Quantifying time scales of pedogenic calcrete formation using U-series disequilibria

Time scales of pedogenic calcrete development are quantified by subsampling carbonate from within a mature (stage V) pedogenic calcrete profile from southeast Spain and dating the material by U-series disequilibria. The location of the earliest and latest cements can be estimated by comparing previous studies of calcrete morphological development with micromorphological analysis of the study profile. Carbonate was sampled and dated from three locations within the profile: (1) below the lower surface of clasts within the hardpan (representing the earliest cement present-207 +/- 11 ka), (2) from the centre of cement filled pores within the hardpan (reflecting the final plugging of the calcrete hardpan-155 +/- 9 ka) and (3) from the laminar calcrete overlying the hardpan (representing the latest cement-112 +/- 15 ka). These results show that the hardpan took between 73 and 31 ka to form, whilst the mature stage V profile took between 121 and 69 ka to form. This is the first time that rates of mature calcrete development have been established by direct radiometric dating of the authigenic carbonate. The technique is appropriate for dating mature calcretes in dryland regions worldwide and offers the opportunity of increasing our understanding of the spatial and temporal variability in rates of pedogenic calcrete development. (C) 2004 Elsevier B.V. All rights reserved.

Vegetation and environmental dynamics in the southern Black Sea region since 18 kyr BP derived from the marine core 22-GC3

Sediments from the Black Sea, a region historically dominated by forests and steppe landscapes, are a valuable source of detailed information on the changes in regional terrestrial and aquatic environments at decadal to millennial scales. Here we present multi-proxy environmental records (pollen, dinoflagellate cysts, Ca, Ti and oxygen isotope data) from the uppermost 305 cm of the core 22-GC3 (42°13.53′N, 36°29.55′E) collected from a water depth of 838 m in the southern part of the Black Sea in 2007. The records span the last ~ 18 kyr (all ages are given in cal kyr BP). The pollen data reveal the dominance of the Artemisia-steppe in the region, suggesting rather dry/cold environments ~ 18–14.5 kyr BP. Warming/humidity increase during melt-water pulses (~ 16.1–14.5 kyr BP), indicated by δ18O records from the 22-GC3 core sediment and from the Sofular Cave stalagmite, is expressed in more negative δ13C values from the Sofular Cave, usually interpreted as the spreading of C3 plants. The records representing the interstadial complex (~ 14.5–12.9 kyr BP) show an increase in temperature and moisture, indicated by forest development, increased primary productivity and reduced surface run-off, whereas the switch from primary terrigenous to primary authigenic Ca origin occurs ~ 500 yr later. The Younger Dryas cooling is clearly demonstrated by more negative δ13C values from the Sofular Cave and a reduction of pines. The early Holocene (11.7–8.5 kyr BP) interval reveals relatively dry conditions compared to the mostly moist and warm middle Holocene (8.5–5 kyr BP), which is characterized by the establishment of the species-rich warm mixed and temperate deciduous forests in the low elevation belt, temperate deciduous beech-hornbeam forests in the middle and cool conifer forest in upper mountain belt. The border between the early and middle Holocene in the vegetation records coincides with the opening of the Mediterranean corridor at ~ 8.3 kyr BP, as indicated by a marked change in the dinocyst assemblages and in the sediment lithology. Changes in the pollen assemblages indicate a reduction in forest cover after ~ 5 kyr BP, which was likely caused by increased anthropogenic pressure on the regional vegetation.

A high resolution late Holocene palaeo environmental record from the central Adriatic Sea

A multi-proxy study of a Holocene sediment core (RF 93-30) from the western flank of the central Adriatic, in 77 m of water, reveals a sequence of changes in terrestrial vegetation, terrigenous sediment input and benthic fauna, as well as evidence for variations in sea surface temperature spanning most of the last 7000 yr. The chronology of sedimentation is based on several lines of evidence, including AMS 14C dates of foraminifera extracted from the core, palaeomagnetic secular variation, pollen indicators and dated tephra. The temporal resolution increases towards the surface and, for some of the properties measured, is sub-decadal for the last few centuries. The main changes recorded in vegetation, sedimentation and benthic foraminiferal assemblages appear to be directly related to human activity in the sediment source area, which includes the Po valley and the eastern flanks of the central and northern Appenines. The most striking episodes of deforestation and expanding human impact begin around 3600 BP (Late Bronze Age) and 700 BP (Medieval) and each leads to an acceleration in mass sedimentation and an increase in the proportion of terrigenous material, reflecting the response of surface processes to widespread forest clearance and cultivation. Although human impact appears to be the proximal cause of these changes, climatic effects may also have been important. During these periods, signs of stress are detectable in the benthic foram morphotype assemblages. Between these two periods of increased terrigeneous sedimentation there is smaller peak in sedimentation rate around 2400BP which is not associated with evidence for deforestation, shifts in the balance between terrigenous and authigenic sedimentation, or changes in benthic foraminifera. The mineral magnetic record provides a sensitive indicator of changing sediment sources: during forested periods of reduced terrigenous input it is dominated by authigenic bacterial magnetite, whereas during periods of increased erosion, anti-ferromagetic minerals (haematite and/or goethite) become more important, as well as both paramagnetic minerals and super-paramagnetic magnetite. Analysis of the alkenone, U37k′, record provides an indication of possible changes in sea surface temperature during the period, but it is premature to place too much reliance on these inferred changes until the indirect effects of past changes in the depth of the halocline and in circulation have been more fully evaluated. The combination of methods used and the results obtained illustrate the potential value of such high resolution near-shore marine sedimentary sequences for recording wide-scale human impact, documenting the effects of this on marine sedimentation and fauna and, potentially, disentangling evidence for human activities from that for past changes in climate.

Rapid changes in the redox conditions of the western Tethys Ocean during the early Aptian oceanic anoxic event

The early Aptian (125 to 121 Ma) records an episode of severe environmental change including a major perturbation of the carbon cycle, an oceanic anoxic event (OAE 1a, 122.5 Ma), a platform drowning episode and a biocalcification crisis. We propose to trace changes in the oxygenation state of the ocean during the early Aptian anoxic event using the redox-sensitive trace-element (RSTE) distribution, phosphorus accumulation rates (PARs) and organic-matter characterization in three different basins of the western Tethys. The following sections have been investigated: Gorgo a Cerbara (central Italy) in the Umbria Marche basin, Glaise (SE France) in the Vocontian basin and Cassis/La Bédoule (SE France) located in the Provencal basin. In the Gorgo a Cerbara section, RSTE distributions show a low background level along the main part of the section, contrasted by different maxima in concentrations within the Selli level. In the Glaise section, the Goguel level displays a weak increase in RSTE contents coeval with moderate TOC values. At Cassis/La Bédoule, no significant RSTE enrichments have been observed in sediments equivalent to the Selli level. These differences in the records of the geochemical proxies of the Selli level or its equivalent indicate the deposition under different redox conditions, probably related to the paleogeography. Our data indicate the development of anoxic–euxinic conditions in the deeper part of the Tethys during OAE 1a, whereas in the shallower environments, conditions were less reducing. Moreover, at Gorgo a Cerbara, the Selli level is characterized by rapid changes in the intensity of reducing conditions in the water column. Ocean eutrophication seems to be a major factor in the development and the persistence of anoxia as suggested by the PAR evolution. Higher PAR values at the onset of OAE 1a suggest an increase in nutrient input, whereas the return to lower values through the first part of the OAE 1a interval may be related to the weakened capacity to retain P in the sedimentary reservoir due to bottom-water oxygen depletion. This general pattern is contrasted by the data of Gorgo a Cerbara, where the sediments deposited during the OAE 1a interval show P-enrichments (mainly authigenic P). This is associated with maxima in TOC values and Corg:Ptot ratios, suggesting that a part of the remobilized P was trapped in the sediments and as such prevented from returning to the water column.

Paleomagnetism and rock magnetism of the Neoproterozoic Itajai Basin of the Rio de la Plata craton (Brazil): Cambrian to Cretaceous widespread remagnetizations of South America

A detailed rock magnetic and paleomagnetic study was performed on samples from the Neoproterozoic Itajai Basin in the state of Santa Catarina, Brazil, in order to better constrain the paleogeographic evolution of the Rio de la Plata craton between 600 and 550 Ma. However, rock magnetic properties typical of remagnetized rocks and negative response in the fold test indicated that these rocks carried a secondary chemical remanent magnetization. After detailed AF and thermal cleaning, almost all samples showed a normal polarity characteristic remanent magnetization component close to the present geomagnetic field. The main magnetic carriers are magnetite and hematite, probably of authigenic origin. The mean paleomagnetic pole of the ltajai Basin is located at Plat= -84 degrees, Plong = 97.5 degrees (A95 = 2 degrees) and overlaps the lower Cretaceous segment of the apparent polar wander path of South America, suggesting a cause and effect with the opening of the South Atlantic Ocean. A compilation of remagnetized paleomagnetic poles from South America is presented that highlights the superposition of several large-scale remagnetization events between the Cambrian and the Cretaceous. It is suggested that some paleomagnetic poles used to calibrate the APWP of Gondwana at Precambrian times need to be revised; the indication of remagnetized areas in southern South America may offer some help in the selection of sites for future paleomagnetic investigations in Precambrian rocks. (C) 2011 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Closing the Clymene ocean and bending a Brasiliano belt: Evidence for the Cambrian formation of Gondwana, southeast Amazon craton

We report new paleomagnetic and geochronological data from Ediacaran rift-drift carbonates in the Paraguai belt at the southern end of the suture zone between the Amazon craton and the Sao Francisco and Rio de Plata cratons, South America. Early thrusting resulted in remagnetization ca. 528 +/- 36 Ma or later; the mean age is established by (40)Ar/(39)Ar encapsulation dating of mixed authigenic and detrital illite from remagnetized carbonates from the unmetamorphosed fold-thrust belt. This remagnetization overlaps with a 525 Ma Gondwana reference pole. Metamorphic illite from the slate belt yields (40)Ar/(39)Ar ages of 496-484 Ma, the timing of peak regional metamorphism. Oroclinal bending of the Paraguai belt was caused by a 90 degrees clockwise rotation of the east-west limb after ca. 528 Ma, probably reflecting the irregular margin of the southeast Amazon craton. The age of the Paraguai belt overlaps with that of the Pampean orogeny farther south along the western margin of the Rio de Plata craton, suggesting a coeval closure for the Clymene ocean separating the Amazon craton from the Sao Francisco and Rio de Plata cratons.

Relation between sedimentary framework and hydrogeology in the Guarani Aquifer System in Sao Paulo state, Brazil

This paper presents the results of a new investigation of the Guarani Aquifer System (SAG) in Sao Paulo state. New data were acquired about sedimentary framework, flow pattern, and hydrogeochemistry. The flow direction in the north of the state is towards the southwest and not towards the west as expected previously. This is linked to the absence of SAG outcrop in the northeast of Sao Paulo state. Both the underlying Piramboia Formation and the overlying Botucatu Formation possess high porosity (18.9% and 19.5%, respectively), which was not modified significantly by diagenetic changes. Investigation of sediments confirmed a zone of chalcedony cement close to the SAG outcrop and a zone of calcite cement in the deep confined zone. The main events in the SAG post-sedimentary history were: (1) adhesion of ferrugineous coatings on grains, (2) infiltration of clays in eodiagenetic stage, (3) regeneration of coatings with formation of smectites, (4) authigenic overgrowth of quartz and K-feldspar in advanced eodiagenetic stage, (5) bitumen cementation of Piramboia Formation in mesodiagenetic stage, (6) cementation by calcite in mesodiagenetic and telodiagenetic stages in Piramboia Formation, (7) formation of secondary porosity by dissolution of unstable minerals after appearance of hydraulic gradient and penetration of the meteoric water caused by the uplift of the Serra do Mar coastal range in the Late Cretaceous, (8) authigenesis of kaolinite and amorphous silica in unconfined zone of the SAG and cation exchange coupled with the dissolution of calcite at the transition between unconfined and confined zone, and (9) authigenesis of analcime in the confined SAG zone. The last two processes are still under operation. The deep zone of the SAG comprises an alkaline pH, Na-HCO(3) groundwater type with old water and enriched delta(13)C values (<-3.9), which evolved from a neutral pH, Ca-HCO(3) groundwater type with young water and depleted delta(13)C values (>-18.8) close to the SAG outcrop. This is consistent with a conceptual geochemical model of the SAG, suggesting dissolution of calcite driven by cation exchange, which occurs at a relatively narrow front recently moving downgradient at much slower rate compared to groundwater flow. More depleted values of delta(18)O in the deep confined zone close to the Parana River compared to values of relative recent recharged water indicate recharge occur during a period of cold climate. The SAG is a ""storage-dominated"" type of aquifer which has to be managed properly to avoid its overexploitation. (C) 2011 Elsevier Ltd. All rights reserved.

A história do intemperismo na Província Borborema Oriental, Nordeste do Brasil: implicações paleoclimáticas e tectônicas

Until some years ago, weathering geochronology was primarily based on the K-Ar and 40Ar/39Ar dating of supergene minerals. Recent advances in the analysis of supergene goethite by the (U-Th)/He method expanded the number of suitable minerals for such purpose, as well as the time of application for weathering geochronology. This study represents the first systematic approach in Brazil, combining both the 40Ar/39Ar e (U-Th)/He methodologies to improve the knowledge on the weathering and the age of nonfossiliferous sediments. Supported by geologic and geomorphologic correlations, we identified different types of weathering profiles occurring in the interior and coastal areas of northeastern Brazil. These profiles were correlated to main regional geomorphological domains: the Borborema Plateau , the Sertaneja Depression , and the Coastal Cuestas and Plains, and respective planation surfaces, which study is fundamental to understand the landscape evolution of the northern portion of the eastern Borborema Province. The depth and stratigraphic organization of the weathering profiles in each of the geomorphological domains permitted to establish that: (i) the profiles on the highlands that cap the Borborema Surface are deeper (up to 100 m) and can be considered as typical lateritic profiles; (ii) on the lowlands that form the Sertaneja Surface , the weathering profiles are shallow and poorly developed (2-5 m deep); (iii) the profiles along the coastal area are moderately developed (up to 25 m deep), and are characterized by thick saprolites and mottle zones. Aiming to establish the timing of the evolution of northeastern Brazil, we studied 29 weathering profiles representing distinct topographic levels of the Borborema Province, from the highlands to the coast, through the analysis of 248 grains of supergene manganese oxides using laser step-heating 40Ar/39Ar geochronology. Additionally, we applied the (U-Th)/He method in 20 weathering profiles, by dating 171 grains of supergene iron oxides and hydroxides. Geochronological results for 248 grains of manganese oxides analyzed by the 40Ar/39Ar method indicate that the weathering profiles in the study area record the history of weathering from the Oligocene to the Pleistocene, with ages in the order of 31.4 ± 1.0 Ma to 0.8 ± 0.4 Ma. Dating of 171 grains of goethite by the (U-Th)/He method yielded ages ranging from 43.2 ± 4.3 Ma to 0.8 ± 0.1 Ma, suggesting the weathering processes last from the Eocene to the Pleistocene. The precipitation of supergene goethite in this interval confirms the age of the weathering processes identified from the manganese oxides record. 105 goethite grains from 8 different occurrences of the Barreiras Formation were dated by the (U-Th)/He method. Five grains collected from the cement in the Barreiras Formation sandstones, in the Lagoa Salgada and Rio do Fogo coastal cuestas, yielded ages of 17.6 ± 1.8 Ma, 17.3 ± 1.7 Ma, 16.3 ± 1.6 Ma, 16.2 ± 1.6 Ma and 13.6 ± 1.4 Ma. Results of 69 goethite grains from authigenic pisoliths collected in 7 different localities also yielded concordant ages, varying from 17.8 ± 1.8 to 7.5 ± 0.8 Ma. Results obtained from 31 detrital grains are concordant in 3 distinct localities (Lagoa Salgada, Praia da Garças e Ponta Grossa); they vary in the range of 43.2 ± 4.3 to 21.6 ± 2.2 Ma, and indicate that the maximum age for the Barreiras Formation deposition is around 22 Ma. 40Ar/39Ar results for 15 manganese oxides grains associated with the Barreiras Formation weathering profiles, in 3 different localities, vary from 13.1 ± 0.9 to 7.7 ± 0.4 Ma, in the same range of ages obtained by the (U-Th)/He method. The systematic application of the 40Ar/39Ar and (U-Th)/He methods, respectively for manganese oxides and goethites, show that the Barreiras Formation sediments were already deposited since ca. 17 Ma, and that the weathering processes were active until ca. 7 Ma ago. The ages obtained from manganese oxides collected in the Cenozoic basalts (Macau Formation) also reveal a weathering history between 19 and 7 Ma, pointing to hot and humid conditions during most of the Miocene. 40Ar/39Ar ages yielded by manganese oxides associated with the Serra do Martins Formation vary from 14.1 ± 0.4 to 10.5 ± 0.3 Ma. On the other hand, (U-Th)/He ages from iron oxides/hydroxides collected in the Serra do Martins Formation mesas vary from 20.0 ± 2.0 to 5.5 ± 0.6 Ma, indicating that those sediments are older than 20 Ma. 40Ar/39Ar and (U-Th)/He results produced in this study are in agreement with paleoclimatic interpretations based on stable isotopes and clay index values measured in the Atlantic Ocean sediments, validating the use of weathering geochronology to investigate paleoclimatic variations. The direct dating of the Barreiras Formation permitted, for the first time, confident inferences on the age of the brittle deformation recorded by this sedimentary unit in the Rio Grande do Norte and Ceará states. The first event, syn-deposition, occurred during the early Miocene; an younger event, related to the post-depositional deformation of the Barreiras Formation, is associated with tectonic activity from the very early Miocene to the Holocene. In agreement with data from other areas, results obtained in this study reveal that the depth and complexity of the weathering profiles reflect the time of exposition of such areas to the weathering agents close to the surface. However, there is no clear relationship between ages vs. altitude. The depth and the stratigraphic organization of weathering profiles in northeastern Brazil, contrary to the southeastern Brazil pattern, do not vary toward the coast. In our study area, field observations reveal the presence of ancient, thick and complex lateritic profiles preserved in the sedimentary mesas on the Borborema Plateau, as younger, narrow and incipient ones occur in the dissected areas. Geochronological results obtained for these profiles yielded older ages on the high altitudes, and younger ages in the lowlands, suggesting the scarp retreatment is the most reliable model to explain the regional landscape evolution. However, in the coastal lowlands, the relatively older ages obtained indicate that more complexes processes were involved in the modeling of the local relief

Proveniência de arenitos albianos (Grupo Itapecuru), borda leste da bacia de São Luís-Grajaú, Maranhão, usando análise de minerais pesados e química mineral

Depósitos albianos da bacia de São Luís-Grajaú, antigamente conhecidos apenas em subsuperfície como ‘Unidade Indiferenciada’ do Grupo Itapecuru, foram recentemente encontrados ao longo do rio Itapecuru, na parte leste desta bacia. São argilitos avermelhados, esverdeados a cinzas, arenitos estratificados e maciços e subordinadamente calcários, interpretados como depósitos de delta progradante para ENE/E e ESE e conectado a uma plataforma restrita. Para determinar a proveniência de arenitos albianos, foram coletadas 18 amostras para estudos de minerais pesados (fração 0,062-0,125 mm) usando-se microscópio petrográfico convencional e microscópio eletrônico de varredura. Os arenitos foram classificados como quartzo-arenito moderadamente a bem selecionado, cimentado por dolomita, cujos principais minerais pesados são zircão (4-70%), granada (12-74%), turmalina (3-20%), estaurolita (1-9%), rutilo (1-8%) e barita (0-55%), enquanto cianita, anatásio (autigênico), anfibólio (hornblenda), andaluzita, sillimanita, espinélio e ilmenita ocorrem raramente. A maioria dos grãos é irregular angulosa, mas grãos bem arredondados, particularmente de turmalina e zircão, também estão presentes. Texturas superficiais incluem fraturas conchoidais, marcas de percussão em V e pequenos buracos, estes últimos em grãos arredondados de turmalina e zircão, enquanto feições de corrosão estão principalmente presentes em barita (cavidades rômbicas), cianita, estaurolita (superfície mamilar) e granada (facetas bem formadas por dissolução). Grãos de zircão, com texturas de zoneamento oscilatório e razões U/Th ≥ 0,5 e Zr/Hf média de 29, indicam proveniência de granitos e migmatitos, enquanto os tipos de turmalina, determinados como dravita e shorlita, são oriundos, principalmente, de metapelitos e metapsamitos aluminosos e/ou pobres em Al, com menor contribuição de granitos e rochas meta-ultramáficas. As granadas, por sua vez, são ricas em almandina e têm baixos teores dos componentes de espessartita, grossulária e piropo. Suas fontes potenciais são rochas metamórficas de baixo a médio grau e granitos. Com base em análises de minerais pesados e progradação do sistema deltaico para ENE/E e ESE, as áreas mais prováveis como fontes potenciais de arenitos albianos são o cráton São Luís, os cinturões neoproterozóicos Araguaia e Gurupi, bem como a bacia paleozóica do Parnaíba, esta fornecendo sedimentos de grãos arredondados.

Records of sedimentary dynamics in the continental shelf and upper slope between Aveiro-Espinho (N Portugal)

The sedimentary unconsolidated cover of the Aveiro-Espinho continental shelf and upper slope (NW Portugal) records a complex interplay of processes including wave energy and currents, fluvial input, sediment transport alongshore and cross-shelf, geological and oceanographic processes and sediment sources and sinks. In order to study this record, a set of surface sediment samples was studied. Sediment grain size and composition, as well as the mineralogical composition (by XRD) of the fine (<63 mu m) and clay (<2 mu m) fractions and benthic microfaunal (foraminifera) data were analysed. Cluster analysis applied to the sedimentological data (grain size, sediment composition and mineralogy) allowed the establishment of three main zones corresponding to the: inner-, mid- and outer-shelf/upper slope. On the inner-shelf, the sedimentary coverture is composed of siliciclastic fine to very fine sand, essentially comprising modern (immature) terrigenous particles. The sediment grain size, as well as mineralogical and microfaunal composition, denote the high energetic conditions of this sector in which the alongshore transport of sand is predominantly southward and occurs mostly during the spring-summer oceanographic regime, when the main river providing sediments to this area, the River Douro, undergoes periods of drought. This effect may emphasize the erosive character of this coastal sector at present, since the Ria de Aveiro provides the shelf with few sediments. On the mid-shelf, an alongshore siliciclastic band of coarse sand and gravel can be found between the 40 m and 60 m isobaths. This gravelly deposit includes relic sediments deposited during lower sea-level stands. This structure stays on the surface due to the high bottom energy, which promotes the remobilization of the fine-grained sediments, and/or events of sediments bypassing. Benthic foraminifera density and "Benthic Foraminifera High Productivity" (BFHP) proxy values are in general low, which is consistent with the overall small supply of organic matter to the oceanic bottom in the inner- and mid-shelf. However, the Ria de Aveiro outflow, which delivers organic matter to the shelf, leaves its imprint mainly on the mid-shelf, identifiable by the increase in foraminifera density and BFHP values in front of the lagoon mouth. The higher values of BFHP along the 100 m isobath trace the present position of an oceanic thermal front whose situation may have changed in the last 3/5 ka BP. This zone marks a clear difference in the density, diversity and composition of benthic foraminifera assemblages. Here, in addition, sediment composition changes significantly, giving rise to carbonate-rich fine to medium sand in the deeper sector. The low bottom energy and the small sedimentation rate of the outer-shelf contributed to the preservation of a discontinuous carbonate-rich gravel band, between the 100 m and 140 m isobaths, also related to paleo-littorals, following the transgression that has occurred since the Last Glacial Maximum. The winter oceanographic regime favours the transport of fine grained sediments to the outer-shelf and upper slope. The inner- and mid-shelf, however, have low amounts of this kind of sediment and the Cretacic carbonated complexes Pontal da Galega and Pontal da Cartola, rocky outcrops located at the mid- and outer-shelf, act as morphological barriers to the cross-shelf transport of sediments. Thus a reduced sedimentation rate occurs in these deeper sectors, as indicated by the lower abundance of detrital minerals, which is compensated for the high sedimentary content of biogenic carbonates. The relatively high BFHP and Shannon Index values indicate water column stratification, high supply of organic matter and environmental stability, which provide favourable conditions for a diversified benthic fauna to flourish. These conditions also encourage authigenic chemical changes, favourable to glauconite formation, as well as illite and kaolinite degradation. Benthic foraminifera and clay mineral assemblages also reveal the effect of the internal waves pushing upward, and downslope losses of the sediments on the outer-shelf and upper slope.

Molybdenum isotope fractionation in pelagic euxinia: Evidence from the modern Black and Baltic Seas

Here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the Black Sea and two deeps of the Baltic Sea. Dissolved molybdenum in all water samples is depleted in salinity-normalized concentration and enriched in the heavy isotope (δ98Mo values up to + 2.9‰) compared to previously published isotope data of sedimentary molybdenum from the same range of water depths. Furthermore, δ98Mo values of all water samples from the Black Sea and anoxic deeps of the Baltic Sea are heavier than open ocean water. The observed isotope fractionation between sediments and the anoxic water column of the Black Sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions. An extrapolation to a theoretical pure MoS42− solution indicates a fractionation constant between MoS42− and authigenic solid Mo of 0.5 ± 0.3‰. Measured waters with all thiomolybdates coexisting in various proportions show larger but non-linear fractionation. The best explanation for our field observations is Mo scavenging by the thiomolybdates, dominantly — but not exclusively — present in the form of MoS42−. The Mo isotopic compositions of samples from the sediments and anoxic water column of the Baltic Sea are in overall agreement with those of the Black Sea at intermediate depth and corresponding sulphide concentrations. The more dynamic changes of redox conditions in the Baltic deeps complicate the Black Sea-derived relationship between thiomolybdates and Mo isotopic composition. In particular, the occasional flushing/mixing, of the deep waters, affects the corresponding water column and sedimentary data. δ98Mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations. The results can be explained by non-conservative behaviour of Mo under suboxic to anoxic conditions in the shallow bottom parts of the basin, most pronounced on the NW shelf of the Black Sea.

Dynamics of the last four glacial terminations recorded in Lake Van, Turkey

A well-dated suite of Lake Van climate-proxy data covering the last 360 ka documents environmental changes over 4 glacial/interglacial cycles in Eastern Anatolia, Turkey. The picture of cold and dry glacials and warm and wet interglacials emerging from pollen, organic carbon, authigenic carbonate content, elemental profiling by XRF and lithological analyses is inconsistent with classical interpretation of ox- ygen isotopic composition of carbonates pointing to a more complex pattern in Lake Van region. Detailed analysis of glacial terminations allows for the constraining of a depositional model explaining different patterns observed in all the proxies. We hypothesize that variations in relative contribution of rainfall, snowmelt and glacier meltwater recharging the basin have a very important role for all sedimentary processes in Lake Van. Lake level of glacial Lake Van, predominantly fed by snowmelt, was low, the water column was oxic, and carbonates precipitating in the epilimnion recorded the light isotopic signature of inflow. During terminations, increasing rainfall and significant supply of mountain glaciers' meltwater contributed to lake level rise. Increased rainfall enhanced density gradients in the water column, and hindered mixing leading to development of bottom-water anoxia. Carbonates precipitating during terminations show large fluctuations in their isotopic composition. Full interglacial conditions in Lake Van are characterized by high or slowly falling lake level. Rainfall and snowmelt feed the lake but due to re-established mixing, the isotopic composition of authigenic carbonates is heavier and closer to that of evaporation-influenced lake water than that of runoff representing snowmelt and atmospheric precipitation.

Provenance versus weathering control on the composition of tropical river mud (southern Africa)

This study presents an integrated mineralogical-geochemical data base on fine-grained sediments transported by all major rivers of southern Africa, including the Zambezi, Okavango, Limpopo, Olifants, Orange and Kunene. Clay mineralogy, bulk geochemistry, Sr and Nd isotopic signatures of river mud, considered as proxy of suspended load, are used to investigate the influence of source-rock lithology and weathering intensity on the composition of clay and silt produced in subequatorial to subtropical latitudes. Depletion in mobile alkali and alkaline-earth metals, minor in arid Namibia, is strong in the Okavango, Kwando and Upper Zambezi catchments, where recycling is also extensive. Element removal is most significant for Na, and to a lesser extent for Sr. Depletion in K, Ca and other elements, negligible in Namibia, is moderate elsewhere. The most widespread clay minerals are smectite, dominant in muds derived from Karoo or Etendeka flood basalts, or illite and chlorite, dominant in muds derived from metasedimentary rocks of the Damara Orogen or Zimbabwe Craton. Kaolinite represents 30-40% of clay minerals only in Okavango and Upper Zambezi sediments sourced in humid subequatorial Angola and Zambia. After subtracting the effects of recycling and of local accumulation of authigenic carbonates in soils, the regional distribution of clay minerals and chemical indices consistently reflect weathering intensity primarily controlled by climate. Bulk geochemistry identifies most clearly volcaniclastic sediments and mafic sources in general, but cannot discriminate the other sources of detritus in detail. Instead, Sr and Nd isotopic fingerprints are insensitive to weathering, and thus mirror faithfully the tectonic structure of the southern African continent. Isotopic tools thus represent a much firmer basis than bulk geochemistry or clay mineralogy in the provenance study of mudrocks.

Diagenesis of a light, tight-oil chert reservoir at the Ediacaran/Cambrian boundary, Sultanate of Oman

The Al Shomou Silicilyte Member (Athel Formation) in the South Oman Salt Basin shares many of the characteristics of a light, tight-oil (LTO) reservoir: it is a prolifi c source rock mature for light oil, it produces light oil from a very tight matrix and reservoir, and hydraulic fracking technology is required to produce the oil. What is intriguing about the Al Shomou Silicilyte, and different from other LTO reservoirs, is its position related to the Precambrian/Cambrian Boundary (PCB) and the fact that it is a ‘laminated chert‘ rather than a shale. In an integrated diagenetic study we applied microstructural analyses (SEM, BSE) combined with state-of-the-art stable isotope and trace element analysis of the silicilyte matrix and fractures. Fluid inclusion microthermometry was applied to record the salinity and minimum trapping temperatures. The microstructural investigations reveal a fi ne lamination of the silicilyte matrix with a mean lamina thickness of ca. 20 μm consisting of predominantly organic matter-rich and fi nely crystalline quartz-rich layers, respectively. Authigenic, micron-sized idiomorphic quartz crystals are the main matrix components of the silicilyte. Other diagenetic phases are pyrite, apatite, dolomite, magnesite and barite cements. Porosity values based on neutron density logs and core plug data indicate porosity in the silicilyte ranges from less than 2% to almost to 40%. The majority of the pore space in the silicilyte is related to (primary) inter-crystalline pores, with locally important oversized secondary pores. Pore casts of the silica matrix show that pores are extremely irregular in three dimensions, and are generally interconnected by a complex web or meshwork of fi ne elongate pore throats. Mercury injection capillary data are in line with the microstructural observations suggesting two populations of pore throats, with an effective average modal diameter of 0.4 μm. The acquired geochemical data support the interpretation that the primary source of the silica is the ambient seawater rather than hydrothermal or biogenic. A maximum temperature of ca. 45°C for the formation of microcrystalline quartz in the silicilyte is good evidence that the lithifi cation and crystallization of quartz occurred in the fi rst 5 Ma after deposition. Several phases of brittle fracturing and mineralization occurred in response to salt tectonics during burial. The sequences of fracture-fi lling mineral phases (dolomite - layered chalcedony – quartz – apatite - magnesite I+II - barite – halite) indicates a complex fl uid evolution after silicilyte lithifi cation. Primary, all-liquid fl uid inclusions in the fracturefi lling quartz are good evidence of growth beginning at low temperatures, i.e. ≤ 50ºC. Continuous precipitation during increasing temperature and burial is documented by primary two-phase fl uid inclusions in quartz cements that show brines at 50°C and fi rst hydrocarbons at ca. 70°C. The absolute timing of each mineral phase can be constrained based on U-Pb geochronometry, and basin modelling. Secondary fl uid inclusions in quartz, magnesite and barite indicate reactivation of the fracture system after peak burial temperature during the major cooling event, i.e. uplift, between 450 and 310 Ma. A number of fi rst-order trends in porosity and reservoir-quality distribution are observed which are strongly related to the diagenetic and fl uid history of the reservoir: the early in-situ generation of hydrocarbons and overpressure development arrests diagenesis and preserves matrix porosity. Chemical compaction by pressure dissolution in the fl ank areas could be a valid hypothesis to explain the porosity variations in the silicilitye slabs resulting in lower porosity and poorer connectivity on the fl anks of the reservoir. Most of the hydrocarbon storage and production comes from intervals characterized by Amthor et al. 114488 preserved micropores, not hydrocarbon storage in a fracture system. The absence of oil expulsion results in present-day high oil saturations. The main diagenetic modifi cations of the silicilyte occurred and were completed relatively early in its history, i.e. before 300 Ma. An instrumental factor for preserving matrix porosity is the diffi culty for a given slab to evacuate all the fl uids (water and hydrocarbons), or in other words, the very good sealing capacity of the salt embedding the slab.

The sediment record of the past 200 years in a Swiss high-alpine lake: Hagelseewli (2339 ma.s.l.)

Sediment cores spanning the last two centuries were taken in Hagelseewli, a high-elevation lake in the Swiss Alps. Contiguous 0.5 cm samples were analysed for biological remains, including diatoms, chironomids, cladocera, chrysophyte cysts, and fossil pigments. In addition, sedimentological and geochemical variables such as loss-on-ignition, total carbon, nitrogen, sulphur, grain-size and magnetic mineralogy were determined. The results of these analyses were compared to a long instrumental air temperature record that was adapted to the elevation of Hagelseewli by applying mean monthly lapse rates. During much of the time, the lake is in the shadow of a high cliff to the south, so that the lake is ice-covered during much of the year and thus decoupled from climatic forcing. Lake biology is therefore influenced more by the duration of ice-cover than by direct temperature effects during the short open-water season. Long periods of ice-cover result in anoxic water conditions and dissolution of authigenic calcites, leading to carbonate-free sediments. The diversity of chironomid and cladoceran assemblages is extremely low, whereas that of diatom and chrysophyte cyst assemblages is much higher. Weak correlations were observed between the diatom and chrysophyte cyst assemblages on the one hand and summer or autumn air temperatures on the other, but the proportion of variance explained is low, so that air temperature alone cannot account for the degree of variation observed in the paleolimnological record. Analyses of mineral magnetic parameters, spheroidal carbonaceous particles and lead suggest that atmospheric pollution has had a significant effect on the sediments of Hagelseewli, but little effect on the water quality as reflected in the lake biota.