Surface and complexation effects on the rate of Mn(II) oxidation in natural waters

Montmorillonite, kaolinite, goethite, and particulate and soluble natural organic materials influence the rate of Mn(II) oxidation. While surfaces accelerate the reaction, apparently by bonding Mn²⁺ in a manner which fulfills the requirements of the transition state, soluble organic materials retard the reaction by complexing the oxidizable species. It is doubtful whether particulate matter would influence the oxidation process under natural loading conditions since 50–500 mg l^?1quantities are required to produce measurable changes in the reaction rate. Complexation by humic materials, however, might be expected to reduce the rate of oxidation by an amount proportional to the dissolved organic carbon concentration. Oxidation followed by precipitation is predicted to be an important mechanism for Mn²⁺ removal in oceanic waters. The situation is less predictable in lake waters.     

Got green? addressing environmental justice in park provision

We present a pragmatic approach to assist planners in addressing racial inequities in park access. Utilizing the Los Angeles metropolitan region as an example, we used Thiessen polygons to delineate a service area for each park, and described potential park congestion or ‘pressure’ in each park service area. Results show that Latinos, African-Americans, and low-income groups in general were likely to live close to parks with higher potential park congestion. On the other hand, predominantly White, high-income areas were typically located close to parks with lower potential park congestion levels. The park service area analysis presented here facilitates the identification of areas with greater park need and provides a pragmatic way to redress existing disparities in park access. Built into a set of web-based decision support tools, the approach fosters greater community participation and empowers local stakeholders in the process of park provision.     

Thermal evolution and physics of melt extraction on the ureilite parent body

We develop a physical model of the thermal history of the ureilite parent body (UPB) that numerically tracks the history of its heating, hydration, dehydration, partial melting and smelting as a function of its formation time and the initial values of its composition, formation temperature and water ice content. Petrologic and chemical data from the main group (non-polymict) ureilite meteorites, which sample the interior of the UPB between depths corresponding to pressures in the range 3-10 MPa, are used to constrain the model. We find that to achieve the ∼30% melting inferred for ureilites from all sampled depths, the UPB must have had a radius between ∼80 and ∼130 km and must have accreted about 0.55 Ma after CAI formation. Melting began in the body at ∼1 Ma after CAI, and the time at which 30% melting was reached varied with depth in the asteroid but was always between ∼4.5 and ∼5.8 Ma after CAI. The total rate at which melt was produced in the UPB varied from more than 100 m³ s⁻¹ in the very early stages of melting at ∼1 Ma after CAI to ∼5 m³ s⁻¹ between 2 and 3 Ma after CAI, decreasing to extremely small values as the end of melting was approached beyond ∼5 Ma. Although the initial period of high melt production occupied only a short time around 1 Ma after CAI, it corresponded to ∼half (16%) of total silicate melting, and all strictly basaltic (i.e. plagioclase-saturated) melts must have been produced during this period.A very efficient melt transport network, consisting of a hierarchy of veins and larger pathways (dikes), developed quickly at the start of melting, ensuring rapid (timescales of months) transport of any single parcel of melt to shallow levels, thus ensuring that chemical interaction between melts and the rocks through which they subsequently passed was negligible. Volatile (mainly carbon monoxide) production due to smelting began at the start of silicate melting in the shallowest parts of the UPB and at later times at greater depths. Except at the very start and very end of melting, the volatile content of the melts produced was always high - generally between 15 and 35 mass % - and most of the melt produced was erupted at the surface of the UPB with speeds well in excess of the escape velocity and was lost into space. However, we show that 30% melting at the 3 MPa pressure level was only possible if ∼15% of the total melt produced in the asteroid was retained as a small number (∼5) of very extensive, sill-like intrusions centered at a depth of ∼7 km below the surface, near the base of the ∼8 km thick outer crust of the asteroid that was maintained at temperatures below the basalt solidus by conductive heat loss to the surface. The horizontal extents of these sills occupied about 75% of the surface area of the UPB, and the sills acted as buffers between the steady supply of melt from depth and the intermittent explosive eruption of the melt into space. We infer that samples from these intrusions are preserved as the rare feldspathic (loosely basaltic) clasts in polymict ureilites, and show that the cooling histories of the sills are consistent with these clasts reaching isotopic closure at ∼5 Ma after CAI, as given by ²⁶Al-²⁶Mg, ⁵³Mn-⁵³Cr and Pb-Pb age dates.     

G-Probe-1 - An International Proficiency Test for Microprobe Laboratories - Report on Round 1 : February 2002 (TB-1 Basaltic Glass)

Results are presented for round one of a new international proficiency testing programme designed for microprobe laboratories involved in the routine analysis of silicate minerals. The sample used for this round was TB-1, a basaltic glass fused and prepared by the USGS. Thirty nine laboratories contributed data to this round, the majority of major element results being undertaken by EPMA and the majority of trace elements by LA-ICP-MS. Assigned values were derived from the median of results produced by nine selected laboratories that analysed powdered material by conventional ICP-MS, INAA and XRF techniques using bulk powders of the sample. Submitted microprobe results were evaluated using a target precision calculated using the Horwitz function, adopting the same criteria as those used for "applied" geochemistry laboratories in the companion GeoPT proficiency testing programme for laboratories involved in the routine bulk analysis of silicate rocks. An evaluation of results from participating microprobe laboratories indicated that overall, data were compatible with this precision function. A comparison between the performance of bulk and microprobe techniques used in the analysis of the basaltic glass showed remarkably good agreement, with significant bias only observed for the major oxide MgO.     

Homogeneity of the Geochemical Reference Material BRP-1 (Paraná Basin Basalt) and Assessment of Minimum Mass

Reference materials (RM) are required for quantitative analyses and their successful use is associated with the degree of homogeneity, and the traceability and confidence limits of the values established by characterisation. During the production of a RM, the chemical characterisation can only commence after it has been demonstrated that the material has the required level of homogeneity. Here we describe the preparation of BRP-1, a proposed geochemical reference material, and the results of the tests to evaluate its degree of homogeneity between and within bottles. BRP-1 is the first of two geochemical RM being produced by Brazilian institutions in collaboration with the United States Geological Survey (USGS) and the International Association of Geoanalysts (IAG). Two test portions of twenty bottles of BRP-1 were analysed by wavelength dispersive-XRF spectrometry and major, minor and eighteen trace elements were determined. The results show that for most of the investigated elements, the units of BRP-1 were homogeneous at conditions approximately three times more rigorous than those strived for by the test of "sufficient homogeneity". Furthermore, the within bottle homogeneity of BRP-1 was evaluated using small beam (1 mm²) synchrotron radiation XRF spectrometry and, for comparison, the USGS reference materials BCR-2 and GSP-2 were also evaluated. From our data, it has been possible to assign representative minimum masses for some major constituents (1 mg) and for some trace elements (1-13 mg), except Zr in GSP-2, for which test portions of 74 mg are recommended.     

From mush to eruption in centuries: assembly of the super-sized Oruanui magma body

The magmatic systems that give rise to voluminous crystal-poor rhyolite magma bodies can be considered to operate on two contrasting timescales: Those governed by longer-term processes by which a magma acquires its chemical and isotopic characteristics (e.g., fractional crystallisation and assimilation), and those operating at shorter timescales during the physical accumulation of the melt-dominant magma body that finally erupts. We explore the compositional and textural relationships between amphibole and orthopyroxene crystals from the 25.4 ka, 530 km³ (magma) Oruanui eruption products (Taupo volcano, New Zealand) to investigate how processes related to the physical assembly of the pre-eruptive magma body are represented in the crystal record. Over 90 % of orthopyroxenes from the volumetrically dominant high-SiO₂ (>74 wt%) rhyolite pumices record textural evidence for a significant disequilibrium event (partial dissolution ± resorption of cores and interiors) prior to the growth of 40–500 μm thick rim zones. This dissolution/regrowth history of orthopyroxene is recorded in the chemistry of co-crystallising amphiboles as a prominent inflection in the concentrations of Mn and Zn, two elements notably enriched in orthopyroxene relative to amphibole. Textural and chemical features, linked with in situ thermobarometric estimates, indicate that a major decompression event preceded the formation of the melt-dominant body. The decompression event is inferred to represent the extraction of large volumes of melt plus crystals from the Oruanui crystal mush/source zone at pressures of 140–300 MPa (~6–12 km depth). Orthopyroxene underwent partial dissolution during ascent before reestablishing in the melt-dominant magma body at pressures of 90–140 MPa (~3.5–6 km). We model Fe–Mg diffusion across the core-rim boundaries along the crystallographic a or b-axes to constrain the timing of this decompression event, which marked establishment of the melt-dominant magma body. Maximum modelled ages indicate that this event did not begin until ~1,600 years before eruption, consistent with constraints from zircon model-age spectra. Once extraction began, it underwent runaway acceleration with a peak extraction age of ~230 years, followed by an apparent period of stasis of ~60 years prior to eruption. The rapidity of the extraction and accumulation processes implies the involvement of a dynamic driving force which, in the rifted continental arc setting of the Taupo Volcanic Zone, seems likely to be represented by magma-assisted extensional tectonic processes.     

地球物理学与大陆成长

引言解释星球和原子的內部运动和活动情况的理論比关于地球的类似理論发展得更为完善,更广泛地为人接受,这是令人惊奇的。但如比較一下,地球比較容易接触到,而星球和原子則十分遙远,那么上述的情况应正好相反。这种情况之所以产生,一部分是由于許多星球和原子有強烈的輻射,因而透露出它們的性貭,一部分是由于原子和星球数量很多,因而我們有时可能对它們其中之一所发生的不寻常变化.     

Seismic and sedimentologic features of Oxfordian-Kimmeridgian syn-rift sediments on the eastern margin of the Lusitanian Basin

Following deposition of widespread middle Oxfordian lacustrine carbonates and evaporites, the Lusitanian Basin was differentiated into a number of sub-basins. The Arruda sub-basin is a half graben basin situated some 30 km north of Lisbon. It accumulated over 2.5 km of Kimmeridgian siliciclastic sediments, and is bounded to the east by the Vila Franca de Xira fault zone. Carbonate deposition persisted over horsts along the fault zone from the Oxfordian to the early Kimmeridgian, and in places to the late Kimmeridgian, and shows a pronounced west-east facies zonation, with higher energy framestones and grainstones accumulating along the exposed western margins. Seismic data indicate a major gap between the horst blocks that acted as a conduit through which basement derived siliciclastics were fed westwards into the sub-basin to form a submarine fan system. The presence of large blocks of framestone carbonates encased in siliciclastics indicates that carbonate sedimentation occurred in abandoned parts of the fan system. The rapid changes of sediment thicknesses and facies types along the eastern margin of the Arruda sub-basin are indicative of contemporaneous strike-slip movements.

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Zusammenfassung Nach der weitverbreiteten Ablagerung mitteloxfordischer Seenkarbonate und Evaporite differenzierte sich das Lusitanische Becken in verschiedene Sub-Becken. Das Arruda Sub-Becken befindet sich ca. 30 km nördlich Lissabon und entspricht einem Halbgraben, in dem über 2.5 km mächtige Siliziklastika des Kimmeridgium zur Ablagerung kamen. Das Sub-Becken wird durch die Störungszone von Vila Franca de Xira nach Osten begrenzt. Auf Horststrukturen entlang der Störungszone wurden im Oxfordium und Unterkimmeridgium, z. T. auch bis ins Oberkimmeridgium Karbonate sedimentiert. Diese Karbonatschelfe weisen eine ausgeprägte Fazieszonierung von West nach Ost auf. Die westlichen Schelfränder sind durch höherenergetische Riffkalke (framestones) und Karbonatsande (grainstones) charakterisiert. Seismische Profile lassen eine große Lücke zwischen den Horstblöcken erkennen, durch welche Siliziklastika aus dem Hinterland ins Sub-Becken gelangten, wo sie einen submarinen Fächer aufbauten. Große Riffkalkblöcke innerhalb der Siliziklastika weisen auf Karbonatsedimentation in verlassenen Fächerbereichen hin. Die schnellen Mächtigkeits- und Fazieswechsel entlang des Ostrandes des Arruda Sub-Beckens sind durch synsedimentäre tektonische Bewegungen zu erklären, welche oftmals eine Dominanz der Lateralkomponente aufweisen.

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Resumo Depois da sedimentação dos calcários lacustres e depósitos evaporíticos da idade Oxfordiano médio, a Bacia Lusitánica diferenciou-se em várias sub-bacias. A sub-bacia de Arruda está situada ca. de 30 km ao norte de Lisboa e corresponde a uma estrutura «half-graben» em que mais do que 2.5 km de sedimentos foram acumulados. Para leste, a sub-bacia é limitada pela zona das falhas de Vila Franca de Xira. Entre o Oxfordiano e o Kimeridgiano, calcários desenvolveram-se em cima dos blocos elevados (horsts) ao longo da zona de falhas. Estes calcários de tipo plataforma exibem uma distincta zonação de facies de oeste a leste. As margens occidentals das plataformas pequenas são caracterisadas por sedimentos recifais e areníticos. Cortes sísmicos indicam uma abertura grande entre os blocos elevados, pelo quai sedimentos siliciclásticos passaram de hinterland à sub-bacia formando um fan submarino. Grandes blocos recifais situados dentro dos depósitos siliciclásticos são evidências para sedimentação carbonática em várias áreas abandonadas dentro do fan. Mudanças rápidas das espessuras e das fácies dos sedimentos ao longo da margem oriental da sub-bacia de Arruda podiam ser explicadas por uma tectónica sinsedimentária dominada por movimentos horizontais.

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