Influence of artificial channels on the source and extent of saline water intrusion in the wind tide dominated wetlands of the southern Albemarle estuarine system (USA)

Saline water intrusion is degrading water quality in the channelized coastal wetlands of the southern Albemarle estuarine system (AES). The source, transport and fate of the saline water in the southern AES was determined by monitoring specific conductivity and water levels in small artificial channels, the Alligator River, the Alligator–Pungo Canal and the groundwater system for ~12 months. Results indicate that water levels are affected by wind tides which trigger the movement of saline water into the interior of the wetlands via the small canals. The wind tides are mostly driven by episodic southerly winds pushing saline water into the canal network and the groundwater regime proximal to the Alligator River. The saline waters persist in the canals as long as the wind tide events last. Specific conductivities from canals and groundwater are shown to be unexpectedly higher closer to the source of the Alligator River than toward the Albemarle Sound, suggesting that the large Alligator–Pungo Canal facilitates the northward migration of saline water from the Pamlico Sound to the Alligator River. Overwash and reversals in the flow directions between groundwater and surface water bodies suggest that saline water that is present during wind tide events may migrate into the groundwater system from surface water bodies. The results of this study reveal that whereas the large Alligator–Pungo Canal channels saline water to the AES, small artificial channels may also play significant roles in degrading water quality in the interior of channelized coastal wetlands.     

A re-examination of petrogenesis and 40Ar/39Ar systematics in the Chain of Ponds K-feldspar: “diffusion domain” archetype versus polyphase hygrochronology

K-feldspar (Kfs) from the Chain of Ponds Pluton (CPP) is the archetypal reference material, upon which thermochronological modeling of Ar diffusion in discrete “domains” was founded. We re-examine the CPP Kfs using cathodoluminescence and back-scattered electron imaging, transmission electron microscopy, and electron probe microanalysis. ⁴⁰Ar/³⁹Ar stepwise heating experiments on different sieve fractions, and on handpicked and unpicked aliquots, are compared. Our results reproduce the staircase-shaped age spectrum and the Arrhenius trajectory of the literature sample, confirming that samples collected from the same locality have an identical Ar isotope record. Even the most pristine-looking Kfs from the CPP contains successive generations of secondary, metasomatic/retrograde mineral replacements that post-date magmatic crystallization. These chemically and chronologically distinct phases are responsible for its staircase-shaped age spectra, which are modified by handpicking. While genuine within-grain diffusion gradients are not ruled out by these data, this study demonstrates that the most important control on staircase-shaped age spectra is the simultaneous presence of heterochemical, diachronous post-magmatic mineral growth. At least five distinct mineral species were identified in the Kfs separate, three of which can be traced to external fluids interacting with the CPP in a chemically open system. Sieve fractions have size-shifted Arrhenius trajectories, negating the existence of the smallest “diffusion domains.” Heterochemical phases also play an important role in producing nonlinear trajectories. In vacuo degassing rates recovered from Arrhenius plots are neither related to true Fick’s Law diffusion nor to the staircase shape of the age spectra. The CPP Kfs used to define the “diffusion domain” model demonstrates the predominance of metasomatic alteration by hydrothermal fluids and recrystallization in establishing the natural Ar distribution among different coexisting phases that gives rise to the staircase-shaped age spectrum. Microbeam imaging of textures is as essential for ⁴⁰Ar/³⁹Ar hygrochronology as it is for U–Pb geochronology.     

Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.     

Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

Equilibrium H/H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of ¹H and ²H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor (α_eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α_eq for C-bound H positions adjacent to carbonyl group (H_α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium ²H/¹H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G** level and used to calculate α_eq values for H_α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081−0.00376T and intercept = 8.404−0.387T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper (Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.     

Effects of grain morphology on critical state: a computational analysis

We introduce a new DEM scheme (LS-DEM) that takes advantage of level sets to enable the inclusion of real grain shapes into a classical discrete element method. Then, LS-DEM is validated and calibrated with respect to real experimental results. Finally, we exploit part of LS-DEM potentiality by using it to study the dependency of critical state (CS) parameters such as critical state line (CSL) slope \(\lambda \), CSL intercept \(\varGamma \), and CS friction angle \(\varPhi _{\mathrm{CS}}\) on the grain’s morphology, i.e., sphericity, roundness, and regularity. This study is carried out in three steps. First, LS-DEM is used to capture and simulate the shape of five different two-dimensional cross sections of real grains, which have been previously classified according to the aforementioned morphological features. Second, the same LS-DEM simulations are carried out for idealized/simplified grains, which are morphologically equivalent to their real counterparts. Third, the results of real and idealized grains are compared, so the effect of “imperfections” on real particles is isolated. Finally, trends for the CS parameters (CSP) dependency on sphericity, roundness, and regularity are obtained as well as analyzed. The main observations and remarks connecting particle’s morphology, particle’s idealization, and CSP are summarized in a table that is attempted to help in keeping a general picture of the analysis, results, and corresponding implications.     

Late Quaternary glaciation and equilibrium-line altitudes of the Mayan Ice Cap, Guatemala, Central America

The Sierra los Cuchumatanes (3837 m), Guatemala, supported a plateau ice cap and valley glaciers around Montaña San Juan (3784 m) that totaled ∼ 43 km² in area during the last local glacial maximum. Former ice limits are defined by sharp-crested lateral and terminal moraines that extend to elevations of ∼ 3450 m along the ice cap margin, and to ca. 3000-3300 m for the valley glaciers. Equilibrium-line altitudes (ELAs) estimated using the area-altitude balance ratio method for the maximum late Quaternary glaciation reached as low as 3470 m for the valley glaciers and 3670 m for the Mayan Ice Cap. Relative to the modern altitude of the 0°C isotherm of ∼ 4840 m, we determined ELA depressions of 1110-1436 m. If interpreted in terms of a depression of the freezing level during maximal glaciation along the modern lapse rate of − 5.3°C km^− 1, this ΔELA indicates tropical highland cooling of ∼ 5.9 to 7.6 ± 1.2°C. Our data support greater glacial highland cooling than at sea level, implying a high tropical sensitivity to global climate changes. The large magnitude of ELA depression in Guatemala may have been partially forced by enhanced wetness associated with southward excursions of the boreal winter polar air mass.     

Relict olivine grains, chondrule recycling, and implications for the chemical, thermal, and mechanical processing of nebular materials

Chondrules and isolated forsterites in five low-subtype ordinary chondrites [NWA 3127 (LL3.1), Sahara 97210 (LL3.2), Wells (LL3.3), Chainpur (LL3.4), and Sahara 98175 (LL3.5)] were studied using petrographic, EMPA, and SIMS techniques to better constrain the origin of chondrules and the olivine grains within them. Our results imply that igneous crystallization, vapor fractionation, redox effects, and open-system behavior were important processes. All olivine grains, including normal, relict, and isolated forsterite grains, show evidence for igneous fractionation under disequilibrium conditions, with olivine crystallizing during rapid cooling (closer to 2000 °C/h than to 100 °C/h). Vapor fractionation is manifested by anti-correlated abundances between refractory elements (Al, Sc, Y, Ti, Ca, V) and volatile elements (Cr, Mn, P, Rb, Fe) in olivine. Redox effects are evidenced in various ways, and imply that Fe, Co, Ni, and P were partitioned more into metal, and V was partitioned more into olivine, under reducing conditions in the most FeO-poor melts. There is no obvious evidence for systematic variations in olivine composition according to meteorite subtype, but shock melting in Sahara 97210 resulted in the injection of glass-derived melt into olivine, resulting in artificially high abundances of Ba, Sr, Na, Ti, and some other incompatible elements in olivine. Terrestrial weathering in a hot desert environment may have mobilized Ba and Sr in some glasses.Our data suggest that chondrules in ordinary chondrites experienced repeated thermal, chemical, and mechanical processing during a “recycling” process over an extended time period, which involved multiple episodes of melting under fluctuating redox and heating conditions, and multiple episodes of chondrule break-up in some cases. Forsterite grains, including normal grains in forsterite-bearing type I chondrules, the cores of isolated forsterites, and relict forsterite in type II chondrules, all crystallized from similar, refractory melts under reducing conditions; relict Mg-olivine and isolated forsterite grains were thus derived from type I chondrules. Olivine in type II chondrules, including normal grains and ferroan overgrowths on relict Mg-olivine, crystallized from more volatile-rich, oxidized, and relatively unfractionated melts. Relict dusty olivine grains in type I chondrules were derived from type II chondrules during incomplete melting episodes involving reduction and some vaporization, with clear (non-dusty) grains in dusty olivine-bearing chondrules crystallizing from the reduced and partly vaporized melts. Melt compositions parental to normal olivine grains in type I and II chondrules are systematically enriched in refractory elements compared to bulk chondrule compositions, implying that chondrules often experienced open-system exchange with more volatile-rich surroundings after some olivine had crystallized, possibly while the chondrules were still partly molten. Type II chondrules could have been derived from type I chondrules by the addition of relatively volatile-rich material, followed by re-melting and little evaporation under oxidizing conditions. In contrast, type I chondrules could have been derived from type II chondrules by re-melting involving more-or-less evaporation under reducing conditions. Chemical, oxygen isotope, and petrographic data are best accommodated by a model in which there were several (>2-3, sometimes ?4-5) melting episodes for most chondrules in ordinary chondrites.     

Rice crop phenology mapping at high spatial and temporal resolution using downscaled MODIS time-series

Satellite data holds considerable potential as a source of information on rice crop growth which can be used to inform agronomy. However, given the typical field sizes in many rice-growing countries such as China, data from coarse spatial resolution satellite systems such as the Moderate Resolution Imaging Spectroradiometer (MODIS) are inadequate for resolving crop growth variability at the field scale. Nevertheless, systems such as MODIS do provide images with sufficient frequency to be able to capture the detail of rice crop growth trajectories throughout a growing season. In order to generate high spatial and temporal resolution data suitable for mapping rice crop phenology, this study fused MODIS data with lower frequency, higher spatial resolution Landsat data. An overall workflow was developed which began with image preprocessing, calculation of multi-temporal normalized difference vegetation index (NDVI) images, and spatiotemporal fusion of data from the two sensors. The Spatial and Temporal Adaptive Reflectance Fusion Model was used to effectively downscale the MODIS data to deliver a time-series of 30 m spatial resolution NDVI data at 8-day intervals throughout the rice-growing season. Zonal statistical analysis was used to extract NDVI time-series for individual fields and signal filtering was applied to the time-series to generate rice phenology curves. The downscaled MODIS NDVI products were able to characterize the development of paddy rice at fine spatial and temporal resolutions, across wide spatial extents over multiple growing seasons. These data permitted the extraction of key crop seasonality parameters that quantified inter-annual growth variability for a whole agricultural region and enabled mapping of the variability in crop performance between and within fields. Hence, this approach can provide rice crop growth data that is suitable for informing agronomic policy and practice across a wide range of scales.