Sediment concentration changes in runoff pathways from a forest road network and the resultant spatial pattern of catchment connectivity

Hydrological connectivity is a term often used to describe the internal linkages between runoff and sediment generation in upper parts of catchments and the receiving waters. In this paper, we identify two types of connectivity: direct connectivity via new channels or gullies, and diffuse connectivity as surface runoff reaches the stream network via overland flow pathways. Using a forest road network as an example of a landscape element with a high runoff source strength, we demonstrate the spatial distribution of these two types of linkages in a 57 km² catchment in southeastern Australia. Field surveys and empirical modelling indicate that direct connectivity occurs primarily due to gully development at road culverts, where the average sediment transport distance is 89 m below the road outlet. The majority of road outlets were characterised by dispersive flow pathways where the maximum potential sediment transport distance is measured as the available hillslope length below the road outlet. This length has a mean value of 120 m for this catchment. Reductions in sediment concentration in runoff plumes from both pathways are modelled using an exponential decay function and data derived from large rainfall simulator experiments in the catchment. The concept of the volume to breakthrough is used to model the potential delivery of runoff from dispersive pathways. Of the surveyed road drains (n=218), only 11 are predicted to deliver runoff to a stream and the greatest contributor of runoff occurs at a stream crossing where a road segment discharges directly into the stream. The methodology described here can be used to assess the spatial distribution and likely impact of dispersive and gullied pathways on in-stream water quality.     

The dynamics of chironomid assemblages and vegetation during the Late Quaternary at Laguna Facil, Chonos Archipelago, southern Chile

We compare high-resolution pollen and chironomid records from the last 15,000 yr in Laguna Facil, southern Chile. Major vegetation and chironomid changes are recorded between ca 14,900 and 14,700 cal. yr BP. During the Lateglacial, changes in the chironomid stratigraphy lag behind changes in the pollen stratigraphy suggesting that the chironomids are responding to changes in the tree canopy or in soil chemistry brought about by vegetational development. At about 7200 cal. yr BP there is a change in the chironomid stratigraphy in advance of changes in the vegetation. This suggests that the response is to regional climatic change. The relatively close correlation of the chironomid and pollen stratigraphies with changes in charcoal concentrations also implicates the importance of fire and/or vulcanism in influencing the dynamics of forest and limnological systems. There is no clear evidence of cooling during the Younger Dryas chronozone in Laguna Facil.     

The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.     

Facies of slurry-flow deposits, Britannia Formation (Lower Cretaceous), North Sea: implications for flow evolution and deposit geometry

ABSTRACT Mud‐rich sandstone beds in the Lower Cretaceous Britannia Formation, UK North Sea, were deposited by sediment flows transitional between debris flows and turbidity currents, termed slurry flows. Much of the mud in these flows was transported as sand‐ and silt‐sized grains that were approximately hydraulically equivalent to suspended quartz and feldspar. In the eastern Britannia Field, individual slurry beds are continuous over long distances, and abundant core makes it possible to document facies changes across the field. Most beds display regular areal grain‐size changes. In this study, fining trends, especially in the size of the largest grains, are used to estimate palaeoflow and palaeoslope directions. In the middle part of the Britannia Formation, stratigraphic zones 40 and 45, slurry flows moved from south‐west and south towards the north‐east and north. Most zone 45 beds lens out before reaching the northern edge of the field, apparently by wedging out against the northern basin slope. Zone 40 and 45 beds show downflow facies transitions from low‐mud‐content, dish‐structured and wispy‐laminated sandstone to high‐mud‐content banded units. In zone 50, at the top of the formation, flows moved from north to south or north‐west to south‐east, and their deposits show transitions from proximal mud‐rich banded and mixed slurried beds to more distal lower‐mud‐content banded and wispy‐laminated units. The contrasting facies trends in zones 40 and 45 and zone 50 may reflect differing grain‐size relationships between quartz and feldspar grains and mud particles in the depositing flows. In zones 40 and 45, quartz grains average 0·30–0·32 mm in diameter, ≈ 0·10 mm coarser than in zone 50. The medium‐grained quartz in zones 40 and 45 flows may have been slightly coarser than the associated mud grains, resulting in the preferential deposition of quartz in proximal areas and downslope enrichment of the flows in mud. In zone 50 flows, mud was probably slightly coarser than the associated fine‐grained quartz, resulting in early mud sedimentation and enrichment of the distal flows in fine‐grained quartz and feldspar. Mud particles in all flows may have had an effective grain size of ≈ 0·25 mm. Both mud content and suspended‐load fallout rate played key roles in the sedimentation of Britannia slurry flows and structuring of the resulting deposits. During deposition of zones 40 and 45, the area of the eastern Britannia Field in block 16/26 may have been a locally enclosed subbasin within which the depositing slurry flows were locally ponded. Slurry beds in the eastern Britannia Field are ‘lumpy’ sheet‐like bodies that show facies changes but little additional complexity. There is no thin‐bedded facies that might represent waning flows analogous to low‐density turbidity currents. The dominance of laminar, cohesion‐dominated shear layers during sedimentation prevented most bed erosion, and the deposystem lacked channel, levee and overbank facies that commonly make up turbidity current‐dominated systems. Britannia slurry flows, although turbulent and capable of size‐fractionating even fine‐grained sediments, left sand bodies with geometries and facies more like those deposited by poorly differentiated laminar debris flows.     

Highly fractionated I-type granites in NE China (II): isotopic geochemistry and implications for crustal growth in the Phanerozoic

NE China is the easternmost part of the Central Asian Orogenic Belt (CAOB). The area is distinguished by widespread occurrence of Phanerozoic granitic rocks. In the companion paper (Part I), we established the Jurassic ages (184–137 Ma) for three granitic plutons: Xinhuatun, Lamashan and Yiershi. We also used geochemical data to argue that these rocks are highly fractionated I-type granites. In this paper, we present Sr–Nd–O isotope data of the three plutons and 32 additional samples to delineate the nature of their source, to determine the proportion of mantle to crustal components in the generation of the voluminous granitoids and to discuss crustal growth in the Phanerozoic.

Despite their difference in emplacement age, Sr–Nd isotopic analyses reveal that these Jurassic granites have common isotopic characteristics. They all have low initial ⁸⁷Sr/⁸⁶Sr ratios (0.7045±0.0015), positive _Nd(T) values (+1.3 to +2.8), and young Sm–Nd model ages (720–840 Ma). These characteristics are indicative of juvenile nature for these granites. Other Late Paleozoic to Mesozoic granites in this region also show the same features. Sr–Nd and oxygen isotopic data suggest that the magmatic evolution of the granites can be explained in terms of two-stage processes: (1) formation of parental magmas by melting of a relatively juvenile crust, which is probably a mixed lithology formed by pre-existing lower crust intruded or underplated by mantle-derived basaltic magma, and (2) extensive magmatic differentiation of the parental magmas in a slow cooling environment.

The widespread distribution of juvenile granitoids in NE China indicates a massive transfer of mantle material to the crust in a post-orogenic tectonic setting. Several recent studies have documented that juvenile granitoids of Paleozoic to Mesozoic ages are ubiquitous in the Central Asian Orogenic Belt, hence suggesting a significant growth of the continental crust in the Phanerozoic.