Infrared and Raman spectroscopy studies of the α–β phase transition in cristobalite

Infrared and Raman spectra of cristobalite are presented as a function of temperature through the phase transition. The modes are assigned and the assignments compared to those of earlier workers. The compatibility of modes at the G-point of the a-phase with the X and G-points of the ß-phase is given. In the transition region of ca. 500–550 K, smooth changes in intensity, frequency and linewidths are seen in many modes, indicative of coexistence of a- and ß-forms.     

Morphology of HCN and CN in Comet Hale-Bopp (1995 O1)

We compare images of Comet Hale-Bopp (1995 O1) in HCN and CN taken near perihelion (April 1, 1997) to determine the origin of CN in comets. We imaged the J=1→0 transition of HCN at λ=3 mm with the BIMA Array. Data from two weeks around perihelion were summed within four phase bins based on the rotational period of the comet. This increases both the signal-to-noise ratio and the u-v coverage while decreasing the smearing of the spatial features. The similarly phased narrowband CN images were taken at Lowell Observatory within the same range of dates as the HCN images. We find that there is a better correlation between HCN and CN than between HCN and the optically dominant dust. If the CN in jets does have a dust source it would have to have a very low albedo and/or small particle size. The production rates are consistent with HCN being a primary parent of CN, although there are discrepancies between the HCN destruction scalelength and the CN production scalelength which we discuss.     

Oceanography of Glacier Bay,Alaska: Implications for biological patterns in a glacial fjord estuary

Alaska, U.S.A, is one of the few remaining locations in the world that has fjords that contain temperate idewater glaciers. Studying such estuarine systems provides vital information on how deglaciation affects oceanographic onditions of fjords and surrounding coastal waters. The oceanographic system of Glacier Bay, Alaska, is of particular interest ue to the rapid deglaciation of the Bay and the resulting changes in the estuarine environment, the relatively high oncentrations of marine mammals, seabirds, fishes, and invertebrates, and the Bay’s status as a national park, where ommercial fisheries are being phased out. We describe the first comprehensive broad-scale analysis of physical and iological oceanographic conditions within Glacier Bay based on CTD measurements at 24 stations from 1993 to 2002. easonal patterns of near-surface salinity, temperature, stratification, turbidity, and euphotic depth suggest that freshwater nput was highest in summer, emphasizing the critical role of glacier and snowmelt to this system. Strong and persistent tratification of surface waters driven by freshwater input occurred from spring through fall. After accounting for seasonal nd spatial variation, several of the external physical factors (i.e., air temperature, precipitation, day length) explained a large mount of variation in the physical properties of the surface waters. Spatial patterns of phytoplankton biomass varied hroughout the year and were related to stratification levels, euphotic depth, and day length. We observed hydrographic atterns indicative of strong competing forces influencing water column stability within Glacier Bay: high levels of freshwater ischarge promoted stratification in the upper fjord, while strong tidal currents over the Bay’s shallow entrance sill enhanced ertical mixing. Where these two processes met in the central deep basins there were optimal conditions of intermediate tratification, higher light levels, and potential nutrient renewal. These conditions were associated with high and sustained hlorophylla levels observed from spring through fall in these zones of the Bay and provide a framework for understanding he abundance patterns of higher trophic levels within this estuarine system.     

Validation of climate model output using Bayesian statistical methods

The growing interest in and emphasis on high spatial resolution estimates of future climate has demonstrated the need to apply regional climate models (RCMs) to that problem. As a consequence, the need for validation of these models, an assessment of how well an RCM reproduces a known climate, has also grown. Validation is often performed by comparing RCM output to gridded climate datasets and/or station data. The primary disadvantage of using gridded climate datasets is that the spatial resolution is almost always different and generally coarser than climate model output. We have used a Bayesian statistical model derived from observational data to validate RCM output. We used surface air temperature (SAT) data from 109 observational stations in California, all with records of approximately 50 years in length, and created a statistical model based on this data. The statistical model takes into account the elevation of the station, distance from coastline, and the NOAA climate region in which the station resides. Analysis indicates that the statistical model provides reliable estimates of the mean monthly SAT at any given station. In our method, the uncertainty in the estimates produced by the statistical model are directly determined by obtaining probability density functions for predicted SATs. This statistical model is then used to estimate average SATs corresponding to each of the climate model grid cells. These estimates are compared to the output of the RCM to assess how well the RCM matches the observed climate as defined by the statistical model. Overall, the match between the RCM output and the statistical model is good, with some deficiencies likely due in part to the representation of topography in the RCM.     

Detection of iodine monoxide radicals in the marine boundary layer using laser induced fluorescence spectroscopy

A Laser Induced Fluorescence (LIF) instrument has been developed to detect iodine monoxide (IO) radicals in the atmosphere. An all solid-state Nd:YAG pumped Ti:Sapphire laser operating at approximately 445 nm was used to excite the (2,0) band of the IO A²Π_3/2 ← X²Π_3/2 electronic transition, with off-resonance fluorescence in the (2,5) band detected at 521 nm. The sensitivity of the instrument was determined by calibration. IO (between 10 and 150 pptV) was generated following the 184.9 nm photolysis of N₂O/CF₃I/N₂ mixtures with O₃ actinometry used to determine the photolysis flux. The detection limit was determined to be 0.3 pptV for a 300 s integration period, with an uncertainty of 23% (1σ). The instrument was deployed in August/September 2006 during the RHaMBLe (Reactive Halogens in the Marine Boundary Layer) campaign in Roscoff, France. Located on a small jetty, a few metres from the water’s edge at high tide, the instrument measured significant levels of IO on 11 days, with a maximum of 27.6 ± 3.2 pptV observed on one day (averaged over 10 s) representing the highest IO mixing ratio recorded in the marine boundary layer to date. IO displayed a clear diurnal profile with a maximum at low tide during the daytime. These results represent the first point measurements of IO in the atmosphere by LIF.     

Solubility of KFe(CrO4)2·2H2O at 4–75°C

The solubility of KFe(CrO₄)₂·2H₂O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO₄)₂·2H₂O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log K_SP for the reaction

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Combined use of spot samples and continuous integrated sampling in a study of storm runoff from a lowland catchment in the south of England

We have used two different sampling techniques to study the geochemical response of a small lowland rural catchment to episodic storm runoff. The first method involves traditional daily spot sampling and has been used to develop a standard end‐member mixing analysis (EMMA) of the relative contributions of ground water flow and surface runoff to the total stream flow. The second method utilizes a continuous sampling device, powered by an osmotic pump, to produce an integrated 24‐h sample of the stream flow. When combined with the EMMA results from the spot samples, analyses of the integrated samples reveal the presence of a third component that makes a significant contribution to the dissolved NO₃, Ca and K export from the catchment during the rising limb of the hydrographic profile of a storm event following a prolonged dry period. The storm occurred in the middle of the night, so that the response of the stream chemistry was not captured by the daily samples. We hypothesize that this third component is derived from the flushing of stored soil water that contains the geochemical signature of decaying vegetation. Copyright © 2011 John Wiley & Sons, Ltd.     

Growth of ferruginous oncoliths in the Bajocian (Middle Jurassic) of Europe

Limonitic oncoliths from the Bajocian of Europe, widely known as ‘snuff-boxes’, grew by accretion of bundles of laminae on one side, followed by overturning and accretion of laminae on the other side. A diverse hard-substrate encrusting fauna grew interleaved with the ferruginous laminations. The palaeoecological preferences of this fauna indicate that its growth, and hence the accumulation of the laminations, took place on the gloomy undersides of the oncoliths. This upsidedown growth is supported by characteristics of the lamination bundles themselves, and by the predominant present-day orientations of the snuff-boxes. The abundance of the associated fauna and the lack of carbonate-dissolving macroborers cutting the laminae suggest an original ferric composition. Precipitation was probably under the control of non-photosynthetic microorganisms that inhabited the microenvironments represented by the oncoliths' lower surfaces.     

Macrobenthos relative to the oxygen minimum zone on the East Indian margin,Bay of Bengal

The Bay of Bengal remains one of the least studied of the world's oxygen minimum zones (OMZs). Here we offer a detailed investigation of the macrobenthos relative to oxygen minimum zone [OMZ – DO (dissolved oxygen), concentration <0.5 ml·1^?1] at 110 stations off the North East Indian margin (16⁰ and 20⁰ N) featuring coastal, shelf and slope settings (10–1004 m). Macrobenthos (>0.5 mm) composition, abundance and diversity were studied in relation to variations in depth, dissolved oxygen, sediment texture and organic carbon. Using multivariate procedures powered by SIMPROF analysis we identified distinct OMZ core sites (depth 150–280 m; DO 0.37 ml·1^?1) that exhibited dense populations of surface‐feeding polychaetes (mean 2188 ind. m^?2) represented by spionids and cossurids (96%). Molluscs and crustaceans were poorly represented except for ampeliscid amphipods. The lower OMZ sites (DO > 0.55 ml·l^?1) supported a different assemblage of polychaetes (cirratulids, amphinomids, eunicids, orbinids, paraonids), crustaceans and molluscs, albeit with low population densities (mean 343 ind. m^?2). Species richness [E(S₁₀₀)], diversity (Margalef d; H’) and evenness (J’) were lower and dominance was higher within the OMZ core region. Multiple regression analysis showed that a combination of sand, clay, organic carbon, and dissolved oxygen explained 62–78% of the observed variance in macrobenthos species richness and diversity: E(S₁₀₀) and H’. For polychaetes, clay and oxygen proved important. At low oxygen sites (DO <1 ml·l^?1), depth accounted for most variance. Residual analysis (after removing depth effects) revealed that dissolved oxygen and sediment organic matter influenced 50–62% of residual variation in E(S₁₀₀), H’ and d for total macrofauna. Of this, oxygen alone influenced up to ~50–62%. When only polychaetes were evaluated, oxygen and organic matter explained up to 58–63%. For low oxygen sites, organic matter alone had the explanatory power when dominance among polychaetes was considered. Overall, macrobenthic patterns in the Bay of Bengal were consistent with those reported for other upwelling margins. However, the compression of faunal gradients at shallower depths was most similar to the Chile/Peru margin, and different from the Arabian Sea, where the depth range of the OMZ is two times greater. The Bay of Bengal patterns may take on added significance as OMZs shoal globally.