FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

Resonant Periodic Orbits of Trans-Neptunian Objects

We study two and three-dimensional resonant periodic orbits, usingthe model of the restricted three-body problem with the Sun andNeptune as primaries. The position and the stability character ofthe periodic orbits determine the structure of the phase space andthis will provide useful information on the stability and longterm evolution of trans-Neptunian objects. The circular planarmodel is used as the starting point. Families of periodic orbitsare computed at the exterior resonances 1/2, 2/3 and 3/4 withNeptune and these are used as a guide to select the energy levelsfor the computation of the Poincaré maps, so that all basicresonances are included in the study. Using the circular planarmodel as the basic model, we extend our study to more realisticmodels by considering an elliptic orbit of Neptune and introducingthe inclination of the orbit. Families of symmetric periodicorbits of the planar elliptic restricted three-body problem andthe three-dimensional problem are found. All these orbitsbifurcate from the families of periodic orbits of the planarcircular problem. The stability of all orbits is studied. Althoughthe resonant structure in the circular problem is similar for allresonances, the situation changes if the eccentricity of Neptuneor the inclination of the orbit is taken into account. All theseresults are combined to explain why in some resonances there aremany bodies and other resonances are empty.     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Toxicity assessment of sediments associated with various land-uses in coastal South Carolina, USA, using a meiobenthic copepod bioassay

Coastal urbanization supplies surrounding estuarine environments with urban-related contaminants such as polycyclic aromatic hydrocarbons (PAHs), metals and pesticide mixtures. In our study, adult female and male copepods (Amphiascus tenuiremis) were chronically exposed to 18 sediment samples collected from sites influenced by different land-uses. Sediment samples were collected from three major suburban areas (Hilton Head, Kiawah Island and the Okatee River watershed) and a pristine site (North Inlet) in coastal South Carolina. Three-sediment bioassays (six sites per bioassay) were conducted by culturing copepods for 14 days in quadruplicate test sediments under flow-through conditions at 20 degrees C and 12:12 LD cycles. Adult survival and copepod reproductive output were quantified. Sediment samples were also analyzed by GC-MS for low and high molecular weight PAHs. Minimal adult mortality was observed in most sediment samples. However, sediments from Hilton Head Island and the Okatee River showed significant effects on copepod reproductive output (i.e., nauplii, copepodites and clutch size). Thus, we determined that reproductive endpoints rather than adult copepod survivorship were more sensitive to effects of contaminated sediments on A. tenuiremis. Furthermore, six (33%) of the 18 sites had a >25% reduction in copepod bioassay endpoints relative to controls, suggesting a high risk to long term A. tenuiremis population maintenance.     

Recent increase of river–floodplain suspended sediment exchange in a reach of the lower Amazon River

We analyzed variation of channel–floodplain suspended sediment exchange along a 140 km reach of the lower Amazon River for two decades (1995–2014). Daily sediment fluxes were determined by combining measured and estimated surface sediment concentrations with river–floodplain water exchanges computed with a two‐dimensional hydraulic model. The average annual inflow to the floodplain was 4088 ± 2017 Gg yr^?1 and the outflow was 2251 ± 471 Gg yr^?1, respectively. Prediction of average sediment accretion rate was twice the estimate from a previous study of this same reach and more than an order of magnitude lower than an estimate from an earlier regional scale study. The amount of water routed through the floodplain, which is sensitive to levee topography and increases exponentially with river discharge, was the main factor controlling the variation in total annual sediment inflow. Besides floodplain routing, the total annual sediment export depended on the increase in sediment concentration in lakes during floodplain drainage. The recent increasing amplitude of the Amazon River annual flood over two decades has caused a substantial shift in water and sediment river–floodplain exchanges. In the second decade (2005–2014), as the frequency of extreme floods increased, annual sediment inflow increased by 81% and net storage increased by 317% in relation to the previous decade (1995–2004). Copyright © 2017 John Wiley & Sons, Ltd.     

Late Wisconsinan glaciation models of northern Maine and adjacent Canada

Surficial stratigraphic units of Aroostook County, Maine, have been mapped and formal stratigraphic names for these units are proposed. Evidence exists for at least two distinct glacial phases which are represented by three tills. Two of these tills were deposited penecontemporaneously either as the result of coalescing ice sheets or as the result of the thermal regime existing within a single ice sheet. The oldest till is named the St. Francis and is correlated with the Chaudière Till of southeastern Quebec. The other tills are named the Mars Hill and Van Buren tills, respectively, and are correlated with the Lennoxville till of southeastern Quebec. Interbedded stratified sediments associated with the St. Francis till are correlated with the Gayhurst Formation. Stratified sediments associated with Van Buren and Mars Hill tills are correlated with post Lennoxville sediments of Quebec. Granite-gneiss erratics of Canadian Shield provenance in the Van Buren till indicate advance of the Laurentide ice into northern Maine during late Wisconsinan time. Moraines in southern Aroostook County with associated outwash and eskers record general recession from coastal Maine. Recession occurred after the formation of the Pineo Ridge moraine in Maine and the St. Antonin-Highland Front moraine complex in Quebec. The Caribou-Winterville moraine complex in northern Maine marks the boundary between the penecontemporaneously deposited Van Buren and Mars Hill surface tills and is correlated with the Grand Falls moraine at Grand Falls, New Brunswick.     

Stratigraphy of total metals in PIRLA sediment cores

Sediment cores from 30 low-alkalinity lakes in northern New England (NE), New York (NY), the northern Great Lakes States (NGLS) of Minnesota, Michigan, and Wisconsin, and Florida (FL) have been dated by ²¹⁰Pb and analyzed for water and organic content, eight major elements (Al, Ti, Fe, Mn, Ca, Mg, Na, K) plus four trace metals (Pb, Zn, Cu, and V). Variations in the percentages of major elements through time are dominated by long-term independent variations in the abundance of SiO₂, FeO, and to a lesser extent Ca and Al. Additional variations are caused by varying proportions of inorganic matter. Major variations in chemistry are generally unrelated to documented distrubances in the watersheds; most disturbances are minor fires or selective logging.Accelerated accumulation of Pb from atmospheric sources into sediment first occurs in sediment dated between 1800 and 1850 in NY and NE, slightly later in the NGLS region, and about 1900 in FL. Modern accumulation rates in all areas are comparable (ca. 1 to 4 g cm^–2 yr^–1). Accumulation rates of Pb in some lakes have declined significantly from 1975 to 1985. Atmospheric deposition of anthropogenic Zn and Cu is also indicated by generally increasing accumulation rates in sediment cores, but the record is not as clear nor are chemical profiles in all lakes parallel to the trends in atmospheric emissions inferred on the basis of fossil fuel consumption, smelting, and other industrial activities. Inter-lake variations in profiles of Cu and Zn are large. Vanadium accumulation rates increase by the 1940s in NY and NE, but not until the 1950s in the NGLS region. This timing correlates with regional trends in the combustion of fuel oil, a major source of atmospheric V.Acidification of some of the lakes is suggested by decreases in the concentration and accumulation rates of Mn, Ca, and Zn in recent sediment, relative to other elements of catchment origin. The decreases generally occur slightly before the onset of acidification as indicated by diatoms. Increased sediment accumulation rates for Fe may indicate the acidification of watershed soils. The use of the accumulation rate of TiO₂ as an indicator of rates of erosion and for normalization of trace metal accumulation rates is in question for lakes where the flux of TiO₂ from the atmosphere varies and is a significant fraction of the total flux of TiO₂ to the sediment.This is the thirteenth of a series of papers to be published by this journal which is a contribution of the Paleoecological Investigation of Recent Lake Acidification (PIRLA) project. Drs. D. F. Charles and D. R. Whitehead are guest editors for this series.     

Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

Meteorite fusion crust formation is a brief event in a high‐temperature (2000–12,000 K) and high‐pressure (2–5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ⁵⁶Fe values up to +0.35‰ relative to the solar system mean. On average, the δ⁵⁶Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ⁵⁶Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ⁵⁶Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ¹⁸O (0.9–1.5‰) than their host chondrites, and the same is true for Δ¹⁷O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high‐pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an ¹⁶O‐poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.     

Corona textures in Proterozoic olivine melanorites of the Equeefa Suite,Natal Metamorphic Province,South Africa

Summary Olivine-plagioclase and phlogopite-plagioclase coronas have been identified from olivine melanorites of the Mid- to Late Proterozoic Equeefa Suite in southern Natal, South Africa. Olivine, in contact with plagioclase, is mantled by a shell of clear orthopyroxene, in turn rimmed by pale green (pargasitic) clinoamphibole. Locally a third rim, composed of a fine pargasite-spinel symplectite is developed adjacent to the plagioclase. The second corona reaction has produced greenish-brown pargasite at phlogopite-plagioclase interfaces. A third, less obvious reaction, between olivine and phlogopite is also noted. Analytical data of all the mineral phases present, along with the coronas, are given. Two-pyroxene thermometry yields magmatic core temperatures ( 1120°C), with rim compositions indicating equilibration at 850°C. Consistent with this, the modelled olivine-plagioclase reaction occurs between 830–1050°C with a_waterbetween 0.1 and 1.0 at 7 kbar. The three reactions took place during a prolonged history of cooling and partial hydration of the magmatic olivine melanorites from over 1000°C down to 600°C. The P-T conditions indicated by the reactions suggest this cooling process was essentially isobaric, indicating that the area was not subjected to rapid uplift or burial throughout this entire period.

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Korona-Texturen in proterozoischen Olivin-Melanoriten der Equeefa Suite, Natal Metamorphic Province, Südafrika

Zusammenfassung Aus Olivin-Melanoriten der mittel- bis spätproterozoischen Equeefa Suite im südlichen Natal, Südafrika, wurden Olivin-Plagioklas und Phlogopit-Plagioklas-Koronartexturen beobachtet. Olivin, der mit Plagioklas im Kontakt steht, wird von einem klaren Saum vom Orthopyroxen ummantelt, der seinerseits von blaßgrünem (pargasitischem) Klinoamphibol umsäumt wird. Stellenweise ist ein dritter Saum, bestehend aus feinkörnigem symplektitischem Pargasit-Spinell im Kontakt mit Plagioklas ausgebildet. Die zweite koronabildende Reaktion resultiert in Bildung eines grünbraunen Pargasites an Phlogopit-Plagioklas Kornkontakten. Eine dritte, weniger auffällige Reaktion zwischen Olivin und Phlogopit wurde ebenfalls beobachtet. Zwei-Pyroxen-Thermometrie ergab magmatische Temperaturen der Kernbereiche ( 1120°C) und belegt eine Gleichgewichtseinstellung in den Randzonen bei ca. 850°C. Olivin-Plagioklas-Modellreaktionen liegen ebenfalls in einem Temperaturbereich von 830–1050°C bei Wasseraktivitäten von 0.1 bis 1.0 und einem Druck von 7 kbar. Die drei Reaktionen liefen im Zuge einer länger andauernden Abkühlung unter teilweiser Hydratisierung der magmatischen Melanorite in einem Temperaturbereich von 1000°C bis ca. 600°C ab. Die aus den Reaktionen ableitbaren P-T-Bedingungen sprechen für eine im wesentlichen isobare Abkhlungsgeschichte und zeigen, daß dieses Gebiet wáhrend dieser gesamten Periode keiner raschen Hebung bzw. keiner Versenkung unterworfen worden ist.

     

Numerical modeling of toxic nonaqueous phase liquid removal from contaminated groundwater systems: mesh effect and discretization error estimation

Numerical modeling has now become an indispensable tool for investigating the fundamental mechanisms of toxic nonaqueous phase liquid (NAPL) removal from contaminated groundwater systems. Because the domain of a contaminated groundwater system may involve irregular shapes in geometry, it is necessary to use general quadrilateral elements, in which two neighbor sides are no longer perpendicular to each other. This can cause numerical errors on the computational simulation results due to mesh discretization effect. After the dimensionless governing equations of NAPL dissolution problems are briefly described, the propagation theory of the mesh discretization error associated with a NAPL dissolution system is first presented for a rectangular domain and then extended to a trapezoidal domain. This leads to the establishment of the finger‐amplitude growing theory that is associated with both the corner effect that takes place just at the entrance of the flow in a trapezoidal domain and the mesh discretization effect that occurs in the whole NAPL dissolution system of the trapezoidal domain. This theory can be used to make the approximate error estimation of the corresponding computational simulation results. The related theoretical analysis and numerical results have demonstrated the following: (1) both the corner effect and the mesh discretization effect can be quantitatively viewed as a kind of small perturbation, which can grow in unstable NAPL dissolution systems, so that they can have some considerable effects on the computational results of such systems; (2) the proposed finger‐amplitude growing theory associated with the corner effect at the entrance of a trapezoidal domain is useful for correctly explaining why the finger at either the top or bottom boundary grows much faster than that within the interior of the trapezoidal domain; (3) the proposed finger‐amplitude growing theory associated with the mesh discretization error in the NAPL dissolution system of a trapezoidal domain can be used for quantitatively assessing the correctness of computational simulations of NAPL dissolution front instability problems in trapezoidal domains, so that we can ensure that the computational simulation results are controlled by the physics of the NAPL dissolution system, rather than by the numerical artifacts. Copyright © 2014 John Wiley & Sons, Ltd.