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.     

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.     

Anaerobic diagenesis of silica and carbon in continental margin sediments: Discrete zones of TCO2 production

Pore water profiles of dissolved Si, Ca²⁺, SO₄^2-, CH₄, and TCO₂ (Dissolved Inorganic Carbon; DIC) were determined from multicores and gravity cores collected at nine sites off Southern California, the west coast of Mexico, and within the Gulf of California. These sites were located within the eastern North Pacific oxygen minimum zone at depths of 400 to 900 m and in settings where bottom water oxygen concentrations were <3 μM and sediments were laminated. Pore water profiles were defined at a resolution of millimeters (whole core squeezing), centimeters (sectioning and squeezing) and meters (gravity core sectioning and squeezing), and diffusive fluxes were calculated for different zones within the sediment column. The flux of dissolved silica across the sediment-water interface (SWI) ranged from 0.3 to 3.4 mmol Si m^-2d^-1, and TCO₂ fluxes ranged from 0.8 to 4.6 mmol C m^-2d^-1. A positive correlation (r = 0.74) existed between these fluxes, yet these two constituents exhibited significantly different diagenetic behavior downcore; dissolved Si generally reached a constant concentration (between 450 and 900 μM) in the upper few cm, whereas TCO₂ concentrations increased monotonically with depth.Methane was detected at micromolar levels in sediment intervals between 0 and 60 cm and at five sites, increased to millimolar levels at depths of 80 to 170 cm. At the horizon marking the appearance of millimolar levels of methane, there was a distinct change in slope of the sulfate and TCO₂ gradients. A flux budget for this horizon was determined by using linear fits to pore water profiles; these budgets indicate that the upward TCO₂ flux away from this horizon is 40 to 50% greater than the downward sulfate flux to this horizon. Given that the TCO₂ flux to this horizon from below was quite small, this imbalance suggests that anaerobic oxidation of methane by sulfate is not the only process producing TCO₂ within this horizon. A budget for TCO₂ at this horizon is balanced when 40 to 80% of the sulfate flux is attributed to organic carbon remineralization. Of the DIC that diffuses across the SWI, 20 to 40% is generated by reactions occurring within or below this deep reaction horizon.     

Strontium-calcium ratios in Cenozoic planktonic foraminifera

The $\text{Sr}\text{Ca}$ ratio and other parameters have been measured in fossil planktonic foraminifera from the Atlantic and Pacific Ocean basins in order to evaluate the $\text{Sr}\text{Ca}$ ratio of seawater during the last 75 million years. Results on well-preserved samples indicate that the ratio has increased to its present value by 10–15% during the Cenozoic, and that minima occurred between 55-45 Ma and 10-5 Ma, when the ratio was 15–25% less than at present. The long-term increase may reflect either decreasing deposition of aragonite with a high $\text{Sr}\text{Ca}$ ratio in shallow seas, or decreasing seafloor spreading rates and consequently decreasing hydrothermal supply of Ca during the Cenozoic. Other geologic evidence suggests that the Eocene minimum (near 50 Ma) may have resulted from increased aragonite sedimentation, while the Late Miocene minimum (between 10-5 Ma) may have been caused by an increased rate of seawater-basalt exchange when seafloor spreading rates increased on the East Pacific Rise near 10 Ma.     

Mapping hydrothermal alteration in the Comstock mining district,Nevada, using simulated satellite‐borne hyperspectral data

Hydrothermal alteration mapping with spaceborne hyperspectral data was simulated in the Comstock mining district, Nevada in order to evaluate the mineral mapping capabilities of the proposed Australian Resource Information and Environment Satellite (ARIES‐1). As a result, a suite of hydrothermal alteration minerals, including kaolinite, dickite, illite, chlorite, alunite and carbonate was identified from the simulated data in the 0.4–2.5 μm wavelength region and their areal abundance variations mapped accordingly. The recognised alteration zoning shows a major change in alteration assemblages across the Comstock and Silver City Faults, and a gradual variation from north to south along the faults. In the bleached Miocene volcanic rocks, dickite, kaolinite, illite and alunite were recognised. Coexistence of dickite of relatively high temperature, high‐crystallinity kaolinite of medium temperature and low‐crystallinity kaolinite of low temperature suggests supergene processes overprinting earlier hypogene alteration. The bleached rocks probably represent hydrothermal alteration in the fluid up‐flow zones in the central and shallower parts of the hydrothermal system. Illite in the bleached zones is characterised by relatively short AI–OH band wavelengths (2190–2200 nm), indicating no or very low Fe and/or Mg contents. Fault‐controlled propylitic alteration is mapped in the central part of the district mainly in the footwall of the Comstock Fault. The associated illite is characterised mainly by medium AI–OH band wavelengths (2200–2208 nm). This propylitic alteration may be contemporaneous with Au–Ag mineralisation. Additional and more extensive propylitic zones, containing illite with long AI–OH band wavelengths (2204–2216 nm), were mapped in the southern part of the district. These zones resulted from either a pre‐mineralisation propylitic alteration, or the peripheral hydrothermal alteration in the fluid down‐flow zones of the Miocene hydrothermal system.     

Evidence for ocean acidification in the Great Barrier Reef of Australia

Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO₂, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ¹¹B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ¹¹B isotopic compositions reflect variations in seawater pH, and the δ¹³C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ¹⁸O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ¹¹B values. The internal precision and reproducibility for δ¹¹B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ¹¹B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ¹¹B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α_(B3-B4) of the boric acid and borate species in seawater. Correlations of δ¹¹B with δ¹³C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO₂ in surface waters from the rapidly increasing levels of atmospheric CO₂, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO₂ in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.     

The African Renaissance and its relation to the geosciences: a South African perspective

Implicit in the African Renaissance is the synergy between government, the private sector, the educated minority and the disadvantaged majority. For this concept to work, belief and commitment must arise first from the African individual, whatever his or her potential contribution may be. The geosciences in South Africa provide a currently vibrant example of such cooperation, which has the potential to contribute significantly to the upliftment of the country and its neighbouring states. Based largely on personal interviews with various role players, from the Presidency of South Africa, through ministerial levels, the corporate sector and down to the individual, we present a spectrum of viewpoints and initiatives which are starting to result in practical implementation of the African revival. An end to conflict and xenophobia, the entrenchment of democratic government and corporate expression of the entrepreneurial spirit are essential to provide the framework within which the individual African can become a “Renaissance Man or Woman”.     

The seismicity of Kohistan, Pakistan: Source studies of the Hamran (1972.9.3), Darel (1981.9.12) and Patan (1974.12.28) earthquakes

Long period body waves are examined to show that the Hamran (1972.9.3), Darel (1981.9.12) and Patan (1974.12.28) earthquakes in Kohistan had focal depths of about 8–10 km. All involved high angle reverse faulting (thrusting) and had seismic moments of about 2.2 to 2.7·10²⁵ dyne cm. These shallow depths contrast with the deeper hypocentres found in the Hindu Kush and northeast Karakoram to the north and in Hazara to the south. The Hamran and Patan shocks were assigned depths of 45 km by the ISC, indicating that even well-recorded events in this region may have focal depths in error by 30 km     

Installation age of limestone masonry determined from its viscous remagnetization

Many rocks passively acquire some time‐dependent or “viscous” remanent magnetism (VRM) at ambient temperatures, without any extraordinary energetic intervention. This magnetization overprints existing remanent magnetization so that it is effectively a remagnetization subparallel to the contemporary geomagnetic field, averaging the geomagnetic field orientation. Certain limestone masonry remagnetizes viscously over an archaeologically useful interval (100 to 8000 Ka) so that the degree of remagnetization is monotonically (but not linearly) related to the construction age. The laboratory unblocking temperature (T_UB) that removes the viscous magnetization is a simple monotonic measure of relative age. The longer a piece of masonry remained stabilized in a certain orientation, the greater is its viscous remagnetization and the higher is its T_UB. Monuments of known age with a similar limestone source permit us to establish a calibration curve of T UB against historical ages. The resulting calibration curve may then be used to predict the ages of otherwise‐undated masonry. Viscous remanent magnetism dating provides precision of <50a in medieval monuments in England and <150a precision for classical to Neolithic monuments in Cyprus; precision depends on the remagnetization rate of the limestone in question. Our calibration curves, for the Jurassic Oolitic Limestone of England and for the Lefkara‐Pakhna Chalks of Cyprus, allowed us to investigate the authenticity of a medieval English synagogue in Lincoln, England, and of a medieval house in Cyprus. Multiple archaeologic VRMs show that masonry was recycled in historical times. © 2006 Wiley Periodicals, Inc.