Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history

Ion microprobe analysis of magnetites from the Adirondack Mountains, NY, yields oxygen isotope ratios with spatial resolution of 2–8 m and precision in the range of 1 (1 sigma). These analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of ¹⁸O at this scale. High precision micro-analyses of this sort will permit wide-ranging new applications in stable isotope geochemistry. The analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite. Textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite. Magnetites are near to Fe₃O₄ in composition, and optically and chemically homogeneous. A combination of ion probe plus conventional BrF₅ analysis shows that individual grains are homogeneous with ¹⁸O=8.9±1 SMOW from the core to near the rim of 0.1–1.2 mm diameter grains. Depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in ¹⁸O. These low ¹⁸O values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite. These are the sharpest intracrystalline gradients measured to date in geological materials. This discovery is confirmed by bulk analysis of 150–350 m diameter magnetites which average 1.2 lower in ¹⁸O than coarse magnetites due to low ¹⁸O rims. Conventional analysis of coexisting calcite yields °¹⁸O=18.19, suggesting that bulk ¹⁸O (Cc-Mt)=9.3 and yielding an apparent equilibration temperature of 525° C, over 200° C below the temperature of regional metamorphism. Consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories. The data for oxygen in calcite under hydrothermal conditions at high P(H₂O) indicates that diffusion is faster in magnetite and modelling of the low ¹⁸O rims on magnetite would suggest that the Adirondacks experienced slow cooling after Grenville metamorphism, followed by a brief period of rapid cooling, possibly related to uplift. Conversely, the data for calcite at low P(H₂O) show slower oxygen diffusion than in magnetite. Modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals, suggesting that the low ¹⁸O rims form by exchange with late, low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets. In either case, the ion microprobe results indicate that two distinct events are recorded in the post-metamorphic exchange history of these magnetites. Recognition of these events is only possible through microanalysis and has important implications for geothermometry.     

Ion microprobe analysis of oxygen isotope ratios in quartz from Skye granite: healed micro-cracks,fluid flow,and hydrothermal exchange

 Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ ¹⁸O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ ¹⁸O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled. Received: 23 October 1995/Accepted: 9 April 1996     

Chemical denudation rates in Kärkevagge, Swedish Lapland

This study examines the spatial and temporal variability of chemical denudation rates in Kärkevagge, northern Sweden. The chemical flux rates within the valley are strongly influenced by the local geology. Chemical denudation rates determined for the study period are more than double those previously reported in the literature for this valley. Rates of greater than 46t km⁻² a⁻¹ were measured at the valley mouth over the course of the melt season. This difference is likely due to differences in measurement technique compared to that used by past researchers. This rate is also much higher than for other arctic and alpine watersheds. Chemical denudation in Kärkevagge is comparable to larger temperate rivers. The rapid chemical denudation in Kärkevagge is likely due to sulfide weathering creating acid solutions.     

Displacement and rectification of planetary fluids

Abstract

Laboratory experiments on the decay (spin-up) of fluid motion on the β-plane are compared with theory. Under weakly dissipative conditions, some particles conserve potential vorticity during the entire decay. We also study the rectified mean flow which is produced by the lateral Reynolds Stress when a low frequency force is applied to the planetary fluid. The possible connection of effects with oceanic phenomena is briefly discussed.     

Surface and subsurface sedimentary structures produced by salt crusts

The growth and subsequent dissolution of salts on or within sediment may alter sedimentary structures and textures to such an extent that it is difficult to identify the depositional origin of that sediment and, as a result, the sediment may be misinterpreted. To help to overcome such problems with investigating ancient successions, results are presented from a comprehensive study of the morphology and fabrics of three large areas of modern salt flats in SE Arabia: the Sabkhat Matti inland region and the At Taf coastal region, both in the Emirate of Abu Dhabi, and the Umm as Samim region in Oman. These salt flats are affected by tidal‐marine, alluvial and aeolian depositional processes and include both clastic‐ and carbonate‐dominated surficial sediments. The efflorescent and precipitated salt crusts in these areas can be grouped into two main types: thick crusts, with high relief (>10 cm) and a polygonal or blocky morphology; or thin crusts, with low relief (<10 cm) and a polygonal or blister‐like appearance. The thin crusts may assume the surface morphology of underlying features, such as ripples or biogenic mats. A variety of small‐scale textures were observed: pustular growths, hair‐like spikes and irregular wrinkles. Evolution of these crusts over time results in a variety of distinctive sedimentary fabrics produced by salt‐growth sediment deformation, salt‐solution sediment collapse, sediment aggradation and compound mixtures of these processes. Salt‐crust processes produce features that may be confused with aeolian adhesion structures. An example from the Lower Triassic Ormskirk Sandstone Formation of the Irish Sea Basin demonstrates how this knowledge of modern environments improves the interpretation of the rock record. A distinctive wavy‐laminated facies in this formation had previously been interpreted as the product of fluvial sheetfloods modified by soft‐sediment deformation and bioturbation. Close inspection of laminations seen in core reveals many of the same sedimentary fabrics seen in SE Arabia associated with salt crusts. This facies is the product of salt growth on aeolian sediment and is not of fluvial origin.     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

Airborne Laser-Induced Fluorescence (LIF) Light Detection and Ranging (LiDAR) for the Quantification of Dissolved Organic Matter Concentration in Natural Waters

Analysis of dissolved organic matter (DOM) concentration and composition is essential to quantifying biological and chemical oxygen demand and atmosphere?Cocean heat flux exchange in natural waters. However, manual water sampling is costly and time consuming over large areas. The purpose of this research was to analyze the applicability of airborne laser-induced fluorescence light detection and ranging (LiDAR) for the detection of DOM in estuarine ecosystems impacted by agriculture. A fluorescence LiDAR system (Airborne Marine) (FLS-AM) was used to assess the DOM concentration of the Annapolis River and Basin, Nova Scotia, Canada, as well as three rivers and their estuaries in Prince Edward Island, Canada. Two FLS-AM flight missions were conducted in the summers of 2008 and 2009 and the resulting datasets were compared with spectral fluorescence signature (SFS DOM) and dissolved organic carbon (DOC) analysis of in situ water samples. Significant positive correlations were found at five of seven sites between the FLS-AM DOM and SFS DOM relationship which indicates that the FLS-AM sensor is a good surrogate for traditional sample collection of DOM data in estuaries in this region. Positive correlations were also found at all sites between FLS-AM DOM values and DOC. FLS-AM DOM patterns show that DOM values are significantly higher in rivers and estuaries that drain watersheds which are heavily impacted by agricultural practices. The results of this study show that the FLS-AM can be used efficiently as a general indicator for how estuaries are affected by runoff from agricultural watersheds in real time and thus reduce the requirement for traditional water sample collection and laboratory analysis methods.     

A case example of near-surface correction for multicomponent VSPS

A deterministic near-surface correction procedure is developed for multicomponent VSP data, shot using directional sources and recorded using three-component receivers. The method is capable of removing unwanted effects of acquisition such as unequal source strengths or misorientations, but may also remove near-surface multiples and anisotropy. This is of considerable benefit for obtaining accurate and consistent estimates of subsurface anisotropy from different source combinations. Application of the technique is illustrated using a dataset from the Romashkino reservoir in Russia, where three or four different directional sources are used at the same source locations. The technique corrects for the large discrepancies which exist between the estimates obtained using different source combinations. Application of the technique to three wells in the survey region reveals a nearly isotropic subsurface, except for a few isolated zones of moderate to high (2 to 8%) anisotropy which lie close to the expected depth for the reservoir. Although there is no significant correlation with the production figures for each well, the qS1 polarization azimuth within the reservoir does vary at each well location, suggesting that this may be a more sensitive indicator of reservoir Drocess.