An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H2O from 300 to 800°C

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Natural recovery from accelerated forest ditch and stream bank erosion five years after harvesting of plantation forest on Plynlimon,mid‐Wales

Erosion rates surveyed using 230 erosion pins on 24 occasions over eight years (1994–2001) on forested stream banks, tributaries and forest ditches in the 0·89 km² Nant Tanllwyth catchment, part of the Hafren Forest on Plynlimon, mid‐Wales, showed statistically significant increases of up to 40 mm a^?1 in mean erosion rates during the two‐year period in which environmentally sensitive plot‐scale timber harvesting operations took place (1996–97). In the four years following timber harvesting mean erosion rates at all sites recovered to levels that were lower than before the harvesting operations began. This is attributed to increased light levels, following canopy removal, allowing vegetation to colonize exposed banks. There was a statistically significant relationship (p < 0·05) between mean erosion rate in 2000–01 (four years after harvesting) and percentage vegetation cover at erosion monitoring sites in the clearfelled (south tributaries) area though the same relationship did not hold for sites on the mainstream banks or for sites on the north (mature forest) ditch sites. The implications of natural vegetation colonization for management of such streams are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Crustal and upper mantle seismic structure of the Australian Plate, South Island, New Zealand

Seismic reflection and refraction data were collected west of New Zealand's South Island parallel to the Pacific–Australian Plate boundary. The obliquely convergent plate boundary is marked at the surface by the Alpine Fault, which juxtaposes continental crust of each plate. The data are used to study the crustal and uppermost mantle structure and provide a link between other seismic transects which cross the plate boundary. Arrival times of wide-angle reflected and refracted events from 13 recording stations are used to construct a 380-km long crustal velocity model. The model shows that, beneath a 2–4-km thick sedimentary veneer, the crust consists of two layers. The upper layer velocities increase from 5.4–5.9 km/s at the top of the layer to 6.3 km/s at the base of the layer. The base of the layer is mainly about 20 km deep but deepens to 25 km at its southern end. The lower layer velocities range from 6.3 to 7.1 km/s, and are commonly around 6.5 km/s at the top of the layer and 6.7 km/s at the base. Beneath the lower layer, the model has velocities of 8.2–8.5 km/s, typical of mantle material. The Mohorovicic discontinuity (Moho) therefore lies at the base of the second layer. It is at a depth of around 30 km but shallows over the south–central third of the profile to about 26 km, possibly associated with a southwest dipping detachment fault. The high, variable sub-Moho velocities of 8.2 km/s to 8.5 km/s are inferred to result from strong upper mantle anisotropy. Multichannel seismic reflection data cover about 220 km of the southern part of the modelled section. Beneath the well-layered Oligocene to recent sedimentary section, the crustal section is broadly divided into two zones, which correspond to the two layers of the velocity model. The upper layer (down to about 7–9 s two-way travel time) has few reflections. The lower layer (down to about 11 s two-way time) contains many strong, subparallel reflections. The base of this reflective zone is the Moho. Bi-vergent dipping reflective zones within this lower crustal layer are interpreted as interwedging structures common in areas of crustal shortening. These structures and the strong northeast dipping reflections beneath the Moho towards the north end of the (MCS) line are interpreted to be caused by Paleozoic north-dipping subduction and terrane collision at the margin of Gondwana. Deeper mantle reflections with variable dip are observed on the wide-angle gathers. Travel-time modelling of these events by ray-tracing through the established velocity model indicates depths of 50–110 km for these events. They show little coherence in dip and may be caused side-swipe from the adjacent crustal root under the Southern Alps or from the upper mantle density anomalies inferred from teleseismic data under the crustal root.     

Building deliberative public-private partnerships for waste management in Asia

Public-private partnerships in environmental policy should not simply be viewed in instrumental terms as means of providing environmental infrastructure and services, but also as sites where norms of environmental concern and political accountability are formulated and replicated. Deliberative public-private partnerships--or partnerships that allow greater public participation in the formulation of these norms--may therefore become an important new form of local environmental governance and help make partnerships more relevant to local environmental needs. This paper examines case studies of public-private partnerships in waste-to-energy projects in the Philippines and India to identify how principles of institutional design may enhance the deliberative nature of public-private partnerships in environmental policy. The paper argues that current approaches to deliberative, or cooperative environmental governance concerning public-private partnerships need to acknowledge insights from network theory concerning the communication of environmental and political norms before they can be successfully transferred to developing countries.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Watershed structural influences on the distributions of stream network water and solute travel times under baseflow conditions

Watershed structure influences the timing, magnitude, and spatial location of water and solute entry to stream networks. In turn, stream reach transport velocities and stream network geometry (travel distances) further influence the timing of export from watersheds. Here, we examine how watershed and stream network organization can affect travel times of water from delivery to the stream network to arrival at the watershed outlet. We analysed watershed structure and network geometry and quantified the relationship between stream discharge and solute velocity across six study watersheds (11.4 to 62.8 km²) located in the Sawtooth Mountains of central Idaho, USA. Based on these analyses, we developed stream network travel time functions for each watershed. We found that watershed structure, stream network geometry, and the variable magnitude of inputs across the network can have a pronounced affect on water travel distances and velocities within a stream network. Accordingly, a sample taken at the watershed outlet is composed of water and solutes sourced from across the watershed that experienced a range of travel times in the stream network. We suggest that understanding and quantifying stream network travel time distributions are valuable for deconvolving signals observed at watershed outlets into their spatial and temporal sources, and separating terrestrial and in‐channel hydrological, biogeochemical, and ecological influences on in‐stream observations. Copyright © 2016 John Wiley & Sons, Ltd.     

Intergranular diffusion rates from the analysis of garnet surfaces: Implications for metamorphic equilibration

Novel approaches to garnet analysis have been used to assess rates of intergranular diffusion between different matrix phases and garnet porphyroblasts in a regionally metamorphosed staurolite‐mica‐schist from the Barrovian‐type area in Scotland. X‐ray maps and chemical traverses of planar porphyroblast surfaces reveal chemical heterogeneity of the garnet grain boundary linked to the nature of the adjacent matrix phase. The garnet preserves evidence of low temperature retrograde exchange with matrix minerals and diffusion profiles documenting cation movement along the garnet boundaries. Garnet–quartz and garnet–plagioclase boundaries preserve evidence of sluggish Mg, Mn and Fe diffusion at comparable rates to volume diffusion in garnet, whereas diffusion along garnet–biotite interfaces is much more effective. Evidence of particularly slow Al transport, probably coupled to Fe³⁺ exchange, is locally preserved on garnet surfaces adjacent to Fe‐oxide phases. The Ca distribution on the garnet surface shows the most complex behaviour, with long‐wavelength heterogeneities apparently unrelated to the matrix grain boundaries. This implies that the Ca content of garnet is controlled by local availability and is thought likely to reflect disequilibrium established during garnet growth. Geochemical anomalies on the garnet surfaces are also linked to the location of triple junctions between the porphyroblasts and the matrix phases, and imply enhanced transport along these channels. The slow rates of intergranular diffusion and the characteristics of different boundary types may explain many features associated with the prograde growth of garnet porphyroblasts. Thus, minerals such as quartz, Fe‐oxides and plagioclase whose boundaries with garnet are characterized by slow intergranular diffusion rates appear to be preferentially trapped as inclusions within porphyroblasts. As such grain boundary diffusion rates may be a significant kinetic impediment to metamorphic equilibrium and garnet may struggle to maintain chemical and textural equilibrium during growth in pelites.     

Rainfall partitioning through a mixed cedar swamp and associated C and N fluxes in Southern Ontario,Canada

Partitioning of rainfall through a forest canopy into throughfall, stemflow, and canopy interception is a critical process in the water cycle, and the contact of precipitation with vegetated surfaces leads to increased delivery of solutes to the forest floor. This study investigates the rainfall partitioning over a growing season through a temperate, riparian, mixed coniferous‐deciduous cedar swamp, an ecosystem not well studied with respect to this process. Seasonal throughfall, stemflow, and interception were 69.2%, 1.5%, and 29.3% of recorded above‐canopy precipitation, respectively. Event throughfall ranged from a low of 31.5 ± 6.8% for a small 0.8‐mm event to a high of 82.9 ± 2.4% for a large 42.7‐mm event. Rain fluxes of at least 8 mm were needed to generate stemflow from all instrumented trees. Most trees had funnelling ratios <1.0, with an exponential decrease in funnelling ratio with increasing tree size. Despite this, stand‐scale funnelling ratios averaged 2.81 ± 1.73, indicating equivalent depth of water delivered across the swamp floor by stemflow was greater than incident precipitation. Throughfall dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) averaged 26.60 ± 2.96 and 2.02 ± 0.16 mg L^?1, respectively, which were ~11 and three times above‐canopy rain levels. Stemflow DOC averaged 73.33 ± 7.43 mg L^?1, 35 times higher than precipitation, and TDN was 4.45 ± 0.56 mg L^?1, 7.5 times higher than rain. Stemflow DOC concentration was highest from Populus balsamifera and TDN greatest from Thuja occidentalis trees. Although total below‐canopy flux of TDN increased with increasing event size, DOC flux was greatest for events 20–30 mm, suggesting a canopy storage threshold of DOC was readily diluted. In addition to documenting rainfall partitioning in a novel ecosystem, this study demonstrates the excess carbon and nitrogen delivered to riparian swamps, suggesting the assimilative capacity of these zones may be underestimated.