Sampling soil water along the pF curve for δ2H and δ18O analysis

Soil water stable isotopes are widely used across disciplines (e.g., hydrology, ecology, soil science, and biogeochemistry). However, the full potential of stables isotopes as a tool for characterizing the origin, flow path, transport processes and residence times of water in different eco-, hydro-, and geological compartments has not yet been exploited. This is mainly due to the large variety of different methods for pore water extraction. While recent work has shown that matric potential affects the equilibrium fractionation, little work has examined how different water retention characteristics might affect the sampled water isotopic composition. Here, we present a simple laboratory experiment with two well-studied standard soils differing in their physico-chemical properties (e.g., clayey loam and silty sand). Samples were sieved, oven-dried and spiked with water of known isotopic composition to full saturation. For investigating the effect of water retention characteristics on the extracted water isotopic composition, we used pressure extractors to sample isotopically labelled soil water along the pF curve. After pressure extraction, we further extracted the soil samples via cryogenic vacuum extraction. The null hypothesis guiding our work was that water held at different tensions shows the same isotopic composition. Our results showed that the sampled soil water differed isotopically from the introduced isotopic label over time and sequentially along the pF curve. Our and previous studies suggest caution in interpreting isotope results of extracted soil water and a need to better characterize processes that govern isotope fractionation with respect to soil water retention characteristics. In the future, knowledge about soil water retention characteristics with respect to soil water isotopic composition could be applied to predict soil water fractionation effects under natural and non-stationary conditions. In this regard, isotope retention characteristics as an analog to water retention characteristics have been proposed as a way forward since matric potential affects the equilibrium fractionation between the bound water and the water vapour.     

Molybdenum Mass Fractions and Stable Isotope Compositions of Sedimentary Carbonate and Silicate Reference Materials

A double‐spike method in combination with MC‐ICP‐MS was applied to obtain molybdenum (Mo) mass fractions and stable isotope compositions in a suite of sedimentary silicate (marine, lake, stream, estuarine, organic‐rich sediment, shales, slate, chert) and carbonate reference materials (coral, dolomite, limestones, carbonatites), and a manganese nodule reference material, poorly characterised for stable Mo isotope compositions. The Mo contents vary between 0.076 and 364 μg g^?1, with low‐Mo mass fractions (< 0.29 μg g^?1) found almost exclusively in carbonates. Intermediate Mo contents (0.73–2.70 μg g^?1) are reported for silicate sediments, with the exception of chert JCh‐1 (0.24 μg g^?1), organic‐rich shale SGR‐1b (36.6 μg g^?1) and manganese nodule NOD‐A‐1 (364 μg g^?1). The Mo isotope compositions (reported as δ⁹⁸Mo relative to NIST SRM 3134) range from ?1.77 to 1.03‰, with the intermediate precision varying between ± 0.01 and ± 0.12‰ (2s) for most materials. Low‐temperature carbonates show δ⁹⁸Mo values ranging from 0.21 to 1.03‰ whereas δ⁹⁸Mo values of ?1.77 and ?0.17‰ were obtained for carbonatites CMP‐1 and COQ‐1, respectively. Silicate materials have δ⁹⁸Mo values varying from ?1.56 to 0.73‰. The range of δ⁹⁸Mo values in reference materials may thus reflect the increasingly important relevance of Mo isotope investigations in the fields of palaeoceanography, weathering, sedimentation and provenance, as well as the magmatic realm.     

Biogeochemistry of a River-Dominated Estuary Influenced by Drought and Storms

Increased frequency and severity of droughts, as well as growing human freshwater demands, in the Apalachicola-Chattahoochee-Flint River Basin are expected to lead to a long-term decrease in freshwater discharge to Apalachicola Bay (Florida). To date, no long-term studies have assessed how river discharge variability affects the Bay’s phytoplankton community. Here a 14-year time series was used to assess the influence of hydrologic variability on the biogeochemistry and phytoplankton biomass in Apalachicola Bay. Data were collected at 10 sites in the bay along the salinity gradient and include drought and storm periods. Riverine dissolved inorganic nitrogen and phosphate inputs were correlated to river discharge, but chlorophyll a (Chl a) was similar between periods of drought and average/above-average river discharge in most of the Bay. Results suggest that the potentially negative impact of decreased riverine nutrient input on Bay phytoplankton biomass is mitigated by the nutrient buffering capacity of the estuary. Additionally, increased light availability, longer residence time, and decreased grazing pressures may allow more Chl a biomass to accumulate during drought. In contrast to droughts, tropical cyclones and subsequent increases in river discharge increased flushing and reduced light penetration, leading to reduced Chl a in the Bay. Analysis of the time series revealed that Chl a concentrations in the Bay do not directly mirror the effect of riverine nutrient input, which is masked by multiple interacting mechanisms (i.e., nutrient loading and retention, grazing, flushing, light penetration) that need to be considered when projecting the response of Bay Chl a to changes in freshwater input.     

Itinerant livelihoods: Street vending‐scapes and the politics of mobility in upland socialist Vietnam

This paper explores the politics of mobility for a group of rural inhabitants attempting to diversify their livelihoods in an especially prescribed environment, namely ethnic minority street vendors living and working in upland socialist Vietnam. These Hmong, Yao and Giáy individuals face a political environment where access and trade rights shift on a near‐daily basis because of the impulses of state officials, and where ethnicity is central to determining who gets to be mobile and how. We analyse three groups of itinerant vendors—those vending on the streets of an upland tourist town, the mobile minority wholesalers who supply them and other traders, and vendors who trek with Western tourists—to reveal the nature of this trade environment, while also highlighting the ways in which ethnic minority vendors negotiate, work around and contest vending restrictions in numerous innovative ways. We find that this focus on the micro‐geographies and everyday politics of mobility is essential to understanding how rural Global South livelihoods are fashioned and diversified, in this case revealing specific relationships and negotiations regarding resource access, ethnicity, state authority and livelihood strategies.     

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer

The stable isotope ratios of groundwater sulfate (³⁴S/³²S, ¹⁸O/¹⁶O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ¹⁸O and/or δ³⁴S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ³⁴S (−6.9 to +20.0‰) and δ¹⁸O (−5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.     

Ressaut de marée et Mascaret – exemples de la Garonne et de la Seine

In this article, we present a study on the tidal bore dynamics based on the analysis of the database acquired in 2011 during two simultaneous field campaigns in the Seine and Garonne Rivers. We have shown that in the Garonne River, contrary to the common view, undular tidal bore can form for a large majority of tides, even sometimes at neap tide when the river discharge is low. We have identified, from surface elevation measurements, low-steepness, low-frequency undular tidal bores which are not visually observable. Such low-frequency tidal bores have been also identified and characterised for the first time in the Seine River. In this river, the first undulation wave height can be higher than 1 m. We have shown that the secondary wave steepness strongly increases when the Froude number exceeds the critical value F_c. The large-steepness tidal bore regime corresponds to what is commonly termed in French mascaret.     

Models of solar irradiance variations: Current status

Regular monitoring of solar irradiance has been carried out since 1978 to show that solar total and spectral irradiance varies at different time scales. Whereas variations on time scales of minutes to hours are due to solar oscillations and granulation, variations on longer time scales are driven by the evolution of the solar surface magnetic field. Here the most recent advances in modelling of solar irradiance variations on time scales longer than a day are briefly reviewed.     

Sinks of iron and manganese in underground coal mine workings

The sources and sinks of manganese in underground coal mine workings are poorly understood compared to those of iron. The geochemical system in the secondary egress drift of Caphouse Colliery near Horbury, UK, is an ideal system for studying these processes. Five locations along the drift and four secondary inflows to the drift were sampled 24 times through the year commencing May 2005. During the sampling period, the pH in the main channel varied from 6.73 to 7.93 and increased along the flow path. The secondary inflows to the drift from the strata were of higher alkalinity (mean = 385 mg/L as CaCO₃) than the main flow (mean = 330 mg/L as CaCO₃); the affects of mixing between the less alkaline main channel and the more alkaline secondary inflows and of carbon dioxide exsolution are evident in the form of carbonate and hydroxide precipitates. SEM and XRD analysis of precipitates collected from the drift confirm the presence of calcium and manganese carbonates and ferric hydroxide. PHREEQC speciation and solubility modelling confirms supersaturation of the water in the main channel with respect to ferric oxy-hydroxides; iron, manganese, magnesium and calcium carbonates; and manganese oxides. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Shock-induced kelyphite formation in the core of a complex impact crater

We present a compositional and textural analysis of shock-induced microtextures in garnet porphyroblasts in migmatitic garnet–cordierite–biotite paragneisses from the centre of the Vredefort impact structure, South Africa. Detailed imaging and major element analysis of deformation features in, and adjacent to, the garnet porphyroblasts record a complex, heterogeneous distribution of shock effects at the microscale. As the most competent silicate mineral in the assemblage, with the highest Hugoniot Elastic Limit and a wide pressure–temperature stability field, the porphyroblastic garnet preserves a more diverse shock deformation response compared to minerals such as quartz and feldspar, which underwent more comprehensive shock metamorphism and subsequent annealing. The garnet porphyroblasts display pre-impact fractures that are overprinted by later intra-granular Hertzian and distinctive planar fractures associated with the impact event. Shock-induced strain localization occurred along internal slip planes and defects, including pre-existing fractures and inclusion boundaries in the garnet. Symplectitic (kelyphitic) coronas commonly enclose the garnet porphyroblasts, and inhabit intra-granular fractures. The kelyphite assemblage in fractures with open communication beyond garnet grain boundaries is characterized by orthopyroxene—cordierite—sapphirine. Conversely, the kelyphite assemblage in closed-off intra-granular fractures is highly variable, comprising spatially restricted combinations of a secondary garnet phase with a majoritic component, Al-rich orthopyroxene, sapphirine and cordierite. The impedance contrast between garnet porphyroblasts and their inclusions further facilitated the formation of shock-induced features (Al-rich orthopyroxene coronas). Together, the textural and mineralogical data suggest that these features provide a record of oscillatory shock perturbations initiated under confining pressure beneath the transient crater floor. This occurred as the shocked rock volume underwent post-shock expansion, forming the core of the central uplift, and was followed by variable textural re-equilibration. This study thus provides a microtextural and mineralogical perspective of the shock regime within confined crust immediately prior to and during central uplift formation.