Groundwater N speciation and redox control of organic N mineralization by O2 reduction to H2O2

Excess N from agriculture induces eutrophication in major river systems and hypoxia in coastal waters throughout the world. Much of this N is from headwaters far up the watersheds. In turn, much of the N in these headwaters is from ground-water discharge. Consequently, the concentrations and forms of N in groundwater are important factors affecting major aquatic ecosystems; despite this, few data exist for several species of N in groundwater and controls on speciation are ill-defined. Herein, we report N speciation for a spring and well that were selected to reflect agricultural impacts, and a spring and well that show little to no agricultural-N impact. Samples were characterized for NO₃⁻, NO₂⁻, N₂O, NH₄⁺, urea, particulate organic N(), and dissolved organic N(). These analytes were monitored in the agricultural spring for up to two years along with other analytes that we reported upon previously. For all samples, when oxidized N was present, the dominant species was NO₃⁻ (88-98% of total fixed N pool) followed by (<4-12%) and only trace fractions of the other N analytes. In the non-agriculturally impacted well sample, which had no quantifiable NO₃⁻ or dissolved O₂, comprised the dominant fraction (68%) followed by NH₄⁺ (32%), with only a trace balance comprised of other N analytes. Water drawn from the well, spring and a wetland situated in the agricultural watershed also were analyzed for dissolved N₂ and found to have a fugacity in excess of that of the atmosphere. H₂O₂ was analyzed in the agricultural spring to evaluate the O₂/H₂O₂ redox potential and compare it to other calculated potentials. The potential of the O₂/H₂O₂ couple was close in value to the NO₃⁻/NO₂⁻ couple suggesting the important role of H₂O₂ as an O₂-reduction intermediate product and that O₂ and NO₃⁻ are reduced concomitantly. The O₂/H₂O₂ and NO₃⁻/NO₂⁻ couples also were close in value to a cluster of other inorganic N and Fe couples indicating near partial equilibrium among these species. Urea mineralization to NO₂⁻ was found to approach equilibrium with the reduction of O₂ to H₂O₂. By modeling as amide functional groups, as justified by recent analytical work, similar thermodynamic calculations support that mineralization to NO₂⁻ proceeds nearly to equilibrium with the reduction of O₂ to H₂O₂ as well. This near equilibration of redox couples for urea- and -oxidation with O₂-reduction places these two couples within the oxidized redox cluster that is shared among several other couples we have reported previously. In the monitored agricultural spring, [NO₃⁻] was lower in the summer than at other times, whereas [N₂O] was higher in the summer than at other times, perhaps reflecting a seasonal variation in the degree of denitrification reaction progress. No other N analytes were observed to vary seasonally in our study. In the well having no agricultural-N impact, C_org/N_org = 5.5, close to the typical value for natural aqueous systems of about 6.6. In the agricultural watershed C_org/N_org varied widely, from ∼1.2 to ?9.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Geochemical mapping using stream sediments in west-central Nigeria: Implications for environmental studies and mineral exploration in West Africa

This paper provides an overview of regional geochemical mapping using stream sediments from central and south-western Nigeria. A total of 1569 stream sediment samples were collected and 54 major and trace elements determined by ICP-MS and Au, Pd and Pt by fire assay. Multivariate statistical techniques (e.g., correlation analysis and principal factor analysis) were used to explore the data, following appropriate data transformation, to understand the data structure, investigate underlying processes controlling spatial geochemical variability and identify element associations. Major geochemical variations are controlled by source geology and provenance, as well as chemical weathering and winnowing processes, more subtle variations are a result of land use and contamination from anthropogenic activity.     

Opacity effects and shock-in-jet modelling of low-level activity in Cygnus X-3

We present simultaneous dual-frequency radio observations of Cygnus X-3 during a phase of low-level activity. We constrain the minimum variability time-scale to be 20 min at 43 GHz and 30 min at 15 GHz, implying source sizes of 2–4 au. We detect polarized emission at a level of a few per cent at 43 GHz which varies with the total intensity. The delay of ∼10 min between the peaks of the flares at the two frequencies is seen to decrease with time, and we find that synchrotron self-absorption and free–free absorption by entrained thermal material play a larger role in determining the opacity than absorption in the stellar wind of the companion. A shock-in-jet model gives a good fit to the light curves at all frequencies, demonstrating that this mechanism, which has previously been used to explain the brighter, longer lived giant outbursts in this source, is also applicable to these low-level flaring events. Assembling the data from outbursts spanning over two orders of magnitude in flux density shows evidence for a strong correlation between the peak brightness of an event, and the time-scale and frequency at which this is attained. Brighter flares evolve on longer time-scales and peak at lower frequencies. Analysis of the fitted model parameters suggests that brighter outbursts are due to shocks forming further downstream in the jet, with an increased electron normalization and magnetic field strength both playing a role in setting the strength of the outburst.     

The complex, variable near-infrared extinction towards the Nuclear Bulge

Using deep J -, H - and K _S-band observations, we have studied the near-infrared extinction of the Nuclear Bulge, and find significant, complex variations on small physical scales. We have applied a new variable near-infrared colour excess (V-NICE) method to measure the extinction; this method allows for variation in both the extinction law parameter α and the degree of absolute extinction on very small physical scales. We see significant variation in both these parameters on scales of 5 arcsec. In our observed fields, representing a random sample of sight lines to the Nuclear Bulge, we measure α to be  2.64 ± 0.52  , compared to the canonical 'universal' value of 2. Our measured levels of     are similar to previously measured results     ; however, the steeper extinction law results in higher values for   A_J (4.5 ≤ A_J ≤ 10  ) and   A_H (1.5 ≤ A_H ≤ 6.5  ). Only when the extinction law is allowed to vary on the smallest scales can we recover self-consistent measures of the absolute extinction at each wavelength, allowing accurate reddening corrections for field star photometry in the Nuclear Bulge. The steeper extinction law slope also suggests that previous conversions of near-infrared extinction to   A_V   may need to be reconsidered. Finally, we find that the measured values of extinction are significantly dependent on the filter transmission functions of the instrument used to obtain the data. This effect must be taken into account when combining or comparing data from different instruments.     

The inverse Compton X-ray-emitting lobes of the high-redshift giant radio galaxy 6C 0905+39

We present new XMM–Newton data of the high-redshift  ( z = 1.883)  , Mpc-sized giant radio galaxy 6C 0905+39. The larger collecting area and longer observation time for our new data means that we can better characterize the extended X-ray emission, in particular its spectrum, which arises from cosmic microwave background photons scattered into the X-ray band by the energetic electrons in the spent synchrotron plasma of the (largely) radio-quiet lobes of 6C 0905+39. We calculate the energy that its jet-ejected plasma has dumped into its surroundings in the last  3 × 10⁷   yr and discuss the impact that similar, or even more extreme, examples of spent, radio-quiet lobes would have on their surroundings. Interestingly, there is an indication that the emission from the hotspots is softer than the rest of the extended emission and the core, implying it is due to synchrotron emission. We confirm our previous detection of the low-energy turnover in the eastern hotspot of 6C 0905+39.     

Using species distribution modelling to predict future distributions of phytoplankton: Case study using species important for the biological pump

Some phytoplankton species have been predicted to contribute more to the biological pump than others. In this study, we examine the potential of species distribution modelling (SDM) for describing current and predicting future global distributions of two phytoplankton species: the diatom Chaetoceros diadema and the coccolithophore Emiliania huxleyi. Species distribution models (SDMs) were constructed using species data from the Ocean Biogeographic Information System and environmental layers from the Coupled Model Intercomparison Project Phase 5. The resulting distributions were evaluated by comparing predicted distributions with those found via a literature survey. The developed SDMs were then applied to predict future changes in the distributions of these species using environmental conditions based on the Intergovernmental Panel on Climate Change's Representative Concentration Pathways scenario 8.5 climate scenario, predicted for the year 2100. The model predicts that the total ocean area covered by C. diadema and E. huxleyi will decline under the examined climate scenario by 8% and 16%, respectively. Furthermore, the future ranges above depths >1,000 m are predicted to decline by 28% for C. diadema. As the biological pump is most active in deep ocean waters, this projected decrease in range in the deeper regions of the ocean may have implications for carbon sequestration, particularly for the diatom species. We conclude that SDM appears to be a robust tool for examining phytoplankton distributions. If the predicted changes in ranges of these two species under future ocean conditions are realised, this may result in a reduced contribution of these two phytoplankton species to carbon sequestration via the biological pump.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Rates of weathering rind formation on Costa Rican basalt

Weathering rind thicknesses were measured on ∼ 200 basaltic clasts collected from three regionally extensive alluvial fill terraces (Qt 1, Qt 2, and Qt 3) preserved along the Pacific coast of Costa Rica. Mass balance calculations suggest that conversion of unweathered basaltic core minerals (plagioclase and augite) to authigenic minerals in the porous rind (kaolinite, allophane, gibbsite, Fe oxyhydroxides) is iso-volumetric and Ti and Zr are relatively immobile. The hierarchy of cation mobility (Ca ≈ Na > K ≈ Mg > Si > Al > Fe ≈ P) is similar to other tropical weathering profiles and is indicative of differential rates of mineral weathering (anorthite > albite ≈ hypersthene > orthoclase ? apatite). Alteration profiles across the cm-thick rinds document dissolution of plagioclase and augite and the growth of kaolinite, with subsequent dissolution of kaolinite and precipitation of gibbsite as weathering rinds age. The rate of weathering rind advance is evaluated using a diffusion-limited model which predicts a parabolic rate law for weathering rind thickness, r_r, as a function of time, t(r_r =), and an interface-limited model which predicts a linear rate law for weathering rind thickness as a function of time (r_r = k_appt). In these rate laws, κ is a diffusion parameter and k_app is an apparent rate constant. The rate of advance is best fit by the interface model.Terrace exposures are confined to the lower reaches of streams draining the Pacific slope near the coast where the stream gradient is less than ∼3 m/km, and terrace deposition is influenced by eustatic sea level fluctuations. Geomorphological evidence is consistent with terrace deposition coincident with sea level maxima when the stream gradient would be lowest. Assigning the most weathered regionally extensive terrace Qt 1 (mean rind thickness 6.9 ± 0. 6cm) to oxygen isotope stage (OIS) 7 (ca. 240 ka), and assuming that at time = 0 rind thickness = 0, it is inferred that terrace Qt 2 (r_r = 2.9 ± 0.1 cm) is coincident with stage 5e (ca. 125 ka) and that Qt 3 (r_r = 0.9 ± 0.1 cm) is consistent with OIS 3 (ca. 37 ka). These assignments yield a value of k_app of 8.6 × 10⁻¹³ cm s⁻¹ (R² = 0.99). Only this value satisfies both the existing age controls and yields ages coincident with sea level maxima. Using this value, elemental weathering release fluxes across a weathering rind from Qt 2 range from 6.0 × 10⁻⁹ mol Si m⁻² s⁻¹ to 2.5 × 10⁻¹¹ mol K m⁻² s⁻¹. The rate of rind advance for the Costa Rican terraces is 2.8 × 10⁻⁷ m yr⁻¹. Basalt rind formation rates in lower temperature settings described in the literature are also consistent with interface-controlled weathering with an apparent activation energy of about 50 kJ mol⁻¹. Rates of rind formation in Costa Rica are an order of magnitude slower than reported for global averages of soil formation rates.