Volcanic resurfacing and the early terrestrial crust: Zircon U-Pb and REE constraints from the Isua Greenstone Belt, southern West Greenland

The oldest known bona fide succession of clastic metasediments occurs in the Isua Greenstone Belt, SW Greenland and consists of a variety of mica schists and rare metaconglomerates. The metasediments are in direct contact with a felsic metavolcanic lithology that has previously been dated to 3.71 Ga. Based on trace element geochemical data for > 30 metasediments, we selected the six samples with highest Zr concentrations for zircon extraction. These samples all yielded very few or no zircon. Those extracted from mica schists yielded ion probe U/Pb ages between 3.70 and 3.71 Ga. One metaconglomerate sample yielded just a single zircon of 3.74 Ga age.The mica schist hosted zircons have U/Pb ages, Th / U ratios, REE patterns and Eu anomalies indistinguishable from zircon in the adjacent 3.71 Ga felsic metavolcanic unit. Trace element modelling requires the bulk of material in the metasediments to be derived from variably weathered mafic lithologies but some metasediments contain substantial contribution from more evolved source lithologies. The paucity of zircon in the mica schists is thus explained by incorporation of material from largely zircon-free volcanic lithologies. The absence of older zircon in the mica schists and the preponderance of mafic source material imply intense, mainly basaltic resurfacing of the early Earth. The implications of this process are discussed.Thermal considerations suggest that horizontal growth of Hadean crust by addition of mafic-ultramafic lavas must have triggered self-reorganisation of the protocrust by remelting. Reworking of Hadean crust may have been aided by burial of hydrated (weathered) metabasalt due to semi-continuous addition of new voluminous basalt outpourings. This process causes a bias towards eruption of Zr-saturated partial melts at the surface with O-isotope compositions potentially different from the mantle. The oldest zircons hosted in sediments would have been buried to substantial depth or formed in plutons that crystallised at some depth, from which it took hundreds of millions of years for them to be exhumed and incorporated into much younger sediments.     

Histogram and variogram inference in the multigaussian model

Several iterative algorithms are proposed to improve the histogram and variogram inference in the framework of the multigaussian model. The starting point is the variogram obtained after a traditional normal score transform. The subsequent step consists in simulating many sets of gaussian values with this variogram at the data locations, so that the ranking of the original values is honored. The expected gaussian transformation and the expected variogram are computed by an averaging operation over the simulated datasets. The variogram model is then updated and the procedure is repeated until convergence. Such an iterative algorithm can adapt to the case of tied data and despike the histogram. Two additional issues are also examined, referred to the modeling of the empirical transformation function and to the optimal pair weighting when computing the sample variogram.     

Compositional variations (major and trace elements) of clinopyroxene and Ti-andradite from pyroxenite, ijolite and nepheline syenite, Alnö Island, Sweden

Clinopyroxenes from pyroxenite, ijolite and nepheline syenite from the main intrusion of the Alnö complex define two sub-parallel compositional trends with respect to Na, Ca and Fe_TOT plotted against alkali-pyroxene fractionation index (Na–Mg). Both trends define a smooth fractionation of increasing Na and Fe_TOT and decreasing Ca with increasing Na–Mg, but one set of samples contain clinopyroxenes that constantly plot at higher Na and lower Fe_TOT and Ca (at similar Na–Mg) than the rest of the samples. Clinopyroxenes with higher Ca and Fe_TOT and lower Na (trend 1) co-exist with substantial amounts of Ti-andradite (up to 70 vol.%), while the sample set defining the more Na-rich trend (trend 2) lack co-existing Ti-andradite. Clinopyroxenes from both trends show fractionated REE patterns with a distinct difference in HREE content, reflecting the content of co-existing Ti-andradite. The rocks of the first Ti-andradite-bearing trend crystallized slightly prior to the rocks of the second trend, probably from a primitive, Ca- and Ti-rich nephelinitic magma. Crystallisation of pyroxenite and melteigite occurred under low aSiO₂ and high aCaO and aTiO₂ as evidenced by the presence of perovskite and sometimes substantial amounts of magnetite. Subsequent increase in aSiO₂ is evidenced in the overgrowth of perovskite by titanite, which in turn is overgrown by Ti-andradite. Nepheline syenitic residuals crystallized under higher aSiO₂ and aNa₂O and lower aCaO and aTiO₂, which reduced Ti-andradite into an accessory phase and produced more Si- and Na-rich clinopyroxenes. Some of these residuals probably also mixed with new primitive magma producing a hybrid magma that crystallised the more Na-rich and Ca- and Fe_TOT-poor clinopyroxenes of trend 2. The complete lack of Ti-andradite in these rocks indicates different crystallisation conditions and also a different magma composition.     

Geochemical characteristics of mineral air particles emitted inside a clay atomisation plant which introduces waste recycling processes

The objective of this work is to assess the concentrations of three factions of air particles (settable particles, TSP and PM10) and the levels of several toxic elements in a clay atomisation industry through aerosol sampling at several points inside an industrial plant. Mechanical activities, which produce diffuse emissions, are the main process of discharge of particles in both indoor and outdoor workplace environments in the atomisation plant. The levels of As, Cd, Pb, Zn, Ba and Ni increase in the zones with higher concentrations of particles and lower ventilation. The concentrations of As and F are not influenced by the recycling processes. The levels of Cd and Pb do not show great enrichment in air particles collected inside the atomisation plant although the content of both elements is associated with ceramic muck recycling. Finally, the content of B in waste water is mainly transferred in gaseous phase to the atmosphere during the process of drying by atomisation.     

A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.     

Modeling the impact of microbial activity on redox dynamics in porous media

The present study investigates the interaction between microbial growth and activity and the redox dynamics in natural porous media. The impact the transport regime has on this interaction is also addressed. Expressions for microbial growth are incorporated into a geochemical reaction network linking redox reaction rates to the activity of the microorganisms. A flexible simulation environment, the Biogeochemical Reaction Network Simulator (BRNS) is used for this purpose. Two reactive transport applications relevant to fields of contaminant hydrology and early diagenesis are simulated with the BRNS. Model results are evaluated based on a comparison with comprehensive datasets on the biodegradation of lactate in a sand column experiment and on the distribution of redox-sensitive chemical species in marine sediments of the Skagerrak, Denmark. It is shown that, despite quite different transport regimes, the geomicrobiological model performs equally well in the reproduction of measured chemical species distribution for both applications. This result emphasizes the broad applicability of the proposed approach. Our simulations support that the competitive behavior between various microbial groups is a process controlling the development of redox stratified environments. Furthermore, it is also shown that the transport regime is a key controlling factor for the degree of spatial correlation between microbial biomass distributions and redox reaction rates. Although all our simulations yield a pronounced stratification of the redox processes in the system, the biomass distribution is related to the associated reaction rates only in case of the advection controlled column experiment. In the early diagenetic application, mixing due to bioturbation is the dominant transport process for particulate matter, hence leading to fairly homogeneous distribution of bacterial biomasses which are unrelated to the spatial distribution of redox reaction rates. This homogeneous biomass distribution combined with the 1G carbon degradation model approach might explain why the steady state concentration profiles in such systems can be reproduced by diagenetic models without explicit representation of microbial growth.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.