What is the source of baseflow in agriculturally fragmented catchments? Complex groundwater/surface‐water interactions in three tributary catchments of the Wabash River,Indiana, USA

Some conceptual models suggest that baseflow in agriculturally fragmented watersheds may contain little, if any, groundwater. This has critical implications for stream quality and ecosystem functioning. Here, we (a) identify the sources and flowpaths contributing to baseflow using ²²²Rn and ⁸⁷Sr/⁸⁶Sr and (b) quantify mean apparent ages of groundwater and baseflow using multiple isotopic tracers (CFC, SF₆, ³⁶Cl, and ³H) in 4 small (0.08 to 0.64 km²) tributary catchments to the Wabash River in Indiana, USA. ²²²Rn activities and ⁸⁷Sr/⁸⁶Sr ratios indicate that baseflow in 3 catchments is sourced primarily from groundwater; baseflow in the fourth is dominated by a source similar to agricultural run‐off. CFC‐12 data indicate that springs in 1 catchment are discharging significant proportions of water that recharged between 1974 (42 ± 2 years) and 1961 (55 ± 2 years). Those same springs have ³⁶Cl/Cl ratios between 1,381.08 ± 29.37 (×10^?15) and 1,530.64 ± 27.65 (×10^?15) indicating that a substantial proportion of the discharge likely recharged between 1975 (41 years) and 1950 (66 years). Groundwater samples collected from streambed mini‐piezometers in a separate catchment have CFC‐12 concentrations indicating that a large proportion of the recharge occurred between 1948 (68 ± 2 years) and 1950 (66 ± 2 years). Repeat sampling conducted in September 2015 after above‐average summer rainfall did not show significant decreases in mean apparent age. The relatively old ages observed in 3 of the catchments can be explained by geological complexities that are likely present in all 4 catchments, but overwhelmed by flow from the shallow phreatic aquifer in the fourth catchment.     

Contribution to the thermal regime of the Provençal Basin based on Flumed heat flow surveys and previous investigations

We present original heat flow determinations carried out during the Flumed surveys by the CEPM along three transects of the Provençal Basin (Gulf of Lions-West Sardinia; Toulon-Ajaccio; Nice-Calvi). A total of 121 thermal gradients and 37 conductivities are examined together with previous heat flow determinations along depth sections based on previous geophysical investigations. The mean observed heat flows are clearly shown to increase from NW to SE along the profiles (expect for the Toulon-Calvi transect, where results are ambiguous). The observed heat flow increases from 55–65 mW m⁻² (Gulf of Lions) to 85 ± 14 mW m⁻² (West Sardinia) and from 55–65 mW m⁻² (Var Basin) to 103–108 mW m⁻² (lower Corsican margin), suggesting an asymmetrical distribution of the observed heat flow. We examine whether this asymmetry could be caused by thermal refraction above salt structures or by any other superficial cause (sedimentation, topography, etc.) and conclude that an asymmetrical distribution of the subcrustal heat flow is probably the cause of this thermal regime. The elevated heat flows observed to the east in the abyssal plain, corrected for sedimentation, cannot be accounted for by the standard age/heat flow relations established for oceanic or attenuated continental lithosphere. The geodynamic significance of this speculative subcrustal origin remains poorly constrained, but could be related to post-rifting magmatic activity. Further investigations are necessary to elucidate the apparent high local variability of the heat flow on the upper margin of the Gulf of Lions and on the Provençal margin of the Ligurian Sea.     

Soil moisture and rainfall intensity thresholds for runoff generation in southwestern Wisconsin agricultural watersheds

The goal of this study was to improve understanding of the factors that influence runoff generation during non‐frozen ground periods in small agricultural watersheds in southwestern Wisconsin where the landscapes are controlled by dolostone bedrock in order to provide agricultural producers with a manure management tool. Six small watersheds (ranging from 6 to 17 ha) within two southwestern Wisconsin farm sites (Discovery Farms Program (DFP) and Pioneer Farm (PF)) were instrumented, and surface runoff was continuously monitored from 2004 to 2007. The soils in all watersheds were formed in deep (~1 m) loessial sites. A direct‐plant management strategy and corn‐soybean crop rotation were utilized within watersheds at DFP. A conventional tillage system (chisel plow in the fall followed by soil finisher in the spring) and a corn‐oat‐alfalfa crop rotation were utilized within watersheds at PF. At PF, the amount of precipitation leaving the landscape as surface runoff (1.8%) was two times greater compared to DFP (0.9%), indicating that the direct‐plant management system was better at retaining precipitation than the chisel plow/soil finisher system. Using breakpoint regression analysis, a non‐linear response in runoff generation with antecedent soil moisture (ASM) was observed with a threshold ASM of 0.39 cm³cm^?3 (approximately 80% of total porosity) for all six watersheds. Below this threshold, runoff coefficients were near zero. Above this threshold, runoff coefficients increased with ASM. A non‐linear response in runoff generation with maximum 30 min rainfall intensity (I30) was also observed, and threshold I30 values increased as ASM decreased and as crop cover increased. Copyright © 2012 John Wiley & Sons, Ltd.     

New insights into the high-pressure polymorphism of SiO<Subscript>2</Subscript> cristobalite

Single-crystal X-ray diffraction experiments with SiO₂ α-cristobalite reveal that the well-known reversible displacive phase transition to cristobalite-II, which occurs at approximately 1.8 GPa, can be suppressed by rapid pressure increase, leading to an overpressurized metastable state, persisting to pressure as high as 10 GPa. In another, slow pressure increase experiment, the monoclinic high-pressure phase-II was observed to form at ~1.8 GPa, in agreement with earlier in situ studies, and its crystal structure has been unambiguously determined. Single-crystal data have been used to refine the structure models of both phases over the range of pressure up to the threshold of formation of cristobalite X-I at ~12 GPa, providing important constraints on the feasibility of the two competing silica densification models proposed in the literature, based on quantum mechanical calculations. Preliminary diffraction data obtained for cristobalite X-I reveal a monoclinic unit cell that contradicts the currently assumed model.     

Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

The sulfide (H₂S/HS^?) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [ $ {\text{S}}_{\text{x}}^{2 - } $ ] and thiosulfate [ $ {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } $ ], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H₂S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10^?3 ??M/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.     

Transport of the environmental radionuclides in an alpine watershed

The radionuclides¹³⁷Cs,²¹⁰Pb and⁷Be have been examined in the alpine Rhoˆne watershed (Switzerland) during a period of two years in order to evaluate their usefulness as tracers of the removal and transport rate of top-soil particles and particle-reactive contaminants of atmospheric origin. The specific activities of the radionuclides in fluvial suspension show a distinct seasonal pattern which depends on the hydrologic regime of the stream and the sources of the suspended matter. Input-output budgets based on the atmospheric deposition and fluvial removal of three radionuclides in the alpine Rhoˆne watershed are used to estimate their erosional residence times. The simplest one box model yields mean residence times of about 800 and 1400 years for¹³⁷Cs and²¹⁰Pb, respectively. The removal rate of short-lived⁷Be suggests that a part of the watershed (0.6–2.3% of the total surface) is exposed to a rapid erosion, in which the mean residence time of the radionuclides is in the range of 1–220 days. This has little influence on the calculated residence time of¹³⁷Cs but increases the estimated residence time of²¹⁰Pb in soil to over 1800 years. The use of²¹⁰Pb-⁷Be pair in fluvial output may be very helpful in the assessment of the impact of atmospheric pollutants on the water quality in rivers and lakes.     

Reduction of Manganese Oxides: Thermodynamic,Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

Manganese oxides, typically similar to δ-MnO₂, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O₂, as the reaction of [Mn(H₂O)₆]²⁺ with O₂ alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λ_max?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO₂ with ammonia (NH₃). Reactions are unfavorable for NH₄⁺ and sulfide with oxidized Fe and Mn solids, and NH₃ with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO₂. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO₂ solutions (λ_max?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO₂, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e _g ^* conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO₂ reduction using laboratory and field data for the reaction of MnO₂ with hydrogen sulfide and other reductants.     

Gem corundum deposits of Madagascar: A review

Madagascar is one of the most important gem-producing countries in the world, including ruby and sapphires. Gem corundum deposits formed at different stages in the geological evolution of the island and in contrasting environments. Four main settings are identified: (1) Gem corundum formed in the Precambrian basement within the Neoproterozoic terranes of southern Madagascar, and in the volcano-sedimentary series of Beforona, north of Antananarivo. In the south, high-temperature (700 to 800 °C) and low-pressure (4 to 5 kbar) granulites contain deposits formed during the Pan-African orogenesis between 565 and 490 Ma. They accompany mafic and ultramafic complexes (ruby deposits of the Vohibory group), skarns at the contact between Anosyan granites and the Proterozoic Tranomaro group (sapphire deposits of the Tranomaro–Andranondambo district), and shear-zone corridors cross-cutting feldspathic gneisses, cordieritites and clinopyroxenites in the Tranomaro, Vohimena and Androyan metamorphic series (biotite schist deposits of Sahambano and Zazafotsy, cordieritites of Iankaroka and Ambatomena). The circulation of fluids, especially along discontinuities, allowed in-situ alkaline metasomatism, forming corundum host rocks related to desilicified granites, biotitites, “sakenites” and “corundumites”. (2) Gem corundum also occurs in the Triassic detrital formations of the Isalo group, as giant palaeoplacers in the Ilakaka–Sakaraha area. Here, sapphires and rubies may come from the metamorphic granulitic terranes of southern Madagascar. (3) Gem corundum deposits occur within the Neogene-Quaternary alkali basalts from Ankaratra (Antsirabe–Antanifotsy area) and in the Ambohitra Province (Nosy Be, Ambato and Ambondromifehy districts). Primary deposits are rare, except at Soamiakatra where ruby in gabbroic and clinopyroxenite xenoliths within alkali-basalts probably derive from mantle garnet peridotites. The blue-green-yellow sapphires typical of basaltic fields are always recovered in palaeoplacer (in karst formed upon Jurassic limestones from the Montagne d'Ambre, Antsiranana Province) and alluvial and soil placers (Ankaratra volcanic massif). (4) Deposits occur within Quaternary eluvial, colluvial and alluvial concentrations, such as high-quality rubies from the Andilamena and Vatomandry deposits.