Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

A diverse Pleistocene marsupial trackway assemblage from the Victorian Volcanic Plains,Australia

A diverse assemblage of late Pleistocene marsupial trackways on a lake bed in south-western Victoria provides the first information relating to the gaits and morphology of several megafaunal species, and represents the most speciose and best preserved megafaunal footprint site in Australia. The 60–110 ka volcaniclastic lacustrine sedimentary rocks preserve trackways of the diprotodontid Diprotodon optatum, a macropodid (probably Protemnodon sp.) and a large vombatid (perhaps Ramsayia magna or ‘Phascolomys’ medius) and possible prints of the marsupial lion, Thylacoleo carnifex. The footprints were imprinted within a short time period, demonstrating the association of the taxa present, rather than the time-averaged accumulations usually observed in skeletal fossil deposits. Individual manus and pes prints are distinguishable in some trackways, and in many cases some digital pad morphology is also present. Several parameters traditionally used to differentiate ichnotaxa, including trackway gauge and the degree of print in-turning relative to the midline, are shown to be subject to significant intraspecific variation in marsupials. Sexual dimorphism in the trackway proportions of Diprotodon, and its potential for occurrence in all large bodied, quadrupedal marsupials, is identified here for the first time.     

Implications of measurement metrics on soil freezing curves: A simulation of freeze–thaw hysteresis

Soil freeze–thaw events have important implications for water resources, flood risk, land productivity, and climate change. A property of these phenomena is the relationship between unfrozen water content and sub-freezing temperature, known as the soil freezing characteristic curve (SFC). It is documented that this relationship exhibits hysteretic behaviour when frozen soil thaws, leading to the definition of the soil thawing characteristic curve (STC). Although explanations have been given for SFC/STC hysteresis, the effect that ‘scale’ – particularly ‘measurement scale’ – may have on these curves has received little attention. The most commonly used measurement scale metric is the ‘support’, which is the spatial (or temporal) unit within which the measured variable is integrated or soil volume sampled. We show (a) measurement support can influence the range and shape of the SFC and (b) hysteresis can be attributed, in part, to the support and location of the measurements comprising the SFC/STC. We simulated lab measured temperature, volumetric water content (VWC), and permittivity from soil samples undergoing freeze–thaw transitions using Hydrus-1D and a modified Dobson permittivity model. To assess the effect of measurement support and location on SFC/STC, we masked the simulated temperature and VWC/permittivity extent to match the instrument's support and location. By creating a detailed simulation of the intra- and inter-support variability associated with the penetration of a freezing front, we demonstrate how measurement support and location can influence the temperature range over which water freezing events are captured. We show it is possible to simulate hysteresis in homogenous media with purely geometric considerations, suggesting that SFC/STC hysteresis may be more of an apparent phenomenon than mechanistically real. Lastly, we develop an understanding of how the location and support of soil temperature and VWC/permittivity measurements influence the temperature range over which water freezing events are captured.     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

Geostatistical features of streambed vertical hydraulic conductivities in Frenchman Creek Watershed in Western Nebraska

This study evaluated the spatial variability of streambed vertical hydraulic conductivity (K_v) in different stream morphologies in the Frenchman Creek Watershed, Western Nebraska, using different variogram models. Streambed K_v values were determined in situ using permeameter tests at 10 sites in Frenchman, Stinking Water and Spring Creeks during the dry season at baseflow conditions. Measurements were taken both in straight and meandering stream channels during a 5 day period at similar flow conditions. Each test site comprised of at least three transects and each transect comprised of at least three K_v measurements. Linear, Gaussian, exponential and spherical variogram models were used with Kriging gridding method for the 10 sites. As a goodness-of-fit statistic for the variogram models, cross-validation results showed differences in the median absolute deviation and the standard deviation of the cross-validation residuals. Results show that using the geometric means of the 10 sites for gridding performs better than using either all the K_v values from the 93 permeameter tests or 10 K_v values from the middle transects and centre permeameters. Incorporating both the spatial variability and the uncertainty involved in the measurement at a reach segment can yield more accurate grid results that can be useful in calibrating K_v at watershed or sub-watershed scales in distributed hydrological models.     

Hydropedology of a mildly‐arid loess covered area,southern Israel

Extensive loess covered areas characterize the mildly arid areas of western Israel, where average annual rainfall is 280 mm. Hydrological data point to a peculiar hydrological behavior of the ephemeral streams. The frequency of sporadic flash floods is very high. However, even in extreme rain events peak discharges are extremely low. Hydrographs are usually characterized by very steep rising and falling limbs, representative of saturated areas, extending over a limited part of the watershed. Following this observation we advanced the hypothesis that storm channel runoff originated in the channel itself, with negligible contribution from the adjoining hillslopes. The study was based on two complementary approaches. The hydrological approach was based on the detailed analysis of rainfall–runoff relationships in a small watershed (11 km²) and on the analysis of the hydrological characteristics of the drainage network. The second approach was based on the toposequence concept. Several boreholes were dug along a hillslope 400 m long. Chemical data obtained show no significant difference in the downslope direction. Similar results were also obtained for the particle size distribution and soil moisture content. Data obtained perfectly fit the concept of ‘Partial Area Contribution’ as it presents an extreme case of hydrological discontinuity at the hillslope–channel interface. The lack of pedological trends in the downslope direction is an additional indication of the limited connectivity between the hillslopes and the adjoining channel. The limited connectivity is attributed to the prevalence of low rain intensities in the study area. The present study is also relevant to our understanding of pedological processes in dryland areas. The high frequency of intermittent low intensity rainstorms limits runoff generation and flow distances, and casts doubt on the general application of the toposequence approach. Copyright © 2016 John Wiley & Sons, Ltd.     

Integrated Deep Soil N and Groundwater Isotope Investigation of N Sources Captured by Municipal Wells

Identification of major nitrate sources that adversely impact groundwater quality in municipal well capture zones in areas of emerging nitrate contamination is essential to minimize leaching and prevent exceedance of the nitrate drinking water standard. Vertical profiles of nitrate leachate in deep soils provide an estimate of the amount of nitrate in transit beneath irrigated, row-cropped fields; depths of peak leachate; and the approximate rate of downward movement. Profiles of pore-water soil-nitrate concentrations in thick 60-feet (~18 m), fine-textured soils near Hastings, Nebraska clearly indicate that considerably more nitrate leached beneath furrow-irrigated than center-pivot irrigated fields. Peak leaching appeared to correlate with recorded periods of poor weather conditions during some growing seasons and may best be controlled by “spoon feeding” fertilizer to the crop through the sprinkler irrigation system at times of nutrient need. The presence of trace levels of atrazine and deethylatrazine to 60 feet (18 m) in core samples indicates that larger, more complex anthropogenic molecules also leach through the fine-textured soils. The light δ¹⁵N_NO3 values in the surficial groundwater beneath fertilized and irrigated cropland indicate that ammonium fertilizer is a major N source and suggest that the natural soil-N contribution is negligible. δ¹⁵N_NO3 values were most enriched in irrigation wells located within municipal well capture zones downgradient of a large feedlot. Dual isotope method (DIM) δ¹⁵N_NO3 and δ¹⁸O_NO3 values suggest that the Hastings’ municipal wells farther downgradient are contaminated with a mixture of nitrate from manure and commercial ammonium-based fertilizer. DIM values indicate an absence of denitrification, which has implications for long-term management of the water resources.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

SPASE 2.0: a standard data model for space physics

SPASE—for Space Physics Archive Search and Extract—is a group with a charter to promote collaboration and sharing of data for the Space Plasma Physics community. A major activity is the definition of the SPASE Data Model which defines the metadata necessary to describe resources in the broader heliophysics data environment. The SPASE Data Model is primarily a controlled vocabulary with hierarchical relationships and with the ability to form associations between described resources. It is the result of many years of effort by an international collaboration (see http://www.spase-group.org) to unify and improve on existing Space and Solar Physics data models. The genesis of the SPASE group can be traced to 1998 when a small group of individuals saw a need for a data model. Today SPASE has a large international participation from many of the major space research organizations. The design of the data model is based on a set of principles derived from evaluation of the existing heliophysics data environment. The development guidelines for the data model are consistent with ISO-2788 (expanded in ANSI/NISO Z39.19) and the administration for the data model is comparable to that described in the ISO standards ISO-11179 and ISO-20943. Since the release of version 1.0 of the data model in 2005, the model has undergone a series of evolutions. SPASE released version 2.0 of its data model in April 2009. This version presents a significant change from the previous release. It includes the capability to describe a wider range of data products and to describe expert annotations which can be associated with a resource. Additional improvements include an enhanced capability to describe resource associations and a more unified approach to describing data products. Version 2.0 of the SPASE Data Model provides a solid foundation for continued integration of worldwide research activities and the open sharing of data.