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.     

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.     

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.     

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.     

U–Pb,Lu–Hf and Sm–Nd isotopic constraints on provenance and depositional timing of metasedimentary rocks in the western Gawler Craton: Implications for Proterozoic reconstruction models

The Gawler Craton forms the bulk of the South Australian Craton and occupies a pivotal location that links rock systems in Antarctica to those in northern Australia. The western Gawler Craton is a virtually unexposed region where the timing of basin development and metamorphism is largely unknown, making the region ambiguous in the context of models seeking to reconstruct the Australian Proterozoic.Detrital zircon data from metasedimentary rocks in the central Fowler Domain in the western Gawler Craton provide maximum depositional ages between 1760 and 1700 Ma, with rare older detrital components ranging in age up to 3130 Ma. In the bulk of samples, ?_Nd(1700 Ma) values range between ?4.3 and ?3.8. The combination of these data suggest on average, comparatively evolved but age-restricted source regions. Lu–Hf isotopic data from the ca 1700 Ma aged zircons provide a wide range of values (?_Hf(1700 Ma) +6 to ?6). Monazite U–Pb data from granulite-grade metasedimentary rocks yield metamorphic ages of 1690–1670 Ma. This range overlaps with and extends the timing of the widespread Kimban Orogeny in the Gawler Craton, and provides minimum depositional age constraints, indicating that basin development immediately preceded medium to high grade metamorphism.The timing of Paleoproterozoic basin development and metamorphism in the western Gawler Craton coincides with that in the northern and eastern Gawler Craton, and also in the adjacent Curnamona Province, suggesting protoliths to the rocks within the Fowler Domain may have originally formed part of a large ca 1760–1700 Ma basin system in the southern Australian Proterozoic. Provenance characteristics between these basins are remarkably similar and point to the Arunta Region in the North Australian Craton as a potential source. In this context there is little support for tectonic reconstruction models that: (1) suggest components of the Gawler Craton accreted together at different stages in the interval ca 1760–1680 Ma; and (2) that the North Australian Craton and the southern Australian Proterozoic were separate continental fragments between 1760 and 1700 Ma.     

Heterogeneous histories of Ni‐bearing pyrrhotite and pentlandite grains in the CI chondrites Orgueil and Alais

Compositional and structural analyses of CI chondrite iron–nickel sulfide grains reveal heterogeneity both across and within the Orgueil and Alais meteorites. Orgueil grains with the 4C monoclinic pyrrhotite structure have variable metal‐to‐sulfur ratios and nickel contents. These range from the nominal ratio of 0.875 for Fe₇S₈ with <1 atom% nickel to a high metal‐to‐sulfur ratio of 0.97 with 15 atom% nickel. These data reveal a previously unrecognized low‐temperature solid solution between Fe₇S₈ and Fe₅Ni₃S₈. We have also identified 6C monoclinic pyrrhotite among the Orgueil iron–nickel sulfides. The occurrence of pentlandite in Orgueil is confirmed for the first time crystallographically. In contrast, sulfide grains in Alais do not show the same spread in composition and structure; rather they represent the endmembers: low‐Ni 4C monoclinic pyrrhotite and pentlandite. We investigate possible formation/alteration scenarios: crystallization from a melt, solid‐state diffusion and/or exsolution, oxidation of pre‐existing sulfides, and precipitation from a fluid. Sulfide grains are sensitive to alteration conditions; these data suggest that the structures and compositions of the sulfide assemblages in Orgueil and Alais were established by late‐stage parent body aqueous alteration, followed in some cases by low‐temperature solid‐state processes. The samples record different alteration histories, with Orgueil experiencing lower equilibration temperatures (25 °C) than Alais (100–135 °C). We conclude that millimeter‐scale heterogeneity existed in alteration conditions (e.g., temperature, pH, oxygen fugacity, sulfur fugacity, duration of alteration) on the parent body. This variability is evidenced by the diversity among sulfide grains located within millimeters of one another.     

Changes in water extractable organic matter during incubation of forest floor material in the presence of quartz, goethite and gibbsite surfaces

The release of dissolved organic matter (DOM) from forest floor material constitutes a significant flux of C to the mineral soil in temperate forest ecosystems, with estimates on the order of 120-500 kg C ha⁻¹ year⁻¹. Interaction of DOM with minerals and metals results in sorptive fractionation and stabilization of OM within the soil profile. Iron and aluminum oxides, in particular, have a significant effect on the quantity and quality of DOM transported through forest soils due to their high surface area and the toxic effects of dissolved aluminum on microbial communities. We directly examined these interactions by incubating forest floor material, including native microbiota, for 154 days in the presence of (1) goethite (α-FeOOH), (2) gibbsite (γ-Al(OH)₃), and (3) quartz (α-SiO₂) sand (as a control). Changes in molecular and thermal properties of water extractable organic matter (WEOM, as a proxy for DOM) were evaluated. WEOM was harvested on days 5, 10, 20, 30, 60, 90, and 154, and examined by thermogravimetry/differential thermal analysis (TG/DTA) and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy. Results indicated significant differences in WEOM quality among treatments, though the way in which oxide surfaces influenced WEOM properties did not seem to change significantly with increasing incubation time. Dissolved organic C concentrations were significantly lower in WEOM from the oxide treatments in comparison to the control treatment. Incubation with goethite produced WEOM with mid-to-high-range thermal lability that was depleted in both protein and fatty acids relative to the control. The average enthalpy of WEOM from the goethite treatment was significantly higher than either the gibbsite or control treatment, suggesting that interaction with goethite surfaces increases the energy content of WEOM. Incubation with gibbsite produced WEOM rich in thermally recalcitrant and carboxyl-rich compounds in comparison to the control treatment. These data indicate that interaction of WEOM with oxide surfaces significantly influences the composition of WEOM and that oxides play an important role in determining the biogeochemistry of forest soil DOM.     

Climate-induced fluvial dynamics in tropical Africa around the last glacial maximum?

The Greenland and East and West Antarctic ice sheets are assessed as being the source of ice that produced an Eemian sea level 6 m higher than present sea level. The most probable source is total collapse of the West Antarctic Ice Sheet accompanied by partial collapse of the adjacent sector of the East Antarctic Ice Sheet in direct contact with the West Antarctic Ice Sheet. This conclusion is reached by applying a simple formula relating the “floating fraction” of ice along flowlines to ice height above the bed. Increasing the floating fraction lowered ice elevations enough to contribute up to 4.7 m to global sea level. Adding 3.3 m resulting from total collapse of the West Antarctic Ice Sheet accounts for the higher Eemian sea level. Partial gravitational collapse that produced the present ice drainage system of Amery Ice Shelf contributes 2.3 m to global sea level. These results cast doubt on the presumed stability of the East Antarctic Ice Sheet, but destabilizing mechanisms remain largely unknown. Possibilities include glacial surges and marine instabilities at the respective head and foot of ice streams.     

Archaeal lipids record paleosalinity in hypersaline systems

We present an ecologically based biomarker method for estimating past salinity, especially in hypersaline conditions. The relative amounts of acyclic diether and tetraether membrane lipids synthesized by Archaea correlate with salinity from 0–250 practical salinity units (psu) in modern settings. We examined the preservation of this lipid biomarker–salinity relationship in ancient sedimentary organic matter using samples from two sequences of marls and diatomites deposited just prior to the Messinian Salinity Crisis. Salinity estimates were consistent with expected absolute salinity, as well as the amplitude of variations leading up to the Messinian Salinity Crisis. This lipid biomarker approach to salinity reconstruction complements existing paleosalinity proxies because (i) Archaea survive and thrive over a broad salinity range, well beyond that of haptophyte algae and other plankton which form the microfossil record and (ii) it provides fine salinity resolution for the wide range broadly defined as hypersaline. With the proxy, there is the potential to provide novel insights into salinity variation within desiccating basins in climatically sensitive seas (e.g. Dead Sea, Permian Delaware Basin), evolution of brines, timing of onset of hypersaline conditions and evaporite deposition.