Diffusion and partition coefficients of minor and trace elements in San Carlos olivine at 1,300°C with some geochemical implications

Lattice diffusion coefficients have been determined for 19 elements (Li, Be, Na, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Eu, Gd, Lu and Hf) in a single crystal of San Carlos olivine as a function of crystallographic orientation, at 1,300°C, 1 bar and fO₂ = 10^−8.3 bars, by equilibration with a synthetic silicate melt. Results for Li, Na, V, Cr, Fe and Zn are from diffusion of these elements out of the olivine, starting from their indigenous concentrations; those for all other elements are from diffusion into the olivine, from the silicate melt reservoir. Our 25-day experiment produced diffusion profiles 50 to > 700 μm in length, which are sufficiently long that precise analyses could be achieved by scanning laser ablation inductively coupled plasma mass spectrometry, even at concentration levels well below 1 μg g⁻¹. For the divalent cations Ca, Mn, Fe and Ni, profiles were also obtained by electron microprobe analysis. The results of the two methods agree well with each other, and are consistent with divalent cation diffusion coefficients previously determined using different experimental methodologies. Olivine/melt partition coefficients retrieved from the data are also consistent with other published partitioning data, indicating that element incorporation and transport in olivine in our experiment occurred via mechanisms appropriate to natural conditions. Most of the examined trace elements diffuse through olivine at similar rates to the major octahedral cations Fe and Mg, showing that cation charge and radius have little direct influence on diffusion rates. Aluminium and P remain low and constant in the olivine, implying negligible transport at our analytical scale, hence Al and P diffusion rates that are at least two orders of magnitude slower than the other cations studied here. All determined element diffusivities are anisotropic, with diffusion fastest along the [001] axis, except Y and the REEs, which diffuse isotropically. The results suggest that element diffusivity in olivine is largely controlled by cation site preference, charge balance mechanisms and point-defect concentrations. Elements that are present on multiple cation sites in olivine (e.g. Be and Ti) and trivalent elements that are charge-balanced by octahedral site vacancies tend to diffuse at relatively fast rates.     

Cenomanian–Turonian transition in a shallow water sequence of the Sinai, Egypt

Environmental and depositional changes across the Late Cenomanian oceanic anoxic event (OAE2) in the Sinai, Egypt, are examined based on biostratigraphy, mineralogy, δ¹³C values and phosphorus analyses. Comparison with the Pueblo, Colorado, stratotype section reveals the Whadi El Ghaib section as stratigraphically complete across the late Cenomanian–early Turonian. Foraminifera are dominated by high-stress planktic and benthic assemblages characterized by low diversity, low-oxygen and low-salinity tolerant species, which mark shallow-water oceanic dysoxic conditions during OAE2. Oyster biostromes suggest deposition occurred in less than 50 m depths in low-oxygen, brackish, and nutrient-rich waters. Their demise prior to the peak δ¹³C excursion is likely due to a rising sea-level. Characteristic OAE2 anoxic conditions reached this coastal region only at the end of the δ¹³C plateau in deeper waters near the end of the Cenomanian. Increased phosphorus accumulations before and after the δ¹³C excursion suggest higher oxic conditions and increased detrital input. Bulk-rock and clay mineralogy indicate humid climate conditions, increased continental runoff and a rising sea up to the first δ¹³C peak. Above this interval, a dryer and seasonally well-contrasted climate with intermittently dry conditions prevailed. These results reveal the globally synchronous δ¹³C shift, but delayed effects of OAE2 dependent on water depth.     

Field report: Exploring the Doonerak fenster of the central Brooks Range,Alaska, USA

Arctic Alaska is a ‘suspect’ terrane that encompasses approximately 20% of Alaska, stretching from the southern Brooks Range all the way to the continental shelves of the Chukchi and Beaufort Seas. Although the origin and subsequent travels of this large crustal fragment are debated among geologists, most researchers agree upon its composite nature and exotic origin. To constrain the early geological history of this terrane, we describe a recent expedition to the Doonerak fenster of the central Brooks Range. This area has long been regarded as a key locality for understanding the structural evolution of the Mesozoic–Cenozoic Brooks Range orogen; however, our target was different: a unique sequence of volcanic and siliciclastic rocks (Apoon assemblage) exposed beneath a profound pre-Mississippian unconformity, which we argue is of key importance to understanding the early Paleozoic tectonic history of northern Alaska and the greater Arctic.     

Estimating the propagation velocity of atmospheric fronts from surface wind observations

Abstract

Surface mesonet winds recorded at 10‐min intervals are used to estimate the propagation velocities of atmospheric fronts in East Coast winter storms during the Canadian Atlantic Storms Program (CASP). The frontal motion is modelled locally as the translation of a line across which there is an abrupt shift in wind direction. The mesonet is used to detect the propagation velocity of the windshift line.

Frontal velocities estimated using mesonet winds for all cases in which fronts passed through the mesonet (two cold fronts and three warm fronts) are in close agreement with those deduced from synoptic charts. Recommendations are given for using the method as a research tool to estimate frontal motions in oceanographic studies of wind‐driven circulation.     

Review of oil spill remote sensing

Remote-sensing for oil spills is reviewed. The use of visible techniques is ubiquitous, however it gives only the same results as visual monitoring. Oil has no particular spectral features that would allow for identification among the many possible background interferences. Cameras are only useful to provide documentation. In daytime oil absorbs light and remits this as thermal energy at temperatures 3–8 K above ambient, this is detectable by infrared (IR) cameras.     

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO₂(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.     

40Ar/39Ar ages of L4, H5, EL6, and feldspathic ureilitic clasts from the Almahata Sitta polymict ureilite (asteroid 2008 TC3)

The Almahata Sitta (AhS) meteorite consists of disaggregated clasts from the impact of the polymict asteroid 2008 TC₃, including ureilitic (70%–80%) and diverse non-ureilitic materials. We determined the ⁴⁰Ar/³⁹Ar release patterns for 16 AhS samples (3–1500 μg) taken from three chondritic clasts, AhS 100 (L4), AhS 25 (H5), and MS-D (EL6), as well as a clast of ureilitic trachyandesite MS-MU-011, also known as ALM-A, which is probably a sample of the crust of the ureilite parent body (UPB). Based on our analyses, best estimates of the ⁴⁰Ar/³⁹Ar ages (Ma) of the chondritic clasts are 4535 ± 10 (L4), 4537–4555 with a younger age preferred (H5), and 4513 ± 17 (EL6). The ages for the L4 and the H5 clasts are older than the most published ⁴⁰Ar/³⁹Ar ages for L4 and H5 meteorites, respectively. The age for the EL6 clast is typical of older EL6 chondrites. These ages indicate times of argon closure ranging up to 50 Ma after the main constituents of the host breccia, that is, the ureilitic components of AhS, reached the >800°C blocking temperatures of pyroxene and olivine thermometers. We suggest that these ages record the times at which the clasts cooled to the Ar closure temperatures on their respective parent bodies. This interpretation is consistent with the recent proposal that the majority of xenolithic materials in polymict ureilites were implanted into regolith 40–60 Ma after calcium–aluminum-rich inclusion and is consistent with the interpretation that 2008 TC₃ was a polymict ureilite. With allowance for its 10-Ma uncertainty, the 4549-Ma ⁴⁰Ar/³⁹Ar age of ALM-A is consistent with closure within a few Ma of the time recorded by its Pb/Pb age either on the UPB or as part of a rapidly cooling fragment. Plots of age versus cumulative ³⁹Ar release for 10 of 15 samples with ≥5 heating steps indicate minor losses of ⁴⁰Ar over the last 4.5 Ga. The other five such samples lost some ⁴⁰Ar at estimated times no earlier than 3800–4500 Ma bp . Clustering of ages in the low-temperature data for these five samples suggests that an impact caused localized heating of the AhS progenitor ~2.7 Ga ago. In agreement with the published work, 10 estimates of cosmic-ray exposure ages based on ³⁸Ar concentrations average 17 ± 5 Ma but may include some early irradiation.     

Exploring the past through lynchet landscapes in the Vosges Mountains and the Lorraine Plateau (France)

Lynchets are ridges formed by erosion and sediment accumulation downstream of agricultural plots and offer valuable insights into past agricultural activity. These microtopographies cover vast areas and serve as indicators of historical changes in land use. As a result, their ubiquity across Europe makes them particularly interesting. In this study, we propose a geoarchaeological approach to analyze six lynchets, four in the Vosges Mountains and two on the Lorraine Plateau (France). The lynchets can be considered soil archives with no stratigraphic organization or chronological sequence from bottom to top, making it difficult to determine the age of the lynchets and identify changes in land use over time. To this end, we propose the analysis of historical and geo-historical archives combined with the “pedosedimentary” archives of lynchets through charcoal identification and dating combined with near-infrared spectroscopy to determine the age, vegetation, and past land use changes associated with lynchet landscapes. By combining these multiple data sources, we are better able to show the chronological development of these ancient agricultural systems and uncover valuable information on landscape history. Charcoal dating suggests a higher frequency of fires from the Middle Ages. The dating aligns with the regional dynamics of anthropogenic fires, indicating a potential use of fire for cultural purposes. We also demonstrate the difficulty of extrapolating the dating of a lynchet to the entire lynchet system. Our results highlight the difficulties of interpreting the formation and dating of lynchets and the lynchet system on the sole basis of charcoal analysis. However, we highlight the value of applying pedoanthracology to lynchets to determine the dynamics of land use change in former fields.