Fe2+-Ti4+ charge transfer in stoichiometric Fe2+,Ti4+-minerals

Optical absorption spectra are presented for taramellite, traskite and neptunite, all of which have both Fe²⁺ and Ti⁴⁺ as major elements. The spectra of each of these minerals are dominated by a single, intense absorption band in the 415 to 460 nm region with 7000 to 9000 cm^?1 halfwidth. These transitions, assigned to Fe²⁺-Ti⁴⁺ intervalence charge transfer, showed little difference in intensity at 80 and 300 K and have molar absorptivities which range from ～100 to ～1300 M^?1 cm^?1. The Fe²⁺-Ti⁴⁺ absorptions in these standards generally compare well to other mineral spectra in which Fe²⁺ — Ti⁴⁺ intervalence absorption has previously been proposed with the exception of the most cited example, blue corundum.     

Airborne Laser-Induced Fluorescence (LIF) Light Detection and Ranging (LiDAR) for the Quantification of Dissolved Organic Matter Concentration in Natural Waters

Analysis of dissolved organic matter (DOM) concentration and composition is essential to quantifying biological and chemical oxygen demand and atmosphere?Cocean heat flux exchange in natural waters. However, manual water sampling is costly and time consuming over large areas. The purpose of this research was to analyze the applicability of airborne laser-induced fluorescence light detection and ranging (LiDAR) for the detection of DOM in estuarine ecosystems impacted by agriculture. A fluorescence LiDAR system (Airborne Marine) (FLS-AM) was used to assess the DOM concentration of the Annapolis River and Basin, Nova Scotia, Canada, as well as three rivers and their estuaries in Prince Edward Island, Canada. Two FLS-AM flight missions were conducted in the summers of 2008 and 2009 and the resulting datasets were compared with spectral fluorescence signature (SFS DOM) and dissolved organic carbon (DOC) analysis of in situ water samples. Significant positive correlations were found at five of seven sites between the FLS-AM DOM and SFS DOM relationship which indicates that the FLS-AM sensor is a good surrogate for traditional sample collection of DOM data in estuaries in this region. Positive correlations were also found at all sites between FLS-AM DOM values and DOC. FLS-AM DOM patterns show that DOM values are significantly higher in rivers and estuaries that drain watersheds which are heavily impacted by agricultural practices. The results of this study show that the FLS-AM can be used efficiently as a general indicator for how estuaries are affected by runoff from agricultural watersheds in real time and thus reduce the requirement for traditional water sample collection and laboratory analysis methods.     

Calcareous nannoplankton, planktonic foraminiferal, and carbonate carbon isotope stratigraphy of the Cenomanian–Turonian boundary section in the Ultrahelvetic Zone (Eastern Alps, Upper Austria)

Ultrahelvetic units of the Eastern Alps were deposited on the distal European continental margin of the (Alpine) Tethys. The Rehkogelgraben section (“Buntmergelserie”, Ultrahelvetic unit, Upper Austria) comprises a 5 m thick succession of upper Cenomanian marl-limestone cycles overlain by a black shale interval composed of three black shale layers and carbonate-free claystones, followed by lower Turonian white to light grey marly limestones with thin marl layers. The main biostratigraphic events in the section are the last occurrence of Rotalipora and the first occurrences of Helvetoglobotruncana helvetica and Quadrum gartneri. The thickest black shale horizon has a TOC content of about 5%, with predominantly marine organic matter of kerogen type II. Vitrinite reflectance and Rock-Eval parameter T_max (<424 °C) indicate low maturity. HI values range from 261 to 362 mg HC/g TOC. δ¹³C values of bulk rock carbonates display the well documented positive shift around the black shale interval, allowing correlation of the Rehkogelgraben section with other sections such as the Global Boundary Stratotype Section and Point (GSSP) succession at Pueblo, USA, and reference sections at Eastbourne, UK, and Gubbio, Italy. Sediment accumulation rates at Rehkogelgraben (average 2.5 mm/ka) are significantly lower than those at Pueblo and Eastbourne.     

Use of composite data sets for source-tracking enterococci in the water column and shoreline interstitial waters on Pensacola Beach, Florida

Sources of Enterococcus faecalis isolates from Pensacola Beach, FL. were identified using a library-based approach by applying the statistical method of average similarity to single and composite data sets generated from separate analyses. Data sets included antibiotic resistance analysis (ARA), rep-fingerprints, and fatty acid methyl ester (FAME) profiles. Use of a composite data set composed of ARA and rep-fingerprints, added to the confidence of the identifications. The addition of FAME data to composite data sets did not add to the confidence of identifications. Source identification was performed to better understand risk associated with higher densities of enterococci found in swash zone interstitial water (SZIW) as compared to adjacent bathing water on Pensacola Beach, FL. The "swash zone" is that area of the beach continually washed over by waves. As the potential sources of enterococci were limited in this environment, only two library units, sea gull and human, were constructed. Identification of the beach isolates using a composite data set indicated a sea gull origin. The clonality of the beach isolates suggested that the beach environment selects certain subspecies of E. faecalis.     

Introducing the decile concept for studying the spatiotemporal characteristics and variability of long-lasting dry and wet periods

Changes in the persistence of dry and wet periods are of particular interest for many sectors, as long-term deviations from normal precipitation strongly affect the water availability. Here, an indicator is introduced to explore variability and trends of long-lasting dry and wet periods by using decile based thresholds. The test of three different thresholds for ending those periods revealed only slight influences of the chosen threshold on the spatiotemporal pattern and trends. The methodology of the deciles indicator is illustrated and studied exemplarily for a spatially highly resolved data set for Saxony, Germany within 1901–2010. Within that region decile wet and dry periods, respectively, occur approximately four times within 10 years, last on average 11 months and cover on average more than 35 % of the stations. Several years to decades long periods with particularly frequent and/or long decile dry or wet periods were identified. The computed trends strongly depend upon the analysis period, as frequency, duration and spatial coverage of decile periods show strong variations up to multi-decadal time scales. Nonetheless, there is some indication that dry period coverage increased within the 20th century, while wet period coverage decreased. However, in the most recent decades the long-term trends reversed.     

Inverted-polarity electrical structures in thunderstorms in the Severe Thunderstorm Electrification and Precipitation Study (STEPS)

Balloon-borne electric field soundings and lightning mapping data have been analyzed for three of the storms that occurred in the Severe Thunderstorm Electrification and Precipitation Study field program in 2000 to determine if the storms had inverted-polarity electrical structures. The polarities of all or some of the vertically stacked charge regions in such storms are opposite to the polarities observed at comparable heights in normal storms. Analyses compared the charge structures inferred from electric field soundings in the storms with charges inferred from three-dimensional lightning mapping data. Charge structures were inferred from electric field profiles by combining the one-dimensional approximation of Gauss's law with additional information from three-dimensional patterns in the electric field vectors. The three different ways of inferring the charge structure in the storms were found to complement each other and to be consistent overall. Charge deposition by lightning possibly occurred and increased the charge complexity of one of the storms.Many of the cloud flashes in each case were inverted-polarity flashes. Two storms produced ground flash activity comprised predominantly of positive ground flashes. One storm, which was an isolated thunderstorm, produced inverted-polarity cloud flashes, but no flashes to ground. The positive and negative thunderstorm charge regions were found at altitudes where, respectively, negative and positive charge would be found in normal-polarity storms. Thus, we conclude that these storms had anomalous and inverted-polarity electrical structures. Collectively, these three cases (along with the limited cases in the refereed literature) provide additional evidence that thunderstorms can have inverted-polarity electrical structures.     

Time-Relative Positioning with a Single Civil GPS Receiver

Time-relative positioning is a recent method for processing GPS phase observations. The operational method undertaken in this paper consists of the following steps: first, recording phase observations at a station of known coordinates; second, moving the GPS receiver to an unknown station (which can be located up to a few hundred meters away, dependint on what type of transportation – e. g., walking, motorcycle – is available) while continuously observing carrier phases; and, third, recording phase observations at a second station of unknown coordinates with a single GPS receiver. To obtain the position of the unknown station relative to the first (known) station, the processing method uses combined observations taken at two different epochs and two different stations with the same receiver. For this reason, the errors that vary between two epochs must be taken into account in an appropriate way, especially errors in satellite clock corrections and ephemerides, and errors related to tropospheric and ionospheric delays. Ionospheric modeling using IONEX files (the ionospheric maps calculated by the International GPS Service) was also tested to correct L1 phase observations. This method has been used to calculate short vectors with an accuracy of a few centimeters (for a processing interval of 30 s) using a single civil GPS receiver. ? 2001 John Wiley & Sons, Inc.     

Long-term hydrology and aquatic biogeochemistry data from H. J. Andrews Experimental Forest,Cascade Mountains,Oregon

The H. J. Andrews Experimental Forest (HJA) encompasses the 6400 ha Lookout Creek watershed in western Oregon, USA. Hydrologic, chemistry and precipitation data have been collected, curated, and archived for up to 70 years. The HJA was established in 1948 to study the effects of harvest of old-growth conifer forest and logging-road construction on water quality, quantity and vegetation succession. Over time, research questions have expanded to include terrestrial and aquatic species, communities and ecosystem dynamics. There are nine small experimental watersheds and 10 gaging stations in the HJA, including both reference and experimentally treated watersheds. Gaged watershed areas range from 8.5 to 6242 ha. All gaging stations record stage height, water conductivity, water temperature and above-stream air temperature. At nine of the gage sites, flow-proportional water samples are collected and composited over 3-week intervals for chemical analysis. Analysis of stream and precipitation chemistry began in 1968. Analytes include dissolved and particulate species of nitrogen and phosphorus, dissolved organic carbon, pH, specific conductance, suspended sediment, alkalinity, and major cations and anions. Supporting climate measurements began in the 1950s in association with the first small watershed experiments. Over time, and following the initiation of the Long Term Ecological Research (LTER) grant in 1980, infrastructure expanded to include a set of benchmark and secondary meteorological stations located in clearings spanning the elevation range within the Lookout Creek watershed, as well as a large number of forest understory temperature stations. Extensive metadata on sensor configurations, changes in methods over time, sensor accuracy and precision, and data quality control flags are associated with the HJA data.     

Connectivity of post-fire runoff and sediment from nested hillslopes and watersheds

Wildfire increases the potential connectivity of runoff and sediment throughout watersheds due to greater bare soil, runoff and erosion as compared to pre-fire conditions. This research examines the connectivity of post-fire runoff and sediment from hillslopes (< 1.5 ha; n = 31) and catchments (< 1000 ha; n = 10) within two watersheds (< 1500 ha) burned by the 2012 High Park Fire in northcentral Colorado, USA. Our objectives were to: (1) identify sources and quantify magnitudes of post-fire runoff and erosion at nested hillslopes and watersheds for two rain storms with varied duration, intensity and antecedent precipitation; and (2) assess the factors affecting the magnitude and connectivity of runoff and sediment across spatial scales for these two rain storms. The two summer storms that are the focus of this research occurred during the third summer after burning. The first storm had low intensity rainfall over 11 hours (return interval <1–2 years), whereas the second event had high intensity rainfall over 1 hour (return interval <1–10 years). The lower intensity storm was preceded by high antecedent rainfall and led to low hillslope sediment yields and channel incision at most locations, whereas the high intensity storm led to infiltration-excess overland flow, high sediment yields, in-stream sediment deposition and channel substrate fining. For both storms, hillslope-to-stream sediment delivery ratios and area-normalised cross-sectional channel change increased with the percent of catchment that burned at high severity. For the high intensity storm, hillslope-to-stream sediment delivery ratios decreased with unconfined channel length (%). The findings quantify post-fire connectivity and sediment delivery from hillslopes and streams, and highlight how different types of storms can cause varying magnitues and spatial patterns of sediment transport and deposition from hillslopes through stream channel networks.     

Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.