy budget. This increases the temperature variation of the surface forcing the near-surface temperature gradient and thereby the diabatic heat flux to higher values than are typical on the Earth, resulting in turn in a deeper daytime boundary layer. As wind speed is much like that of the Earth, this larger diabatic heat flux is carried mostly by larger maximal values of T_*, the surface scale temperature. The higher kinematic viscosity yields a Kolmogorov scale of the order of ten times larger than on Earth, influencing the transition between rough and smooth flow for the same surface features.The scaling laws have been validated analysing the Martian surface-layer data for the relations between the power spectra of wind and temperature turbulence and the corresponding mean values of wind speed and temperature. Usual spectral formulations were used based on the scaling laws ruling the Earth atmospheric surface layer, whereby the Earth's atmosphere is used as a standard for the Martian atmosphere.     

Impact melt rocks from the Late Paleocene Hiawatha impact structure,northwest Greenland

Impact melt rocks formed during hypervelocity impact events are ideal for studying impact structures. Here, we describe impact melt rock samples collected proximal to the 31 km wide 58 Ma Hiawatha impact structure, northwest Greenland, which is completely covered by the Greenland Ice Sheet. The melt rocks contain diagnostic shock indicators (e.g., planar deformation features [PDF] in quartz and shocked zircon) and form three groups based on melt textures and chemistry: (i) hypocrystalline, (ii) glassy, and (iii) carbonate-based melt rocks. The exposed foreland directly in front of the structure consists of metasedimentary successions and igneous plutons; however, the carbonate-based impactites indicate a mixed target sequence with a significant carbonate-rich component. Well-preserved organic material in some melt rocks indicates that North Greenland at the time of impact was host to abundant organic material, likely a dense high-latitude temperate forest. Geochemical signatures of platinum-group elements in selected samples indicate an extraterrestrial component and support previous identification of a highly fractionated iron impactor in glaciofluvial sand. Our results illustrate the possibility to study impact structures hidden beneath a thick ice sheet based on transported samples and this opens a new avenue for identifying other potential impact craters in Greenland and Antarctica.