Layer description, carbon and nitrogen content and stable isotope record of bulk sedimentary organic matter from Laguna Potrok Aike

An investigation of stable isotope (d13C TOC and d15N TN) and elemental parameters (TOC, TN contents and TOC/TN ratios) of bulk organic matter (<200 µm) from sediment cores recovered from the Patagonian lake Laguna Potrok Aike (Argentina) in the framework of the ICDP deep drilling project PASADO provided insights into past changes in lake primary productivity and environmental conditions in South Patagonia throughout the last Glacial-Interglacial transition. Stratigraphically constrained cluster analyses of all proxy parameters suggest four main phases. From ca 26,100 to 17,300 cal. years BP, lacustrine phytoplankton was presumably the predominant organic matter source in an aquatic environment with low primary productivity rates. At around 17,300 cal. years BP, abrupt and distinct shifts of isotopic and elemental values indicate that the lacustrine system underwent a rapid reorganization. Lake primary productivity (phytoplankton and aquatic macrophytes) shows higher levels albeit with large variations during most of the deglaciation until 13,000 cal. years BP. The main causes for this development can be seen in improved growing conditions for primary producers because of deglacial warming in combination with expedient availability of nutrients and likely calm wind conditions. After 13,000 cal. years BP, decreased d13C TOC values, TOC, TN contents and TOC/TN ratios indicate that the lake approached a new state with reduced primary productivity probably induced by unfavourable growing conditions for primary producers like strengthened winds and reduced nutrient availability. The steady increase in d15N TN values presumably suggests limitation of nitrate supply for growth of primary producers resulting from a nutrient shortage after the preceding phase with high productivity. Nitrate limitation and consequent decreased lacustrine primary productivity continued into the early Holocene (10,970-8400 cal. years BP) as reflected by isotopic and elemental values.

Sedimentary and carbonate preservation of ODP Sites 1262, 1263 and 1266

Rapid carbon input into the ocean-atmosphere system caused a dramatic shoaling of the lysocline during the Paleocene-Eocene thermal maximum (PETM), a transient (~170 kyr) global warming event that occurred roughly 55 Ma. Carbon cycle models invoking an accelerated carbonate-silicate feedback mechanism to neutralize ocean acidification predict that the lysocline would subsequently deepen to depths below its original position as the marine carbonate system recovered from such a perturbation. To test this hypothesis, records of carbonate sedimentation and preservation for PETM sections in the Weddell Sea (ODP Site 690) and along the Walvis Ridge depth transect (ODP Sites 1262, 1263, and 1266) were assembled within the context of a unified chronostratigraphy. The meridional gradient of undersaturation delimited by these records shows that dissolution was more severe in the subtropical South Atlantic than in the Weddell Sea during the PETM, a spatiotemporal pattern inconsistent with the view that Atlantic overturning circulation underwent a transient reversal. Deepening of the lysocline following its initial ascent is signaled by increases in %CaCO3 and coarse-fraction content at all sites. Carbonate preservation during the recovery period is appreciably better than that seen prior to carbon input with carbonate sedimentation becoming remarkably uniform over a broad spectrum of geographic and bathymetric settings. These congruent patterns of carbonate sedimentation confirm that the lysocline was suppressed below the depth it occupied prior to carbon input, and are consistent with the view that an accelerated carbonate-silicate geochemical cycle played an important role in arresting PETM conditions.

Petroleum System Analysis: Middle Magdalena Valley Basin, Colombia, South America

The purpose of this study is to create a petroleum system model and to assess whether or not the La Luna Formation has potential for unconventional exploration and production in the Middle Magdalena Valley Basin (MMVB), Colombia. Today, the Magdalena River valley is an intermontane valley located between the Central and Eastern Cordillera of Colombia. The underlying basin, however, represents a major regional sedimentary basin that received deposits from the Triassic through the Cenozoic. In recent years Colombia has been of great exploration interest because of its potentially vast hydrocarbon resources, existing petroleum infrastructure, and skilled workforce. Since the early 1900s when the MMVB began producing, it has led to discoveries of 1.9 billion barrels of oil (BBO) and 2.5 trillion cubic feet (Tcf) of gas (Willatt et al., 2012). Colombia is already the third largest producer of oil in South America, and there is good potential for additional unconventional exploration and production in the Cretaceous source rocks (Willatt et al., 2012). Garcia Gonzalez et al. (2009) estimate the potential remaining hydrocarbons in the La Luna Formation in the MMVB to be between 1.15 and 10.33 billion barrels of oil equivalent (BBOE; P90 and P10 respectively), with 2.02 BBOE cumulative production to date. Throughout the 1900s and early 2000s, Cenozoic continental and transitional clastic reservoirs were the primary exploration interest in the MMVB (Dickey, 1992). The Cretaceous source rocks, such as the La Luna Formation, are now the target for unconventional exploration and production. In the MMVB, the La Luna formation is characterized by relatively high total organic carbon (TOC) values, moderate maturity, and adequate thickness and depth (Veigal and Dzelalijal, 2014). The La Luna Formation is composed of Cenomanian-Santonian aged shales, marls, and limestones (Veigal and Dzelalijal, 2014). In addition to the in-situ hydrocarbons, the fractured limestones in the La Luna formation act as secondary reservoirs for light oil from other formations (Veigal and Dzelalijal, 2014). Thus the system can be considered more of a hybrid play, rather than a pure unconventional play. The Cretaceous source rocks of the MMVB exhibit excellent potential for unconventional exploration and production. Due to the complex structural nature of the MMVB, an understanding of the distribution of rocks and variations in rock qualities is essential for reducing risk in this play.

METEX: An expert system for metamorphic petrography

Classification of metamorphic rocks is normally carried out using a poorly defined, subjective classification scheme making this an area in which many undergraduate geologists experience difficulties. An expert system to assist in such classification is presented which is capable of classifying rocks and also giving further details about a particular rock type. A mixed knowledge representation is used with frame, semantic and production rule systems available. Classification in the domain requires that different facets of a rock be classified. To implement this, rocks are represented by 'context' frames with slots representing each facet. Slots are satisfied by calling a pre-defined ruleset to carry out the necessary inference. The inference is handled by an interpreter which uses a dependency graph representation for the propagation of evidence. Uncertainty is handled by the system using a combination of the MYCIN certainty factor system and the Dempster-Shafer range mechanism. This allows for positive and negative reasoning, with rules capable of representing necessity and sufficiency of evidence, whilst also allowing the implementation of an alpha-beta pruning algorithm to guide question selection during inference. The system also utilizes a semantic net type structure to allow the expert to encode simple relationships between terms enabling rules to be written with a sensible level of abstraction. Using frames to represent rock types where subclassification is possible allows the knowledge base to be built in a modular fashion with subclassification frames only defined once the higher level of classification is functioning. Rulesets can similarly be added in modular fashion with the individual rules being essentially declarative allowing for simple updating and maintenance. The knowledge base so far developed for metamorphic classification serves to demonstrate the performance of the interpreter design whilst also moving some way towards providing a useful assistant to the non-expert metamorphic petrologist. The system demonstrates the possibilities for a fully developed knowledge base to handle the classification of igneous, sedimentary and metamorphic rocks. The current knowledge base and interpreter have been evaluated by potential users and experts. The results of the evaluation show that the system performs to an acceptable level and should be of use as a tool for both undergraduates and researchers from outside the metamorphic petrography field. .

Compilation of 220 sediment core d13C data from the glacial Atlantic Ocean

We compare a compilation of 220 sediment core d13C data from the glacial Atlantic Ocean with three-dimensional ocean circulation simulations including a marine carbon cycle model. The carbon cycle model employs circulation fields which were derived from previous climate simulations. All sediment data have been thoroughly quality controlled, focusing on epibenthic foraminiferal species (such as Cibicidoides wuellerstorfi or Planulina ariminensis) to improve the comparability of model and sediment core carbon isotopes. The model captures the general d13C pattern indicated by present-day water column data and Late Holocene sediment cores but underestimates intermediate and deep water values in the South Atlantic. The best agreement with glacial reconstructions is obtained for a model scenario with an altered freshwater balance in the Southern Ocean that mimics enhanced northward sea ice export and melting away from the zone of sea ice production. This results in a shoaled and weakened North Atlantic Deep Water flow and intensified Antarctic Bottom Water export, hence confirming previous reconstructions from paleoproxy records. Moreover, the modeled abyssal ocean is very cold and very saline, which is in line with other proxy data evidence.

X-ray diffraction analysis, binocular component analysis and radiocarbon dating of sediment cores from the NW Iberian shelf system

Based on a well-established stratigraphic framework and 47 AMS-14C dated sediment cores, the distribution of facies types on the NW Iberian margin is analysed in response to the last deglacial sea-level rise, thus providing a case study on the sedimentary evolution of a high-energy, low-accumulation shelf system. Altogether, four main types of sedimentary facies are defined. (1) A gravel-dominated facies occurs mostly as time-transgressive ravinement beds, which initially developed as shoreface and storm deposits in shallow waters on the outer shelf during the last sea-level lowstand; (2) A widespread, time-transgressive mixed siliceous/biogenic-carbonaceous sand facies indicates areas of moderate hydrodynamic regimes, high contribution of reworked shelf material, and fluvial supply to the shelf; (3) A glaucony-containing sand facies in a stationary position on the outer shelf formed mostly during the last-glacial sea-level rise by reworking of older deposits as well as authigenic mineral formation; and (4) A mud facies is mostly restricted to confined Holocene fine-grained depocentres, which are located in mid-shelf position. The observed spatial and temporal distribution of these facies types on the high-energy, low-accumulation NW Iberian shelf was essentially controlled by the local interplay of sediment supply, shelf morphology, and strength of the hydrodynamic system. These patterns are in contrast to high-accumulation systems where extensive sediment supply is the dominant factor on the facies distribution. This study emphasises the importance of large-scale erosion and material recycling on the sedimentary buildup during the deglacial drowning of the shelf. The presence of a homogenous and up to 15-m thick transgressive cover above a lag horizon contradicts the common assumption of sparse and laterally confined sediment accumulation on high-energy shelf systems during deglacial sea-level rise. In contrast to this extensive sand cover, laterally very confined and maximal 4-m thin mud depocentres developed during the Holocene sea-level highstand. This restricted formation of fine-grained depocentres was related to the combination of: (1) frequently occurring high-energy hydrodynamic conditions; (2) low overall terrigenous input by the adjacent rivers; and (3) the large distance of the Galicia Mud Belt to its main sediment supplier.

(Table 1) Comparison of diatom-bound and bulk sedimentary d15N values of ODP Holes 175-1082A and 175-1084A

The Matuyama Diatom Maximum (MDM) is a time of peak opal accumulation from 2.6 to ~2.0 Ma within the Benguela Current upwelling system that was initiated by increased influence of Southern Ocean water on the eastern South Atlantic. We measured opal, total organic carbon (TOC), and CaCO3 fluxes and C and N stable isotopes in sediments deposited from 2.4 to 1.95 Ma at Sites 1082 and 1084 to explore the biogeochemical dynamics within the Benguela region. The infusion of Southern Ocean water delivered dissolved nutrients and Southern Ocean flora and fauna, resulting in local opal accumulation increasing up to 8 g/cm**2/ky and the production of diatom mats. Some d15N measurements of diatom-bound organic matter indicate that the mats grew within the Benguela region. The bulk sediment d15N records are taken to reflect changes in the d15N of nitrate in the incoming water, where lower values at 2.4 Ma reflect less nitrate utilization in the Antarctic. A long-term increase in relative nitrate uptake in the Southern Ocean is evidenced by the gradual increase in d15N toward 1.9 Ma.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Sedimentary n-alkanes, their hydrogen isotopes, GDGTs and d15N as well as d13Corg of lake Nam Co, Tibet

The transition from the last Glacial to the current Interglacial, the Holocene, represents an important period with climatic and environmental changes impacting ecosystems. In this study, we examined the interplay between the Indian Ocean Summer Monsoon (IOSM) and the Westerlies at lake Nam Co, southern Tibet to understand the climatic effects on the ecosystem. Different organic geochemical proxies (n-alkanes, glycerol dialkyl glycerol tetraethers, dD, d13Corg, d15N) are applied to reconstruct the environmental and hydrological changes on one of the longest available paleorecords at the Tibetan Plateau. Based on our paleohydrological dD proxies, the aquatic signal lags the terrestrial one due to specific ecological thresholds, which, in addition to climatic changes, can influence aquatic organisms. The aquatic organisms' response strongly depends on temperature and associated lake size, as well as pH and nutrient availability. Because the terrestrial vegetation reacts faster and more sensitively to changes in the monsoonal and climatic system, the dD of n-C29 and the reconstructed inflow water signal represent an appropriate IOSM proxy. In general, the interplay of the different air masses seems to be primarily controlled by solar insolation. In the Holocene, the high insolation generates a large land-ocean pressure gradient associated with strong monsoonal winds and the strongest IOSM. In the last glacial period, however, the weak insolation promoted the Westerlies, thereby increasing their influence at the Tibetan Plateau. Our results help to elucidate the variable IOSM, and they illustrate a remarkable shift in the lake system regarding pH, d13Corg and d15N from the last glacial to the Holocene interglacial period.

Revisiting the Late Jurassic-Early Cretaceous of the NW South Iberian Basin: new ages and sedimentary environments

The study of the Upper Jurassic-Lower Cretaceous deposits (Higueruelas, Villar del Arzobispo and Aldea de Cortés Formations) of the South Iberian Basin (NW Valencia, Spain) reveals new stratigraphic and sedimentological data, which have significant implications on the stratigraphic framework, depositional environments and age of these units. The Higueruelas Fm was deposited in a mid-inner carbonate platform where oncolitic bars migrated by the action of storms and where oncoid production progressively decreased towards the uppermost part of the unit. The overlying Villar del Arzobispo Fm has been traditionally interpreted as an inner platform-lagoon evolving into a tidal-flat. Here it is interpreted as an inner-carbonate platform affected by storms, where oolitic shoals protected a lagoon, which had siliciclastic inputs from the continent. The Aldea de Cortés Fm has been previously interpreted as a lagoon surrounded by tidal-flats and fluvial-deltaic plains. Here it is reinterpreted as a coastal wetland where siliciclastic muddy deposits interacted with shallow fresh to marine water bodies, aeolian dunes and continental siliciclastic inputs. The contact between the Higueruelas and Villar del Arzobispo Fms, classically defined as gradual, is also interpreted here as rapid. More importantly, the contact between the Villar del Arzobispo and Aldea de Cortés Fms, previously considered as unconformable, is here interpreted as gradual. The presence of Alveosepta in the Villar del Arzobispo Fm suggests that at least part of this unit is Kimmeridgian, unlike the previously assigned Late Tithonian-Middle Berriasian age. Consequently, the underlying Higueruelas Fm, previously considered Tithonian, should not be younger than Kimmeridgian. Accordingly, sedimentation of the Aldea de Cortés Fm, previously considered Valangian-Hauterivian, probably started during the Tithonian and it may be considered part of the regressive trend of the Late Jurassic-Early Cretaceous cycle. This is consistent with the dinosaur faunas, typically Jurassic, described in the Villar del Arzobispo and Aldea de Cortés Fms.

On the microstructure, growth pattern and original porosity of belemnite rostra: insights from calcitic Jurassic belemnites

Calcitic belemnite rostra are usually employed to perform paleoenvironmental studies based on geochemical data. However, several questions, such as their original porosity and microstructure, remain open, despite they are essential to make accurate interpretations based on geochemical analyses.This paper revisits and enlightens some of these questions. Petrographic data demonstrate that calcite crystals of the rostrum solidum of belemnites grow from spherulites that successively develop along the apical line, resulting in a “regular spherulithic prismatic” microstructure. Radially arranged calcite crystals emerge and diverge from the spherulites: towards the apex, crystals grow until a new spherulite is formed; towards the external walls of the rostrum, the crystals become progressively bigger and prismatic. Adjacent crystals slightly vary in their c-axis orientation, resulting in undulose extinction. Concentric growth layering develops at different scales and is superimposed and traversed by a radial pattern, which results in the micro-fibrous texture that is observed in the calcite crystals in the rostra.Petrographic data demonstrate that single calcite crystals in the rostra have a composite nature, which strongly suggests that the belemnite rostra were originally porous. Single crystals consistently comprise two distinct zones or sectors in optical continuity: 1) the inner zone is fluorescent, has relatively low optical relief under transmitted light (TL) microscopy, a dark-grey color under backscatter electron microscopy (BSEM), a commonly triangular shape, a “patchy” appearance and relatively high Mg and Na contents; 2) the outer sector is non-fluorescent, has relatively high optical relief under TL, a light-grey color under BSEM and low Mg and Na contents. The inner and fluorescent sectors are interpreted to have formed first as a product of biologically controlled mineralization during belemnite skeletal growth and the non-fluorescent outer sectors as overgrowths of the former, filling the intra- and inter-crystalline porosity. This question has important implications for making paleoenvironmental and/or paleoclimatic interpretations based on geochemical analyses of belemnite rostra.Finally, the petrographic features of composite calcite crystals in the rostra also suggest the non-classical crystallization of belemnite rostra, as previously suggested by other authors.

Direction, legitimacy and structuration in technological innovation systems upscaling-insights from roadmaps for deepwater offshore wind energy

This research investigates strategies aiming to accelerate the up-scaling of low- carbon innovations. We adopt the technological innovation systems (TIS) perspective to focus on structuration or system building processes, including key innovative activities. We analyze national roadmaps that have been developed for offshore wind energy in deep waters - more than 50 meters deep where most of the potential is expected but whose technologyis more immature . in Europe. The roadmaps analysis not only reveals how actors expect the TIS grow but also enables the understanding about the critical functions at this stage, such as direction of search and legitimacy.