Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Statistical biases and errors inherent in photoclinometric surface slope estimation with natural light

Photoclinometry is the most common method used to obtain high-resolution topographic maps of planetary terrain. We derive the likelihood function of photoclinometric surface slope from (1) the probability distribution of the measured photon count of natural sunlight through a Charge-Coupled Device (CCD) including uncertainty due to camera shot noise, camera read noise, small-scale albedo fluctuation and atmospheric haze, and (2) a photometric model relating photocount to surface orientation. We then use classical estimation theory to determine the theoretically exact biases and errors inherent in photoclinometric surface slope and show when they may be approximated by asymptotic expressions for sufficiently high sample size. We show how small-scale albedo variability often dominates biases and errors, which may become an order of magnitude larger than surface slopes when surface reflectance has a weak dependence on surface tilt. We provide bounds on the minimum possible error of any unbiased photoclinometric surface slope estimate, and compute the sample sizes necessary to constrain errors within desired design thresholds.     

Late Quaternary paleoclimate of western Alaska inferred from fossil chironomids and its relation to vegetation histories

Fossil Chironomidae assemblages (with a few Chaoboridae and Ceratopogonidae) from Zagoskin and Burial Lakes in western Alaska provide quantitative reconstructions of mean July air temperatures for periods of the late-middle Wisconsin (～39,000–34,000 cal yr B.P.) to the present. Inferred temperatures are compared with previously analyzed pollen data from each site summarized here by indirect ordination. Paleotemperature trends reveal substantial differences in the timing of climatic warming following the late Wisconsin at each site, although chronological uncertainty exists. Zagoskin Lake shows early warming beginning at about 21,000 cal yr B.P., whereas warming at Burial Lake begins ～4000 years later. Summer climates during the last glacial maximum (LGM) were on average ～3.5 °C below the modern temperatures at each site. Major shifts in vegetation occurred from ～19,000 to 10,000 cal yr B.P. at Zagoskin Lake and from ～17,000 to 10,000 cal yr B.P. at Burial Lake. Vegetation shifts followed climatic warming, when temperatures neared modern values. Both sites provide evidence of an early postglacial thermal maximum at ～12,300 cal yr B.P. These chironomid records, combined with other insect-based climatic reconstructions from Beringia, indicate that during the LGM: (1) greater continentality likely influenced regions adjacent to the Bering Land Bridge and (2) summer climates were, at times, not dominated by severe cold.     

Fractional Crystallization and Liquid Immiscibility Processes in the Alkaline-Carbonatite Complex of Juqui (So Paulo, Brazil)

The Juqui circular intrusion, which is Cretaceous in age (130–135Ma), crops out in the Precambrian gneissic basement in Brazilover an area of 14 km2. It consists of olivine clinopyroxen-itecumulates (with minor olivine gabbros) in the northeastern sector(74 vol.%), whereas ijolites-melteigites-urtites (4%) and nephelinesyenites with minor essexites and syenodiorites (21%) outlinesubannular concentric patterns with an Mg-carbonatite core (1%), in the southwestern part of the complex. Petrographical, bulk rock, and mineral compositional trendsindicate that the origin of the complex can be largely accountedfor by shallow-level fractional crystallization of a carbonatedbasanitic parental magma. Such a magma was generated deep inthe subcontinental lithosphere by low-degree partial meltingof a garnet-phlogopite peridotite source. Mass-balance calculations in agreement with field volume estimatespermit definition of several fractionation stages of the magmaticevolution under nearly closed-system conditions, with inwarddevelopment of zonally arranged side-wall cumulates. These stagesinvolved: (1) fractionation from basanite to essexite magma(liquid fraction F = 33–5%) by crystallization of olivineclinopyroxenite plus minor olivine alkali gabbro cumulates;(2) derivation of the least differentiated mafic nepheline syenite(F = 5–5 %) from essexitic magma by subtraction of a syenodioriteassemblage; (3) exsolution of a carbonatite liquid (5%) froma CO₂-enriched mafic nepheline syenite magma, which also underwentcontinuous fractionation giving rise to ijolite-melteigite-urtitecumulates. The proportion of cumulus clinopyroxene and biotiteand intercumulus nepheline and alkali feldspar in these lastrocks, as well as the absence of alkalis in carbonatite, maybe attributed, at least in part, to loss of alkali-rich hydrousfluids released during and after the unmixing formation of thetwo conjugate liquids. The KD values determined for Mg-carbonatite/nepheline syeniteare lower (1–4–2–9) for light rare earth elements(LREE) than for REE from Eu to Yb (4–6–7–8),in contrast to recent experimental results (Hamilton et al.,1989). A possible explanation is that Juquia Mg-carbonatiterepresents an alreadydifferentiated magma, which underwent extensivefractionation of LREE-enriched calcite. In this way, the highvariability of K₀ REE patterns observed in several alkaline-carbonatitecomplexes can also be accounted for. The remarkably constant initial ⁸⁷Sr/⁸⁶Sr ratios (mostly between0–7052 and 0–7057) support the interpretation ofthe intrusion as having been generated by fractrional crystallizationand liquid immiscibility from a common parental magma. Iligherisotopic ratios (0–7060–0–7078), found mainlyin dykes and in the border facies of the intrusion, may be dueto contamination by the gecissic basement.     

Assessing landslide movements in volcanic islands using near-shore marine geophysical data: south Pico island,Azores

Marine geophysical data from around the submarine flanks of volcanic islands can potentially help to resolve whether large-scale instability of an edifice has been geologically recently active. We use geophysical data to investigate part of the coast of Pico Island of the Azores where, above sea-level, a major slump of Topo volcano has been interpreted previously from arcuate escarpments and a rugged irregular topography seaward of them. Multibeam echo-sounder data collected offshore of this feature show remarkably little evidence for slump fault movements in the island's submarine slope. Mid-slope benches, like those associated with the Hilina Slump of Kilauea, are absent. The high-resolution data extends onto the island's shelf, allowing us to evaluate evidence for continuing activity there. In particular, as the shelf's rock platform will have been last modified by surf erosion during the postglacial period of sea-level transgression, it provides a reference surface of intermediate age (7–19 ka) that can potentially reveal whether any movements occurred in pre-historic times. Where the arcuate escarpments are continued offshore, the modern seabed shows no bathymetric evidence for active faults where the shelf rock platform crops out in the multibeam data. Elsewhere, mobile shelf sediments could be disguising evidence for active faulting so we examined boomer profiles able to image the rock platform beneath them. The data reveal a platform that is steep (6.6°) compared with the dips of platforms that we have studied previously around the coast of adjacent Faial Island and steeper than the platform outside the proposed slump. This suggests that it was created by coastal erosion over a shorter period and hence is consistent with a younger age of the coastline. As with the multibeam data, where escarpments are continued offshore onto the shelf, the rock surface imaged with these boomer data also shows no clear evidence of major slump-related fault displacements. This study therefore illustrates how high-resolution boomer seismic and multibeam data could usefully contribute to hazard assessment of volcanic islands, by helping to evaluate areas with no historical movements. Explanations to reconcile the onshore and offshore data here are also put forward.     

Tellurides from Sunrise Dam gold deposit, Yilgarn Craton, Western Australia: a new occurrence of nagyágite

Summary The Cu–Fe–Au–Mo (W) deposits in southeastern Hubei are an important component of the Middle–Lower Yangtze River metallogenic belt. Molybdenite from the Fengshandong Cu- (Mo), Ruanjiawan W–Cu- (Mo), Qianjiawan Cu–Au, Tongshankou Cu–Mo and Tonglüshan Cu- (Fe) deposits yielded Re–Os ages of 144.0 ± 2.1 Ma, 143.6 ± 1.7 Ma, 137.7 ± 1.7 Ma, 142.3 ± 1.8–143.7 ± 1.8 Ma and 137.8 ± 1.7–138.1 ± 1.8 Ma, respectively. Phlogopite from the Tieshan Fe- (Cu) deposit yielded an Ar–Ar age of 140.9 ± 1.2 Ma. These data and other published isotopic ages (Re–Os molybdenite and Ar–Ar mica ages) for the Cu–Fe–Au–Mo (W) deposits in the Middle–Lower Yangtze River metallogenic belt show that Cu–Fe–Au–Mo (W) mineralisation in the Tongling, Anqing, Jiurui and Edong ore districts developed in a narrow time span between 135.5 and 144.9 Ma, reflecting an important regional metallogenic event. An integrated study of available petrological and geochronological data, together with relationships to magmatism and the regional geodynamic framework, indicate that the Cu–Fe–Au–Mo (W) mineralisation in the Middle–Lower Yangtze River belt occurred during a regime of lithospheric extension. This extension is probably related to Late Mesozoic processes of lower crustal delamination and lithospheric thinning in East China.     

Particulate dispersion from sources within a forest

Particulate dispersion from sources within a 10- to 13-m tall pine forest was studied experimentally at Brookhaven National Laboratory using stained ragweed pollen and other tracers ranging from 14 to 58 m in size. Forty-seven continuous point source releases lasting from 22 to 55 min were made at heights from 1.75 to 14.0 m from locations having a long fetch through the forest. In most experiments, differently colored ragweed pollen were emitted simultaneously from three locations. In other tests, several particle types were released from a single point. The sampling network consisted of 119 rotoslide samplers at heights from 0.5 to 21.0 m at 57 positions within and at the edge of the forest. Deposition to the ground was sampled by greased microscope slides at each position. Meteorological measurements were taken in and near the forest.Data were classified by particle characteristics, source height and meteorological parameters. Concentration patterns were illustrated on scale diagrams of the sampling grid. Changes in centerline and crosswind integrated concentrations, plume width and height, mass flux, deposition and deposition velocity were studied as a function of distance, particle size and wind speed. Results were compared to those obtained from similar releases over open terrain.In the forest, vertical predominates over lateral dispersion and considerable interchange occurs through the canopy. Flow is channelled somewhat by vegetation density differences but is generally in the direction of the mean wind above the forest. No systematic turning of the wind with height was observed. Most particles are lost to the foliage rather than to the ground and large particles are lost more rapidly than smaller ones. Rate of change in mass flux is similar to that over open terrain and is greater with light than with stronger wind speeds.This research was carried out under the auspices of the New York State Museum and Science Service and the U.S. Atomic Energy Commission (now Energy Research and Development Administration) and was partially supported by Research Grant No. R-800677 from the Division of Meteorology, U.S. Environmental Protection Agency.