Offshore granulites from the Bay of Biscay margins: fission tracks constrain a Proterozoic to Tertiary thermal history

Zircon and apatite fission track ages were determined on granulites dredged along the Bay of Biscay margins. A sample from Ortegal Spur (Iberia margin) yielded 725 ± 67 Ma (zircon). A sample from Le Danois Bank (Iberia margin) yielded 284 ± 58 Ma (zircon), indicating post‐Variscan cooling. Apatite from this sample gave 52 ± 2 Ma, interpreted as final cooling after ‘Pyrenean’ thrust imbrication. Two other samples from Le Danois Bank have Early Cretaceous apatite ages (138 ± 7 and 120 ± 8 Ma), interpreted to result from exhumation during rifting. Finally, a granulite from Goban Spur (Armorican margin) gave 212 ± 10 Ma (apatite), coinciding with a precursory rifting phase. Together with published radiometric results, these data indicate a Precambrian high‐grade terrane at the site of the current margins. The distribution of the granulites on the seafloor reflects tectonic and erosional processes related to (a) Mesozoic rifting and (b) Early Tertiary incipient subduction of the Bay of Biscay beneath Iberia.     

Detailed <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of geologic events associated with the Mantos Blancos copper deposit,northern Chile

The ⁴⁰Ar/³⁹Ar geochronological method was applied to date magmatic and hydrothermal alteration events in the Mantos Blancos mining district in the Coastal Cordillera of northern Chile, allowing the distinction of two separate mineralization events. The Late Jurassic Mantos Blancos orebody, hosted in Jurassic volcanic rocks, is a magmatic-hydrothermal breccia-style Cu deposit. Two superimposed mineralization events have been recently proposed. The first event is accompanied by a phyllic hydrothermal alteration affecting a rhyolitic dome. The second mineralization event is related to the intrusion of bimodal stocks and sills inside the deposit. Because of the superposition of several magmatic and hydrothermal events, the obtained ⁴⁰Ar/³⁹Ar age data are complex; however, with a careful interpretation of the age spectra, it is possible to detect complex histories of successive emplacement, alteration, mineralization, and thermal resetting. The extrusion of Jurassic basic to intermediate volcanic rocks of the La Negra Formation is dated at 156.3 ± 1.4 Ma (2σ) using plagioclase from an andesitic lava flow. The first mineralization event and associated phyllic alteration affecting the rhyolitic dome occurred around 155–156 Ma. A younger bimodal intrusive event, supposed to be equivalent to the bimodal stock and sill system inside the deposit, is probably responsible for the second mineralization event dated at ca. 142 Ma. Other low-temperature alteration events have been dated on sericitized plagioclase at ca. 145–146, 125, and 101 Ma. This is the first time that two distinct mineralization events have been documented from radiometric data for a copper deposit in the metallogenic belt of the Coastal Cordillera of northern Chile. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Temporal variability in phytodetritus and megabenthic activity at the seabed in the deep Northeast Atlantic

We report a ten-year study of the abundance and activity of megabenthos on the Porcupine Abyssal Plain, northeast Atlantic, together with observations on the occurrence of phytodetritus at the deep-sea floor (4850 m). Using the Southampton Oceanography Centre time-lapse camera system, ‘Bathysnap’, we have recorded a radical change in the abundance and activity of megabenthos between the two periods of study (1991–1994 and 1997–2000). In 1991–1994, the larger megabenthos occurred at an abundance of c. 71.6/ha and were dominated by large holothurians. In addition, there were very substantial populations of smaller megabenthic ophiuroids (c. 4979/ha). Together, the total megabenthos are estimated to track over some 17 cm²/m²/d (exploiting 100% of the surface of the seabed in c. 2.5 years). In 1997–2000, the larger megabenthos increased to an abundance of c. 204/ha and were joined by exceptional numbers of a small holothurian species (Amperima rosea, 6457/ha) and ophiuroids (principally Ophiocten hastatum, 53,539/ha). The total megabenthos population was tracking at an estimnated rate of c. 247 cm²/m²/d (exploiting 100% of seabed in just 6 weeks). Coincident with these increases in the abundance and activity of the megabenthos, there were apparently no mass depositions of aggregated phytodetritus to the seabed in the summers of 1997–1999. Mass occurrences of phytodetritus had been noted during the summer months of the three years previously studied (1991, 1993 and 1994), with covering between 50 and 96% of the sediment surface. There is a statistically significant (p<0.02) negative correlation between maximum extent of this seabed cover of phytodetritus and seabed tracking by megabenthos. Additional studies [Lampitt et al., Progr. Ocean. 50 (2001)], indicate that there were no substantial changes in surface ocean primary productivity, in export flux, or in the composition of the flux that might otherwise account for the apparent absence of observable concentrations of phytodetritus during the summers of 1997–1999. We postulate that the marked increase in megabenthic tracking activity resulted in the removal (via consumption, disaggregation, burial etc.) of the bulk of the incoming phytodetrital flux during these years. A simple conceptual model, based on the apparent phytodetrital fluxes observed in 1991 and 1993, suggests that the megabenthos tracking rates estimated for 1997–1999 are sufficient to account for near-total removal of this flux. However, we are not able to estimate other processes removing phytodetritus (i.e. other elements of the benthos) that may also have increased between 1991–1994 and 1997–1999. Other independent studies [e.g. Ginger et al., Progr. Ocean. 50 (2001)] of flux constituents support the possibility that just a few species of megabenthos (e.g. A. rosea, and O. hastatum) could well have consumed a major proportion of the incoming flux and so substantially modified the composition of the organic matter available to other components of the benthos.     

Seasonality and selectivity in the feeding ecology and reproductive biology of deep-sea bathyal holothurians

Chlorophyll and carotenoid pigments were determined from the gut sediments of five species of bathyal holothurian in the NE Atlantic, sampled shortly after the spring/summer phytoplankton bloom in 2001 and prior to the spring bloom in 2002. Three species, Laetmogone violacea, Paroriza pallens and Bathyplotes natans, sampled within a similar depth range (900–1100 m) in the summer of 2001 showed significant differences in their chlorophyll and carotenoid pigment concentrations. This suggests they may select for slightly different components from the available food resource. Four species sampled in early spring 2002, Laetmogone violacea, Paroriza pallens, Benthogone rosea and Benthothuria funebris, also had significant differences in their pigment concentrations. These species were sampled over a wider depth range (1000–3100 m) showing a bathymetric trend in pigment concentrations. There was a distinct seasonal change in the composition and concentration of the pigments, linked to a reduction in the availability of fresh organic material during autumn and winter periods.Ovarian tissue was also examined. The carotenoid pigments found in the ovary also occurred in the OM ingested by the holothurians. The dominant gonadal carotenoid pigments were β-carotene, echinenone and zeaxanthin. The potential for using these carotenoids to gain a competitive advantage through selectivity of chlorophyll and carotenoid pigment biomarkers are discussed in relation to competition for food resources by deposit-feeders. The results were also compared with selectivity in abyssal species.