39Ar‐40Ar ages of eucrites and thermal history of asteroid 4 Vesta

Abstract— Eucrite meteorites are igneous rocks that derived from a large asteroid, probably 4 Vesta. Past studies have shown that after most eucrites formed, they underwent metamorphism in temperatures up to ≥800°C. Much later, many were brecciated and heated by large impacts into the parent body surface. The less common basaltic, unbrecciated eucrites also formed near the surface but, presumably, escaped later brecciation, while the cumulate eucrites formed at depths where metamorphism may have persisted for a considerable period. To further understand the complex HED parent body thermal history, we determined new ³⁹Ar‐⁴⁰Ar ages for 9 eucrites classified as basaltic but unbrecciated, 6 eucrites classified as cumulate, and several basaltic‐brecciated eucrites. Precise Ar‐Ar ages of 2 cumulate eucrites (Moama and EET 87520) and 4 unbrecciated eucrites give a tight cluster at 4.48 ± 0.02 Gyr (not including any uncertainties in the flux monitor age). Ar‐Ar ages of 6 additional unbrecciated eucrites are consistent with this age within their relatively larger age uncertainties. By contrast, available literature data on Pb‐Pb isochron ages of 4 cumulate eucrites and 1 unbrecciated eucrite vary over 4.4–4.515 Gyr, and ¹⁴⁷Sm‐¹⁴³Nd isochron ages of 4 cumulate and 3 unbrecciated eucrites vary over 4.41–4.55 Gyr. Similar Ar‐Ar ages for cumulate and unbrecciated eucrites imply that cumulate eucrites do not have a younger formation age than basaltic eucrites, as was previously proposed. We suggest that these cumulate and unbrecciated eucrites resided at a depth where parent body temperatures were sufficiently high to cause the K‐Ar and some other chronometers to remain as open diffusion systems. From the strong clustering of Ar‐Ar ages at ?4.48 Gyr, we propose that these meteorites were excavated from depth in a single large impact event ?4.48 Gyr ago, which quickly cooled the samples and started the K‐Ar chronometer. A large (?460 km) crater postulated to exist on Vesta may be the source of these eucrites and of many smaller asteroids thought to be spectrally or physically associated with Vesta. Some Pb‐Pb and Sm‐Nd ages of cumulate and unbrecciated eucrites are consistent with the Ar‐Ar age of 4.48 Gyr, and the few older Pb‐Pb and Sm‐Nd ages may reflect an isotopic closure before the large cratering event. One cumulate eucrite gives an Ar‐Ar age of 4.25 Gyr; 3 additional cumulate eucrites give Ar‐Ar ages of 3.4–3.7 Gyr; and 2 unbrecciated eucrites give Ar‐Ar ages of ?3.55 Gyr. We attribute these younger ages to a later impact heating. Furthermore, the Ar‐Ar impact‐reset ages of several brecciated eucrites and eucritic clasts in howardites fall within the range of 3.5–4.1 Gyr. Among these, Piplia Kalan, the first eucrite to show evidence for extinct ²⁶Al, was strongly impact heated ?3.5 Gyr ago. When these data are combined with eucrite Ar‐Ar ages in the literature, they confirm that several large impact heating events occurred on Vesta between ?4.1–3.4 Gyr ago. The onset of major impact heating may have occurred at similar times for both Vesta and the moon, but impact heating appears to have persisted for a somewhat later time on Vesta.     

Sensitivity analysis of a deterministic water temperature model to forest canopy and soil temperature in Catamaran Brook (New Brunswick,Canada)

A coupled deterministic hydrological and water temperature model, CEQUEAU, was modified to include soil temperature and crown closure in its calculation of local advective terms in the heat budget. The modified model was than tested to verify its sensitivity to these modifications. An analysis of the heat budget of a small forested catchment in eastern Canada revealed that the advective term related to interflow plays a significant role in the daily water heat budget, providing on average 28% of the local advective budget (which also includes advective heat terms from surface runoff and groundwater) and nearly 14% of the total heat budget (which includes all radiative terms at the water surface, convection and evaporation, as well as the local advective terms). Relative sensitivity indices (RSIs) were used to verify the impact of the newly introduced parameters and variables. Among them, parameters related to the forest cover (crown closure and leaf area index) have a maximum RSI of ?0·6; i.e. a 100% increase in value produces a 60% decrease in the local advective term. Parameters with the greatest influence are the volume of water contributing to interflow and the amplitude of the net radiative flux at the soil surface, which, if doubled, would double the contribution of the local interflow advective term to the heat budget. Copyright © 2003 John Wiley & Sons, Ltd.     

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.     

RELAXING ASSUMPTIONS OF PERFECT INFORMATION IN PARK VISITATION MODELS*

Variables related to urban park awareness are identified and methods for relaxing assumptions of perfect information in park use models are discussed. Park awareness is related to park characteristics (age and degree of development of the park), population characteristics (race, age, length of residence, recreation participation), and distance. Park attributes are stronger predictors of both park awareness and use than is distance. These findings parallel similar research on the cognitive aspects of shopping decisions.     

Natural recolonization of a productive tropical pond: Day to day variations in the photosynthetic parameters

Chlorophyll pigments (CHL), primary productivity (PP) and particulate nitrogen (N_p) in relation to several environmental factors were monitored during planktonic colonization of an aquaculture pond (Layo, Côte d'Ivoire). How interactions between the organisms are established in an initially azoic environment were investigated. From March, 15 (D1) to March, 31 (D16), the system transformation went through three stages. First, a precolonization by heterotrophic microbial community from D1 to D2 (N_p < 1 m maximum at D2: 243 mg m^–2; CHL around 0). Then, a pioneer microalgal community developped from D3 to D7 (maximum CHL on D6: 19 mg m^–2; PP: 1.0 g C m^–2 d^–1) with a significant contribution of picoplankton (CHL and PP < 3 m: 33 and 23% of the total, respectively). Finally, a second microalgal colonization was noticed from D9 to D12 (maximum CHL: 55 mg m^–2, PP: 2.8 g C m^–2 d^–1), largely dominated by nanoplankton (CHL and PP > 3 m: 95 and 99% of the total, respectively). Overall, photosynthetic activity appeared to be closely linked to algal biomass. The study of autotrophic biomass and activity in different size classes in relation to the other parameters allowed us to precise the origin of the biomass fluctuations. The first bloom appeared to be controlled by selective grazing on small algae. The second algal development ended when N requirement represented at least 69% of N supply (in the N — NH₄ form). This control was enhanced by the appearance of rotifers, leading to a more complex equilibrium.     

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.     

Aerobic methanotrophy at ancient marine methane seeps: A synthesis

The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of ¹³C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, ¹³C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ¹³C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ¹³C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ¹³C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs.     

Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O₂(d), pH, Conductivity, T°), major elements (SO₄, NO₃) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.