Oxidation inhibitors occuring in bioproducers, recent sediments, ancient rocks and oils

Native antioxidants (AO) are involved in the transformation of organic matter (OM) in different stages of diagenesis. In the early stages, the geochemical significance of AO can be estimated by using AO consumption index (I). The positive I values suggest that the OM fossilization proceeded under reducing conditions which favoured the formation of oil-source rocks, while the negative I values indicate oxidizing conditions which are characterized by the formation of rocks having a low oil-generation potential. In the late stages of diagenesis, the AO content is indicative of the degree of catagenic (thermal) or biodegradation (oxidative) transformation of oils. The AO contents of Paleogenic, Mesozoic and Paleozoic oils have been found to differ approximately by one order of magnitude. A major portion of AO is concentrated in oil resins and asphaltenes. The ratio of AO to resins and asphaltenes can be used as criterion of catagenic transformation of OM.     

3D subsidence analyses above gas reservoirs accounting for an unconventional plasticity model

The coupled hydro‐mechanical state in soils coming from consolidation/subsidence processes and undergoing plasticity phenomena is here evaluated by means of the subloading surface model. The most important feature of this theory is the abolition of the distinction between the elastic and plastic domains, as it happens in the conventional elastoplastic models. This means that plastic deformations are generated whenever there is a change in stress and a smoother elastoplastic transition is produced. The plasticity algorithm has been implemented in the PLASCON3D FE code, coupling hydro‐thermo‐mechanical fields within a saturated (locally partially saturated) porous medium subjected to external loads and water/gas withdrawals from deep layers (aquifers/reservoirs). The 3D model has been first calibrated and validated against examples taken from the literature, and then subsidence analyses at regional scales due to gas extractions have been developed to predict the evolution of settlements and pore pressure in soils for long‐term scenarios. Copyright © 2011 John Wiley & Sons, Ltd.     

Quantitative biome reconstruction using modern and late Quaternary pollen data from the southern part of the Russian Far East

In this study we present a recent compilation of 286 modern surface pollen spectra from the southern part of the Russian Far East (42–54°N, 131–141°E) and use it to test the biome reconstruction method. Seventy terrestrial pollen taxa were assigned to plant functional types and then classified to eight regional biomes. When applied to 286 surface pollen spectra, the method assigns about 70% (201 sites) of the samples to the cool mixed forest biome, 17% – to the taiga, 2% – to the cool conifer forest, 3% – to the temperate deciduous forest, and 7% – to the steppe. The steppe reconstruction is characteristic of the pollen spectra from the agricultural areas around Lake Khanka. A visual comparison shows good agreement between pollen-derived biomes and actual vegetation distribution in the region. However, pollen and botanical data, compared with the potential vegetation distribution simulated from the modern climate dataset using the BIOME1 model, demonstrate that spatial distribution of cool mixed forest is underrepresented in the model simulation. The model sets the mean temperature of the coldest month of −15 °C as the factor limiting distribution of the temperate deciduous broadleaf taxa, while vegetation and pollen data from the region demonstrate that this limit should be lowered to −26 °C. Application of the method to the Gur 3–99 pollen record (50°00^′N, 137°03^′E) demonstrates that tundra vegetation predominated around the site prior to 14 ka BP (1 ka = 1000 cal. years). However, the local presence of boreal trees and mixed forest-tundra vegetation is suggested by relatively high taiga scores. Soon after 14 ka BP the scores of taiga become slightly higher than tundra scores. During 11.4–10.5 ka BP a cool conifer forest is reconstructed. Establishment of the full interglacial conditions is marked by the onset of cool mixed forest by 10.5 ka BP. Between 10.3 and 2.5 ka BP the scores of temperate deciduous forest are close to those of cool mixed forest and become distinctly lower during the late Holocene.     

New Olivine Reference Material for In Situ Microanalysis

A new olivine reference material – MongOL Sh11‐2 – for in situ analysis has been prepared from the central portion of a large (20 × 20 × 10 cm) mantle peridotite xenolith from a ~ 0.5 My old basaltic breccia at Shavaryn‐Tsaram, Tariat region, central Mongolia. The xenolith is a fertile mantle lherzolite with minimal signs of alteration. Approximately 10 g of 0.5–2 mm gem quality olivine fragments were separated under binocular microscope and analysed by EPMA, LA‐ICP‐MS, SIMS and bulk analytical methods (ID‐ICP‐MS for Mg and Fe, XRF, ICP‐MS) for major, minor and trace elements at six institutions world‐wide. The results show that the olivine fragments are sufficiently homogeneous with respect to major (Mg, Fe, Si), minor and trace elements. Significant inhomogeneity was revealed only for phosphorus (homogeneity index of 12.4), whereas Li, Na, Al, Sc, Ti and Cr show minor inhomogeneity (homogeneity index of 1–2). The presence of some mineral and fluid‐melt micro‐inclusions may be responsible for the inconsistency in mass fractions obtained by in situ and bulk analytical methods for Al, Cu, Sr, Zr, Ga, Dy and Ho. Here we report reference and information values for twenty‐seven major, minor and trace elements.     

Improved Monte Carlo inversion of surface wave data

Inversion of surface wave data suffers from solution non‐uniqueness and is hence strongly biased by the initial model. The Monte Carlo approach can handle this non‐uniqueness by evidencing the local minima but it is inefficient for high dimensionality problems and makes use of subjective criteria, such as misfit thresholds, to interpret the results. If a smart sampling of the model parameter space, which exploits scale properties of the modal curves, is introduced the method becomes more efficient and with respect to traditional global search methods it avoids the subjective use of control parameters that are barely related to the physical problem. The results are interpreted drawing inference by means of a statistical test that selects an ensemble of feasible shear wave velocity models according to data quality and model parameterization. Tests on synthetic data demonstrate that the application of scale properties concentrates the sampling of model parameter space in high probability density zones and makes it poorly sensitive to the initial boundary of the model parameters. Tests on synthetic and field data, where boreholes are available, prove that the statistical test selects final results that are consistent with the true model and which are sensitive to data quality. The implemented strategies make the Monte Carlo inversion efficient for practical applications and able to effectively retrieve subsoil models even in complex and challenging situations such as velocity inversions.     

The impact of glaciation, river-discharge and sea-level change on Late Quaternary environments in the southwestern Kara Sea

Sedimentary records from the southwestern Kara Sea were investigated to better understand the extent of the last glaciation on the Eurasian Arctic shelf, sea-level change, and history of the Ob' and Yenisey river discharge. Sediment-core and seismic-reflection data indicate that the Quaternary depositional sequence in the southwestern Kara Sea consists of glacial, glaciomarine, and marine sedimentary units. Glaciogenic sediments in the deep Novaya Zemlya Trough are presumably related to the Last Glacial Maximum (LGM), whereas further east they may represent an earlier glaciation. Thus, it is inferred that the southeastern margin of the LGM Barents-Kara ice sheet was contained in the southwestern Kara Sea east of the Novaya Zemlya Trough. Changes in mineralogical, foraminiferal, and stable-isotopic composition of sediment cores indicate that riverine discharge strongly influenced sedimentary and biotic environments in the study area during the Late Weichselian and early Holocene until ca. 9 ka, consistent with lowered sea levels. Subsequent proxy records reflect minor changes in the Holocene hydrographic regime, generally characterized by reduced riverine inputs.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

The distribution of trace metals in Florida Bay sediments

The distribution of trace metals based on surface sediments collected at 40 stations across Florida Bay was done in June, November and February 2000-2001. Concentrations of Sc, V, Ba, Cd, Cr, Co, Cu, Pb, Mn, Ni, Zn, Al and Mg were determined by ICP-MS, and the total Fe was determined by spectrophotometry. Organic carbon (OC), nitrogen (N), and calcium carbonate (CaCO3) were also measured. Eleven of 13 metals showed a similar distribution pattern for the various months studied. Maximum concentrations of metals were lower than those found in most estuarine systems and were concentrated in the north-central and western zones of the Bay. The Mn and Fe concentrations, unlike the other metals, gradually decreased from north (Everglades) to south (Florida Keys). Some metals (Ni, Zn, Cu, Cr, Pb and Ba) associated with petroleum use showed high concentrations at stations near the Tavernier marina. Florida Bay sediments are predominately CaCO3 (65.9-92.5%). The greatest value for OC (5.5%) and the lowest value of CaCO3 (65.9%) were found in the western zone. Trace metal distribution patterns are similar to the OC and N in the sediments. There was a strong correlation between most metals (V>Cu>Ni>Cr>Al>Co>Ba>Zn>Pb>Mg) and the percentage of OC. The maximum C/N values (9-12) were observed at the stations with the highest OC, where dense colonies of seagrass are found and most of the metals are concentrated. All metals except Mg, Mn and Co showed a strong correlation with Al and the fine fraction of the sediments (aluminosilicates) associated with continental input and river runoff.     

Effects of climate, invasive species and anthropogenic impacts on the growth of the seagrass Posidonia oceanica (L.) Delile in Liguria (NW Mediterranean Sea)

Eight shallow water Posidonia oceanica meadows were sampled in June 1999 along 300 km of the Ligurian coast and were compared through shoot density and lepidochronology. The growth of the seagrass was examined in the light of climate fluctuations and local stresses, colonisation by alien, invasive alga Caulerpa taxifolia, and effects of the oil spill from the tanker "Haven", and other anthropogenic impacts. Both shoot density and lepidochronology pointed to a generalised state of regression of all the meadows. The analysis of long-term growth curves of the rhizomes showed a positive trend parallel to the increase of air temperature. Two main groups of meadows were individuated on the basis of growth curve similarity. The first included four meadows, namely Ventimiglia, Imperia, Noli and Prelo, that were characterised by average values of rhizome growth of 8-9.1 mmyear(-1) and shoot density greater than 200 shootsm(-2). Although the Imperia meadow was the only one where the alien invasive alga C. taxifolia was found, it did not show differences for rhizome growth in comparison to the other meadows. The second group was formed by meadows that had suffered past anthropogenic impacts: Arenzano and Monterosso al Mare. They showed higher rhizome growth rates (9.4-10.6 mmyear(-1)) and shoot densities between 200 and 100 shootsm(-2). At Arenzano, where "Haven" oil was stranded in April 1991, no rhizome older than 8 years was found, thus confirming the shoot mortality induced by the oil spill event. The two last meadows exhibited growth curves very different from all the others: Portovenere, is a shallow meadow where P. oceanica merely survives in an extremely degraded situation with highest rhizome growth rate (12 mmyear(-1)), the other, Riva Trigoso, is the only meadow implanted on rock and had the lowest growth rates (7.1 mm year(-1)).