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At least 1,369 records · Page 76Linked to original sources

Airborne lidar sensing of massive stony coral colonies on patch reefs in the northern Florida reef tract

In this study we examined the ability of the NASA Experimental Advanced Airborne Research Lidar (EAARL) to discriminate cluster zones of massive stony coral colonies on northern Florida reef tract (NFRT) patch reefs based on their topographic complexity (rugosity). Spatially dense EAARL laser submarine topographic soundings acquired in August 2002 were used to create a 1-m resolution digital rugosity map for adjacent NFRT study areas characterized by patch reefs (Region A) and diverse substratums (Region B). In both regions, sites with lidar-sensed rugosities above 1.2 were imaged by an along-track underwater videography system that incorporated the acquisition of instantaneous GPS positions. Subsequent manual interpretation of videotape segments was performed to identify substratum types that caused elevated lidar-sensed rugosity. Our study determined that massive coral colony formation, modified by subsequent physical and biological processes that breakdown patch reef framework, was the primary source of topographic complexity sensed by the EAARL in the NFRT. Sites recognized by lidar scanning to be topographically complex preferentially occurred around the margins of patch reefs, constituted a minor fraction of the reef system, and usually reflected the presence of massive coral colonies in cluster zones, or their derivatives created by mortality, bioerosion, and physical breakdown.

Florida↗

Western Lake Erie Basin: Soft-data-constrained, NHDPlus resolution watershed modeling and exploration of applicable conservation scenarios

Complex watershed simulation models are powerful tools that can help scientists and policy-makers address challenging topics, such as land use management and water security. In the Western Lake Erie Basin (WLEB), complex hydrological models have been applied at various scales to help describe relationships between land use and water, nutrient, and sediment dynamics. This manuscript evaluated the capacity of the current Soil and Water Assessment Tool (SWAT2012) to predict hydrological and water quality processes within WLEB at the finest resolution watershed boundary unit (NHDPlus) along with the current conditions and conservation scenarios. The process based SWAT model was capable of the fine-scale computation and complex routing used in this project, as indicated by measured data at five gaging stations. The level of detail required for fine-scale spatial simulation made the use of both hard and soft data necessary in model calibration, alongside other model adaptations. Limitations to the model's predictive capacity were due to a paucity of data in the region at the NHDPlus scale rather than due to SWAT functionality. Results of treatment scenarios demonstrate variable effects of structural practices and nutrient management on sediment and nutrient loss dynamics. Targeting treatment to acres with critical outstanding conservation needs provides the largest return on investment in terms of nutrient loss reduction per dollar spent, relative to treating acres with lower inherent nutrient loss vulnerabilities. Importantly, this research raises considerations about use of models to guide land management decisions at very fine spatial scales. Decision makers using these results should be aware of data limitations that hinder fine-scale model interpretation.

Lake Erie Basin↗

Stable isotopes provide insight into sources and cycling of N compounds in the Sacramento-San Joaquin Delta, California, USA

River deltas and their diverse array of aquatic environments are increasingly impacted by anthropogenic inputs of nitrogen (N). These inputs can alter the N biogeochemistry of these systems and promote undesirable phenomena including harmful algae blooms and invasive aquatic macrophytes. To examine N sources and biogeochemical processes in the Sacramento-San Joaquin Delta, a river delta located in central California, USA, that is fed primarily by the Sacramento River, we utilized a multi-tracer approach that measured N species concentrations and stable isotope values monthly from April 2011 to November 2012 in samples collected from the channelized mainstem of the Sacramento River, two channelized distributaries of the Sacramento River, and the Cache Slough Complex, a network of Sacramento River tributaries and shallow water wetland habitat. We found that the Sacramento River and its channelized distributaries received N primarily in the form of NH 4 + from treated wastewater effluent and that NH 4 + was lost rapidly while NO 3 − was gained more slowly during subsequent downstream transit, driven by an array of biogeochemical processes whose identities could be constrained via examination of stable isotope values. The Cache Slough Complex, which was characterized by lower net flows and higher water residence times than the Sacramento River and its distributaries, received variable inputs of low conductivity water elevated in NH 4 + from the Sacramento River and higher conductivity water elevated in NO 3 − from landward tributaries. Deviations from expected conservative mixing of these sources were spatially variable but broadly indicative of local inputs of treated wastewater effluent NO 3 − , conversion of Sacramento River NH 4 + to NO 3 − via nitrification, uptake of NH 4 + and NO 3 − by phytoplankton, and remineralization of organic N. These findings highlight both the diversity in N dynamics in anthropogenically impacted river delta environments and the utility of a multi-tracer approach in constraining these processes in such complex systems.

California↗

Intrinsic controls on the range of volumes, morphologies, and dimensions of submarine lobes

Submarine lobe dimensions from six different systems are compared: 1) the exhumed Permian Fan 3 lobe complex of the Tanqua Karoo, South Africa; 2) the modern Amazon fan channel-mouth lobe complex, offshore Brazil; 3) a portion of the modern distal Za??re fan, offshore Angola/Congo; 4) a Pleistocene fan of the Kutai basin, subsurface offshore Indonesia; 5) the modern Golo system, offshore east Corsica, France; and 6) a shallow subsurface lobe complex , offshore Nigeria. These six systems have significantly different source-to-sink configurations (shelf dimension and slope topography), sediment supply characteristics (available grain size range and supply rate), tectonic settings, (palaeo) latitude, and delivery systems. Despite these differences, lobe deposits share similar geometric and dimensional characteristics. Lobes are grouped into two distinct populations of geometries that can be related to basin floor topography. The first population corresponds to areally extensive but thin lobes (average width 14km??length 35km??thickness 12m) that were deposited onto low relief basin floor areas. Examples of such systems include the Tanqua Karoo, the Amazon, and the Za??re systems. The second population corresponds to areally smaller but thicker lobes (average width 5km??length 8km??thickness 30m) that were deposited into settings with higher amplitude of relief, like in the Corsican trough, the Kutai basin, and offshore Nigeria. The two populations of lobe types, however, share similar volumes (a narrow range around 1 or 2km3), which suggests that there is a control to the total volume of sediment that individual lobes can reach before they shift to a new locus of deposition. This indicates that the extrinsic processes control the number of lobes deposited per unit time rather than their dimensions. Two alternative hypotheses are presented to explain the similarities in lobe volumes calculated from the six very different systems. The first states that the wide range of starting flow volume and grain size across all systems enters the basin floor as a narrow range due to slope 'filtering' via more overspill and intra-channel deposition in larger systems. The second hypothesis is a result of the gradual decrease in downstream gradient from the distributive channel base to the lobe top during lobe growth. This is not sustainable as the channel will start to aggrade, and when a steeper lateral gradient is present, an avulsion will occur to an adjacent depositional low, which will be used for flows to fill and build a new lobe. This analysis of submarine lobe volumes indicates that the basin floor topography influences lobe geometry, but the fact that lobe volumes have a narrow range indicates a strong influence of intrinsic processes. ?? 2010 Elsevier B.V.

Sedimentary Geology↗

Development of a deep-crustal shear zone in response to syntectonic intrusion of mafic magma into the lower crust, Ivrea-Verbano zone, Italy

A 1 to 1.5 km-thick, high-temperature shear zone is localized in wall rocks subparallel to the eastern intrusive contact of the Permian Mafic Complex of the Ivrea-Verbano zone (IVZ), Italy. The shear zone is characterized by concentrated ductile deformation manifested by a penetrative foliation subparallel to the intrusive contact and a northeast-plunging sillimanite lineation. Evidence of noncoaxial strain and transposition is widespread in the shear zone including such features as rootless isoclinal folds, dismemberment of competent layers, and scattered kinematic indicators. The metasedimentary rocks in the shear zone are migmatitic, and the accumulation of leucosome is variable within the shear zone. Near the intrusive contact with the Mafic Complex leucosome forms ~20 vol% of the wall rock, whereas leucosome concentrations may locally reach ~60 vol% of the wall rock near the outer limits of the shear zone. This variation in vol% leucosome suggests melt/magma migration from the inferred site of anatexis along the intrusive contact to lower-strain regions within and near the margins of the shear zone. The leucosome accumulations chiefly occur as layer-parallel concentrations, but are also folded and boudined, and locally are associated with tension gashes and fracture arrays. Networks of granitic dikes and small plutons in the eastern IVZ suggest that some magmas migrated out of the high-temperature shear zone. Some magma apparently migrated laterally along the strike of the shear zone and concentrated in areas of lower strain where the intrusive contact takes a major westward bend. The high-temperature shear zone is interpreted as a 'stretching fault' (or stretching shear zone) after Means [W.D. Means, Stretching faults, Geology 17 (1989) 893-896], whereupon the metasedimentary wall rocks and associated leucosome deformed synchronously with the multistage emplacement and deformation flow of the Mafic Complex. The recognition of a high-temperature shear zone associated with the emplacement of mafic igneous rocks into the deep crust is an example of the progressive stratification of the lower crust during magmatic under- or intraplating that has consequences for seismic imaging and its interpretation.

Earth and Planetary Science Letters↗

From safe yield to sustainable development of water resources - The Kansas experience

This paper presents a synthesis of water sustainability issues from the hydrologic perspective. It shows that safe yield is a flawed concept and that sustainability is an idea that is broadly used but perhaps not well understood. In general, the sustainable yield of an aquifer must be considerably less than recharge if adequate amounts of water are to be available to sustain both the quantity and quality of streams, springs, wetlands, and ground-water-dependent ecosystems. To ensure sustainability, it is imperative that water limits be established based on hydrologic principles of mass balance. To establish water-use policies and planning horizons, the transition curves of aquifer systems from ground-water storage depletion to induced recharge of surface water need to be developed. Present-day numerical models are capable of generating such transition curves. Several idealized examples of aquifer systems show how this could be done. Because of the complexity of natural systems and the uncertainties in characterizing them, the current philosophy underlying sustainable management of water resources is based on the interconnected systems approach and on adaptive management. Examples of water-resources management from Kansas illustrate some of these concepts in a real-world setting. Some of the hallmarks of Kansas water management are the formation of local ground-water management districts, the adoption of minimum streamflow standards, the use of modified safe-yield policies in some districts, the implementation of integrated resource planning by the City of Wichita, and the subbasin water-resources management program in potential problem areas. These are all appropriate steps toward sustainable development. The Kansas examples show that local decision-making is the best way to fully account for local variability in water management. However, it is imperative that public education and involvement be encouraged, so that system complexities and constraints are better understood and overly simplistic solutions avoided. (C) 2000 Elsevier Science B.V.This paper presents a synthesis of water sustainability issues from the hydrologic perspective. It shows that safe yield is a flawed concept and that sustainability is an idea that is broadly used but perhaps not well understood. In general, the sustainable yield of an aquifer must be considerably less than recharge if adequate amounts of water are to be available to sustain both the quantity and quality of streams, springs, wetlands, and ground-water-dependent ecosystems. To ensure sustainability, it is imperative that water limits be established based on hydrologic principles of mass balance. To establish water-use policies and planning horizons, the transition curves of aquifer systems from ground-water storage depletion to induced recharge of surface water need to be developed. Present-day numerical models are capable of generating such transition curves. Several idealized examples of aquifer systems show how this could be done. Because of the complexity of natural systems and the uncertainties in characterizing them, the current philosophy underlying sustainable management of water resources is based on the interconnected systems approach and on adaptive management. Examples of water-resources management from Kansas illustrate some of these concepts in a real-world setting. Some of the hallmarks of Kansas water management are the formation of local ground-water management districts, the adoption of minimum streamflow standards, the use of modified safe-yield policies in some districts, the implementation of integrated resource planning by the City of Wichita, and the subbasin water-resources management program in potential problem areas. These are all appropriate steps toward sustainable development. The Kansas examples show that local decision-making is the best way to fully account for local variability in water management. However, it is imperative that public education and involv

Journal of Hydrology↗

Constraining controls on carbonate sequences with high-resolution chronostratigraphy: Upper Miocene, Cabo de Gata region, SE Spain

A high-resolution chronostratigraphy has been developed for Miocene shallow-water carbonate strata in the Cabo de Gata region of SE Spain for evaluation of local, regional and global factors that controlled platform architecture prior to and during the Messinian salinity crisis. Paleomagnetic data were collected from strata at three localities. Mean natural remanent magnetization (NRM) ranges between 1.53 ?? 10-8 and 5.2 ?? 10-3 Am2/kg. Incremental thermal and alternating field demagnetization isolated the characteristic remanent magnetization (ChRM). Rock magnetic studies show that the dominant magnetic mineral is magnetite, but mixtures of magnetite and hematite occur. A composite chronostratigraphy was derived from five stratigraphic sections. Regional stratigraphic data, biostratigraphic data, and an 40Ar/39Ar date of 8.5 ?? 0.1 Ma, for an interbedded volcanic flow, place the strata in geomagnetic polarity Chrons C4r to C3r. Sequence-stratigraphic and diagenetic evidence indicate a major unconformity at the base of depositional sequence (DS)3 that contains a prograding reef complex, suggesting that approximately 250 000 yr of record (Subchrons C3Br.2r to 3Br.1r) are missing near the Messinian-Tortonian boundary. Correlation to the GPTS shows that the studied strata represent five third- to fourth-order DSs. Basal units are temperate to subtropical ramps (DS1A, DS1B, DS2); these are overlain by subtropical to tropical reefal platforms (DS3), which are capped by subtropical to tropical cyclic carbonates (Terminal Carbonate Complex, TCC). Correlation of the Cabo de Gata record to the Melilla area of Morocco, and the Sorbas basin of Spain indicate that early - Late Tortonian ramp strata from these areas are partially time-equivalent. Similar strata are extensively developed in the Western Mediterranean and likely were influenced by a cool climate or influx of nutrients during an overall rise in global sea-level. After ramp deposition, a sequence boundary (SB3) in Cabo de Gata correlates with a sequence boundary in Morocco and a published third-order eustatic fall suggesting at least a partial eustatic control for the sequence boundary. Coral reefs began to develop earlier in Cabo de Gata than at Melilla or Sorbas, arguing for local factors affecting this major environmental transition. Later Messinian reefs (DS3) from all areas are time-equivalent, suggesting a regional or global control on their formation. Some Halimeda-rich horizons in the Western Mediterranean are not time-equivalent event strata as hypothesized by others. Correlation of the relative sea-level curve for the fringing reef complex (DS3) with a published eustatic curve suggests at least a partial third-order global eustatic control for the highstand part of the sequence. Downstepping DS3 reefs and initial subaerial exposure of earlier DS3 reef strata approximately correlate with initiation of a series of subaerial unconformities in the South Pacific. The longer-term relative fall in sea-level during DS3 downstepping reef progradation does not correlate with a published third-order eustatic fall. Eustatic sea-level fluctuations may have been associated with initiation of the Mediterranean Messinian salinity crisis, but the longer-term fall may have been linked to tectonic uplift in the Mediterranean region. Widespread distribution of 'TCC-style' cycles of approximately the same age suggests a regional (Western Mediterranean) or global control on sea-level change responsible for TCC cycles. In addition, four subaerial exposure-capped TCC cycles may correlate with similar subaerial unconformities in the South Pacific, suggesting at least a partial eustatic control on TCC cyclicity. The high rates of relative sea-level change needed to generate a minimum of 25-30 m sea-level changes associated with each cycle are consistent with glacio-eustacy along with rapid evaporitic drawdown in the Mediterranean. ?? 2001 Elsevier Science B.V. All rights reserved.

Palaeogeography, Palaeoclimatology, Palaeoecology↗

Controls on facies and sequence stratigraphy of an upper Miocene carbonate ramp and platform, Melilla basin, NE Morocco

Upwelling of cool seawater, paleoceanographic circulation, paleoclimate, local tectonics and relative sea-level change controlled the lithofacies and sequence stratigraphy of a carbonate ramp and overlying platform that are part of a temporally well constrained carbonate complex in the Melilla basin, northeastern Morocco. At Melilla, from oldest to youngest, a third-order depositional sequence within the carbonate complex contains (1) a retrogradational, transgressive, warm temperate-type rhodalgal ramp; (2) an early highstand, progradational, bioclastic platform composed mainly of a temperate-type, bivalve-rich molechfor facies; and (3) late highstand, progradational to downstepping, subtropical/tropical-type chlorozoan fringing Porites reefs. The change from rhodalgal ramp to molechfor platform occurred at 7.0±0.14 Ma "> 7.0±0.14Ma near the Tortonian/Messinian boundary. During a late stage in the development of the bioclastic platform a transition from temperate-type molechfor facies to subtropical/tropical-type chlorozoan facies occurred and is bracketed by chron 3An.2n (∼6.3–6.6 Ma). Comparison to a well-dated carbonate complex in southeastern Spain at Cabo de Gata suggests that upwelling of cool seawater influenced production of temperate-type limestone within the ramp and platform at Melilla during postulated late Tortonian–early Messinian subtropical/tropical paleoclimatic conditions in the western Paleo-Mediterranean region. The upwelling of cool seawater across the bioclastic platform at Melilla could be related to the beginning of ‘siphoning’ of deep, cold Atlantic waters into the Paleo-Mediterranean Sea at 7.17 Ma. The facies change within the bioclastic platform from molechfor to chlorozoan facies may be coincident with a reduction of the siphoning of Atlantic waters and the end of upwelling at Melilla during chron 3An.2n. The ramp contains one retrogradational parasequence and the bioclastic platform three progradational parasequences. Minor erosional surfaces that bound the upper surface of the ramp and upper surface of the oldest platform parasequence are related to relative falls in sea level induced by local volcanism and associated tectonic uplift. These local relative falls had little influence on a broader-scale rise to stillstand in relative sea level that controlled development of the transgressive and early highstand systems tracts represented in the ramp and platform, respectively.

Melilla basin↗

Description and comparison of geologic maps with FRAGSTATS - A spatial statistics program

FRAGSTATS is a public-domain GIS implementation of a set of spatial statistics that address a fundamental problem in GIS applications, description and comparison of maps. The spatial statistics from the 1:2,500,000-scale United States geologic map of Nevada, the central United States, and the northeastern United States quantify the differences in complexity and variability between these three geologic terranes. Nevada is defined by a large number of patches of small size and low size variability, whereas the Central area has a small number of patches with smaller relative size variability. All three areas have similar map-unit shape complexity with Nevada having the lowest. Based on the density of edges, the areas can be ranked from highest to lowest, as Nevada, Central, and Northeast. The Shannon diversity index ranks the areas from highest to lowest, as Northeast, Nevada, and Central, but the Shannon evenness index ranks them from highest to lowest, as Northeast, Central, and Nevada. These rankings may reflect the influence of folding in the Northeast and Central areas as opposed to basin and range extension in Nevada. The core areas statistic ranks the areas for spatial accuracy from highest to lowest, as Central, Northeast, and Nevada, with Northeast and Nevada being similar. For a scale comparison, the FRAGSTATS statistics quantify the increased complexity and spatial accuracy that is inherent in going from small- to larger-scale maps. For example for 1:2,500,000-1:500,000-scale maps of Nevada, respectively, the area weighted fractal dimension increase from 1.1 to 1.18, and the total core areas index almost doubles from 39.09 to 63.38. In addition, the fractal dimensions discriminate gross lithology and tectonic terranes. ?? 2002 Elsevier Science Ltd. All rights reserved.

Computers & Geosciences↗

A procedure for quantitation of total oxidized uranium for bioremediation studies

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio. Various strengths of NaHCO 3 , Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO 3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO 3 . Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Journal of Microbiological Methods↗

Juxtaposition of Neoproterozoic units along the Baruda - Tulu Dimtu shear-belt in the East African Orogen of western Ethiopia

Amalgamation of East and West Gondwanaland during the Neoproterozoic East African Orogen is recorded by several shear-belts or 'suture zones', some of which are associated with ultramafic and mafic complexes that have been interpreted as ophiolite fragments. The Baruda shear-belt is a major structure of this type that belongs to the N-S trending Barka - Tulu Dimtu zone. The significance of this zone has been studied within a transect in western Ethiopia which covers a variety of metasedimentary and metavolcanic sequences, ultramafic rocks and synkinematic intrusive complexes. All rocks participated in the regional D1 event as reflected in a penetrative steep foliation in supracrustal rocks and marginal parts of the intrusions. Highly strained rocks contain a stretching lineation that plunge to the east. The several-km thick Baruda shear-belt, comprising mylonitic supracrustal and plutonic rocks including mafic-ultramafic mega-lenses, is the most prominent expression of this event. Shear-sense indicators demonstrate top-to-the-west shear. Subsequent D2 deformation is recorded in 2-300 m wide, N-S striking, subvertical shear-zones with subhorizontal stretching lineation relatable to sinistral transcurrent movements. Our data indicate that rock units on either side of the Baruda shear-belt are related, rather than being exotic to each other as implied in suture zone models, since there is no major lithologic or metamorphic difference, geochemical data on metavolcanic rocks and pre-tectonic intrusions suggest a paleotectonic link, and style and extent of deformation is similar across the shear-belt. A tentative model for the transect suggests an arc and back-arc setting which experienced later continental collision and tectonic shortening. The initial setting was that of a shallow marine platform characterised by carbonates and sandstones, which covered extensive areas prior to break-up of a pre-existing supercontinent. Continental convergence is first recorded in high-K calc-alkaline volcanism characterised by pyroclastic deposits of andesitic composition, at an active continental margin at about 800 Ma. Subaerial arc volcanism was temporally and spatially overlapping with limited arc rifting, represented by submarine basalts compositionally transitional between enriched MORB and calc-alkaline magmas, and associated dyke swarms in the older carbonate-sandstone platform sequence. It is suggested that the large, mafic-ultramafic, bodies relate to this event and were originally formed as intrusions along one or more propagating rift axis within the arc complex. The regional Baruda shear-belt formed in response to contractional D1 deformation, and its location may have been largely controlled by competence contrasts between the array of rift-related intrusions and the marble-dominated lithologies. Associated shortening of the arc and back-arc region led to crustal thickening and emplacement of synkinematic, composite, batholiths at about 570-550 Ma. These are composed of moderately peraluminous granite and coeval, intermediate to mafic intrusions of shoshonitic affinity. D2 sinistral movements succeeded the contractional deformation. ?? 2001 Elsevier Science B.V.

Precambrian Research↗

Theoretical stusy of the reaction between 2,2',4' - trihydroxyazobenzene-5-sulfonic acid and zirconium

Zirconium reacts with 2,2',4'-trihydroxyazobenzene-5-sulfonic acid in acid solutions to Form two complexes in which the ratios of dye to zirconium are 1 to 1 and 2 to 1. Both complexes are true chelates, with zirconium acting as a bridge between the two orthohydroxy dye groups. Apparent equilibrium constants for the reactions to form each of the complexes are determined. The reactions are used as a basis for the determination of the active component in the dye and a graphical method for the determination of reagent purity is described. Four absorption spectra covering the wave length region from 350 to 750 mu are given, which completely define the color system associated with the reactions in solutions where the hydrochloric acid concentration ranges from 0.0064N to about 7N.

Analytical Chemistry↗

Quercetin as colorimetric reagent for determination of zirconium

Methods described in the literature for the determination of zirconium are generally designed for relatively large amounts of this element. A good procedure using colorimetric reagent for the determination of trace amounts is desirable. Quercetin has been found to yield a sensitive color reaction with zirconium suitable for the determination of from 0.1 to 50 of zirconium dioxide. The procedure developed involves the separation of zirconium from interfering elements by precipitation with p-dimethylaminoazophenylarsonic acid prior to its estimation with quercetin. The quercetin reaction is carried out in 0.5N hydrochloric acid solution. Under the operating conditions it is indicated that quercetin forms a 2 to 1 complex with zirconium; however, a 2 to 1 and a 1 to 1 complex can coexist under special conditions. Approximate values for the equilibrium constants of the complexes are K 1 = 0.33 x 10 -5 and K 2 = 1.3 x 10 -9 . Seven Bureau of Standards samples of glass sands and refractories were analyzed with excellent results. The method described should find considerable application in the analysis of minerals and other materials for macro as well as micro amounts of zirconium.

Analytical Chemistry↗

Spectrophotometric study of the thorium-morin mixed-color system

A spectrophotometric study was made of the thoriummorin reaction to evaluate the suitability of morin as a reagent for the determination of trace amounts of thorium. At pH 2, the equilibrium constant for the reaction is 1 x 10 6 , and a single complex having a thorium-morin ratio of 1 to 2 is formed. The complex shows maximum absorbance at a wave length of 410 m μ , and its absorbance obeys Beer's law. The absorbance readings are highly reproducible, and the sensitivity is relatively high, an absorbance difference of 0.001 being equivalent to 0.007 γ of ThO 2 per sq. cm. The effects of acid, alcohol, and morin concentration, time, temperature, and age of the morin reagent as well as the behavior of morin with zirconium(IV), iron(III), aluminum(III), ytterbium(III), yttrium(III), uranium(VI), praseodymium(III), lead(II), lanthanum(III), and calcium(II) ions are discussed. A method is presented for the determination of thorium in pure solutions. Appropriate separations for the isolation of thorium may extend the usefulness of the method and permit the determination of trace amounts of thorium in complex materials.

Analytical Chemistry↗

Fluorometric study of the magnesium—Bissalicylidene-ethylenediamine aystem

Magnesium ions combine with bissalicylidene-ethylenediamine in slightly alkaline N,N′-dimethylformamide to form a highly fluorescent complex which serves for the determination of trace amounts of magnesium. The yellow complex fluoresces blue when irradiated with ultraviolet light. The chelate shows maximum fluorescence excitation at 355 mμ and has a fluorescence emission maximum at 439 mμ. A complex having a metal to ligand ratio of 1 to 1 is formed. The method is sensitive to 7 × 10 −6 μmole of magnesium per ml. The analysis of Bureau of Standards samples with the reagent showed excellent correlation between the fluorometric and spectrophotometric procedures

Analytical Chemistry↗

Fluorometric study of the beryllium-morin system

Three principal beryllium-morin complexes, a (1 + 1) monomer, a (1 + 1) dimer, and a (1 + 2) complex are found and conditional equilibrium constants for their formation are evaluated. Approximate ionization constants, absorption spectra, and the relative fluorescence intensities for five ionic species of morin are also determined in a spectrophotometric and fluorometric study of morin. The following interrelationships are discussed: pH, ionization of morin, absorption spectra of the various ionic species of morin and of the berylliummorin complexes, equilibria for the reactions between beryllium and morin, the period of time between preparation of the solution and measurement of the fluorescence, and fluorescence intensity.

Analytical Chemistry↗

Mechanism of SO2 removal by carbon

The reaction of SO 2 with carbon (C) in the presence of O 2 and H 2 O involves a series of reactions that leads to the formation of sulfuric acid as the final product. The rate-determining step in the overall process is the oxidation of SO 2 to SO 3 . Three SO 2 oxidation reactions are possible. Adsorbed SO 2 (C−SO 2 ) can react either with gas phase O 2 or with adsorbed oxygen (C−O complex) to form sulfur trioxide (SO 3 ), or gas phase SO 2 can react directly with the C−O complex. In optimizing the SO 2 removal capabilities of carbon, most studies only assume a given mechanism for SO 2 adsorption and conversion to H 2 SO 4 to be operable. The appropriate SO 2 oxidation step and role of the C−O complex in this mechanism remain to be determined. The ultimate goal of this study was to prepare activated char from Illinois coal with optimal properties for low-temperature (80−150°C) removal of sulfur dioxide from coal combustion flue gas. The SO 2 adsorption capacity of activated char was found to be inversely proportional to the amount of oxygen adsorbed on its surface. A temperature-programmed desorption technique was developed to titrate those sites responsible for adsorption of SO 2 and conversion to H 2 SO 4 . On the basis of these results, a mechanism for SO 2 removal by carbon was proposed. The derived rate expression showed SO 2 adsorption to be dependent only on the fundamental rate constant and concentration of carbon atoms designated as free sites. Recent studies indicate a similar relationship exists between the rate of carbon gasification (in CO 2 or H 2 O) and the number of reactive sites as determined by transient kinetics experiments. Utilizing the concept of active or free sites, it was possible to produce a char from Illinois coal having an SO 2 adsorption capacity surpassing that of a commercial catalytic activated carbon.

Energy and Fuels↗

Oxidation of dimethylselenide by δMnO 2 : oxidation product and factors affecting oxidation rate

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

Environmental Science & Technology↗