Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Sensitivity of GRACE-derived estimates of groundwater-level changes in southern Ontario,Canada

Amidst changing climates, understanding the world’s water resources is of increasing importance. In Ontario, Canada, low water conditions are currently assessed using only precipitation and watershed-based stream gauges by the Conservation Authorities in Ontario and the Ministry of Natural Resources and Forestry. Regional groundwater-storage changes in Ontario are not currently measured using satellite data by research institutes. In this study, contributions from the Gravity Recovery and Climate Experiment (GRACE) data are compared to a hydrogeological database covering southern Ontario from 2003 to 2013, to determine the suitability of GRACE total water storage estimates for monitoring groundwater storage in this location. Terrestrial water storage data from GRACE were used to determine monthly groundwater storage (GWS) anomaly values. GWS values were also determined by multiplying groundwater-level elevations (from the Provincial Groundwater Monitoring Network wells) by specific yield. Comparisons of GRACE-derived GWS to well-based GWS data determined that GRACE is sufficiently sensitive to obtain a meaningful signal in southern Ontario. Results show that GWS values produced by GRACE are useful for identifying regional changes in groundwater storage in areas with limited available hydrogeological characterization data. Results also indicate that GRACE may have an ability to forecast changes in groundwater storage, which will become useful when monitoring climate shifts in the near future.     

Peat porewater chloride concentration profiles in the Everglades during wet/dry cycles from January 1996 to June 1998: field measurements and theoretical analysis

Water quality is a key aspect of the Everglades Restoration Project, the largest water reclamation and ecosystem management project proposed in the United States. Movement of nutrients and contaminants to and from Everglades peat porewater could have important consequences for Everglades water quality and ecosystem restoration activities. In a study of Everglades porewater, we observed complex, seasonally variable peat porewater chloride concentration profiles at several locations. Analyses and interpretation of these changing peat porewater chloride concentration profiles identifies processes controlling conservative solute movement at the peat–surface water interface, that is, solutes whose transport is minimally affected by chemical and biological reactions. We examine, with an advection–diffusion model, how alternating wet and dry climatic conditions in the Florida Everglades mediate movement of chloride between peat porewater and marsh surface water. Changing surface water–chloride concentrations alter gradients at the interface between peat and overlying water and hence alter chloride flux across that interface. Surface water chloride concentrations at two frequently monitored sites vary with marsh water depth, and a transfer function was developed to describe daily marsh surface water chloride concentration as a function of marsh water depth. Model results demonstrate that porewater chloride concentrations are driven by changing surface water chloride concentrations, and a sensitivity analysis suggests that inclusion of advective transport in the model improves the agreement between the calculated and the observed chloride concentration profiles. Published in 2007 by John Wiley & Sons, Ltd.     

Sub-micron scale distributions of trace elements in zircon

Sub-micron scale zoning of Ti concentrations and correlations between concentrations of Ti and other trace elements (P, Ce, and Y) and cathodoluminescent (CL) banding is observed in natural zircons. Ion images were made using the Caltech Microanalysis Center’s CAMECA NanoSIMS 50L with an O⁻ primary beam focused to ~300 nm on the sample surface. The high spatial resolution of this technique allows for interrogation of chemical variations at or below the scale of CL banding in natural zircons. Images produced in this manner display two types of correlations among Ti, P, Ce, and Y (which appears to be a proxy for CL intensity): strong (correlation coefficients >0.8) and subtle (correlation coefficients ~0.15–0.4). Strongly correlated images, which display Ti variations of ca. a factor of 3 between adjacent CL bands and overall elevated trace element concentrations in CL-dark bands, were found within an oscillatory-zoned, trace element enriched sector of a CL sector-zoned zircon. Three possible causes for such correlations include: temperature-dependent equilibrium partitioning, trace element partitioning limited by diffusion in the host melt and surface-controlled, non-equilibrium growth. Comparison of our data with the expected results of these processes suggests that: (1) Ti partitioning in zircon is dependent upon non-equilibrium effects in addition to temperature and/or (2) the incorporation of elements that co-vary with Ti in zircon (e.g., Y, P and Ce) is also temperature-dependent. Sub-micron scale, high-Ti regions are also found within Proterozoic Adirondack and >4 Ga Jack Hills zircons as well as trace element enrichments (including Ti) along cracks within Jack Hills zircons.     

Morphology of step-pools in a wilderness headwater stream: The importance of standardizing geomorphic measurements

The morphology of step-pools and cascades reflect the geological and climatic factors affecting channels in mountain watersheds. This study uses longitudinal and cross-section surveys to describe a headwater stream in the Boston Mountains of the Ozarks Plateau region in Arkansas and develop morphological relationships for comparisons with other regions. In the Bowers Hollow Creek watershed (3.5 km²), located within the boundaries of the Upper Buffalo Wilderness Area, step height and wavelength relationships are generally similar to those reported from other regions. Step-pool reaches were widely distributed in a discontinuous manner throughout the watershed. Average values of the sampled reaches are: reach slopes, 0.105 m/m; width, 6.10 m; crest particle sizes, 440 mm; step heights, 0.87 m; and step wavelengths, 6.62 m. The mean step steepness for the watershed was 0.13, whereas the mean length of a reach step to height ratio was 9:1. A comparison of morphological definitions found that the values of step height and steepness can vary by > 30% according to how step parameters are defined. Step height is particularly sensitive; thus, comparison of step height-based relationships from published data requires great care.     

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.     

WIYN Open Cluster Study – XVI. Optical/infrared photometry and comparisons with theoretical isochrones

We present combined optical/near-infrared photometry ( BVIK ) for six open clusters – M35, M37, NGC 1817, NGC 2477, NGC 2420 and M67. The open clusters span an age range from 150 Myr to 4 Gyr and have metal abundances from  [Fe/H]=−0.27  to +0.09 dex. We have utilized these data to test the robustness of theoretical main sequences constructed by several groups as denoted by the following designations – Padova, Baraffe, Y², Geneva and Siess. The comparisons of the models with the observations have been performed in the  [ M_V , ( B − V )₀], [ M_V , ( V − I )₀]  and  [ M_V , ( V − K )₀]  colour–magnitude diagrams as well as the distance-independent  [( V − K )₀, ( B − V )₀]  and  [( V − K )₀, ( V − I )₀]  two-colour diagrams. We conclude that none of the theoretical models reproduces the observational data in a consistent manner over the magnitude and colour range of the unevolved main sequence. In particular, there are significant zero-point and shape differences between the models and the observations. We speculate that the crux of the problem lies in the precise mismatch between theoretical and observational colour–temperature relations. These results underscore the importance of pursuing the study of stellar structure and stellar modelling with even greater intensity.