Phytochemical, Physicochemical and GC-MS Screening of Dyes Extracted from Tagetes Erecta and Tithonia Diversifolia

Seismic images are fundamental to interpret subsurface setting on both continental and marine environments. However, in carbonate systems, seismic response can be very difficult to be analyzed due to the petrophysical heterogeneities, being the interpretation particularly complicated when faults are present. In fact, faults rocks are generally characterized by different petrophysical properties with respect to the host rocks. Synthetic seismic forward modeling is a powerful tool to quantifying the seismic response associated with fault-related petrophysical changes, since input parameters can be modified. In this study, field and laboratory measurements are used to analyze the spectrum of the carbonate-bearing fault seismic response. Here, we focused on the carbonate ramp setting outcropping in the Majella Massif since it represents an excellent surface analogue of buried porous and faulted carbonate reservoirs worldwide. Density and porosity were measured through a helium pycnometer on representative fault (damage zone) rocks sampled at increasing distances from fault planes. Investigated damage zone samples, show both increased and decreased porosity with respect to the host rock, depending on the single fault characteristics. A 2D (12 km long) synthetic profile from the platform top to the basin, oriented SSE-NNW, was then carried out in Matlab simulating the outcropping architecture and spatial distribution of the sedimentary facies and of the faults. Together with a proper porosity variation related to facies distribution, the porosity along the damage zones (DZ) of the simulated faults was set according to the laboratory measurements. The low-frequency (40Hz) synthetic seismic profile shows marked diffraction hyperbolas in the modeled fault zones for faults characterized by higher porosity DZ where lower seismic velocity is expected. On the contrary, fault zone characterized by lower porosity DZ with respect to the host rock resulted to give a less clear seismic image. Going into the details, faults with decreased porosity and consequent increased seismic velocity of 1000 m/s in the damage zone respect to the host rock, do not show a visible difference in the seismic response if compared with the seismic image without modified petrophysical characteristics within the faults. On the other hand, faults with increased porosity and decreased seismic velocity of just 500 m/s respect to the host rock, show clear diffraction hyperbolas where their apexes correspond to the fault planes. Ongoing laboratory measurements and simulations changing geometries, thicknesses and orientations of the damage zones, are expected to help in improving the knowledge of fault seismic response. This work helps in bridging the gap between forward modeling and actual seismic imaging with large implications for hydrocarbon-reservoir characterization and the identification of potential CO2 or hydrogen storage sites.

Synthetic seismic forward modeling as a tool to assess the seismic signature of carbonate-bearing fault zones

The role of sea-bottom topography in the dispersal of shallow water-derived calciturbidites across a submarine rift, as determined by the local extensional architecture, is under-investigated, namely with pelagic settings along ancient passive continental margins. A comparison with modern carbonate platform/basin analogues, or with siliciclastic systems, is not always feasible, as ancient carbonate systems were commonly home to anachronistic environments (e.g. the Western Tethyan Mesozoic). Geological mapping of the Jurassic rift basin exposed in the Apennines of Central Italy revealed a complex pattern of intrabasinal highs (pelagic carbonate platforms) and intervening basins, controlled by the high density, and oddly variable trends, of faults rooted in a shallow detachment layer corresponding to thick Triassic salt. A map pairing the occurrences of resedimented beds in pelagic successions with an updated palaeogeography becomes therefore the natural descriptor of the itineraries followed by sediment gravity flows. This qualitative method represents a companion, or even alternative, approach to the one strictly based on physical stratigraphy, and it greatly improves our knowledge of regional geology and rift-basin analysis. Our study focuses on: i) a reconstruction of the palaeotectonic architecture of the Umbria-Marche Basin in the Jurassic, and on ii) how this architecture produced a submarine topography which governed the dispersal of sediment, shed by the neighbouring Lazio-Abruzzo Carbonate Platform, for >40 million years. Geological mapping, coupled with the measurement and correlation of stratigraphic sections, shows that the marginal palaeoescarpments of pelagic carbonate platforms formed obstacles to the gravity flows as sediment load was discharged in confined basins at their toes and/or flows were deflected and forced along alternative itineraries. While turbidity currents were locally vigorous enough to climb the escarpments, leaving graded and laminated overbank deposits on the pelagic carbonate platform-tops, a “shelter” effect is evidenced by the resediment-free nature of those basins lying downflow, which were shielded by the highs. Our case study potentially represents the analogue of hydrocarbon fields both inland and in the offshore.

Role of Early Jurassic rift architecture in the dispersal of calciturbidites, as revealed by geological mapping in Central and Northern Apennines

We present a brand new multi-proxy dataset of thermal maturity indicators, which derive from the application of several analytical techniques on surface and subsurface sedimentary successions. The study area spans from the Greater Caucasus to the Adjara-Trialeti fold-and-thrust belt (FTB), comprising the intervening western Kura Basin, in Georgia, and represents a region of continental deformation in the hinterland of the Arabia-Eurasia collision zone. Original and published clay mineralogy, Raman spectroscopy and petrography on dispersed organic matter, and pyrolysis data are integrated for the first time in a coherent tectono-sedimentary scenario. Thermal maturity spans from the low diagenetic realm (60-80°C) in the Upper Miocene section of the Kura sedimentary fill, to the oil window in the Cretaceous to Lower Miocene successions of Adjara-Trialeti FTB, Kakheti ridge and Kura Basin (70-120°C), up to about 400°C in the Greater Caucasus core. Integration of different indicators, besides allowing the estimation of maximum burial temperatures acquired through time, enabled to draw the tectonic evolution of the area. Different maturity trends and thermal histories, coupled with structural and stratigraphic data, highlight that the study area comprises two domains derived from positive tectonic inversion: the E-W Adjara-Trialeti doubly-verging FTB from an Eocene back-arc rift basin and the SSW-verging Georgian Greater Caucasus from a Mesozoic rift basin. Between the two, thin-skinned south-verging thrusts deform the Kura Basin and the Kakheti ridge successions, originally deposited on an extensional structural high which was later flexured during compression. The similar thermal maturity degree in the Adjara-Trialeti FTB and the Kakheti ridge/Kura Basin areas has been acquired in different time spans: during Paleogene extension and during Miocene thin-skinned shortening, respectively. The results indicate that thermal maturation of the sedimentary successions in the Adjara-Trialeti FTB can be ascribed to burial during rift evolution. The same conclusion can be drawn for the axial zone of the Greater Caucasus, whereas tectonic overburden may have contributed to the thermal maturity of the rocks in the southern foothills of the Greater Caucasus: this area needs further work to assess its tectonic evolution.

Using multi-proxy thermal maturity datasets to validate deformation styles from the Adjara-Trialeti fold-and-thrust belt to the Greater Caucasus (Georgia)A

The different environmental conditions produced by the progressive restriction at the Mediterranean-Atlantic gateways during the early Messinian are abundantly investigated in the deeper water succession, while the shallow-water record is less explored. Throughout the Mediterranean, the pre-evaporite deposits in the deep-water record display changing lithologies, from hemipelagic marls and limestone alternation to sapropelitic marly limestone and euxinic clays. The shallow water successions are generally characterised by luxurious coral reefs developed in the Mediterranean area, with some, locally restricted, exceptions. During the early Messinian a first record of the progressive decay of trophic conditions in shallow water environment has been reported in the Majella structure (Central Apennines, Italy). Here the lower Messinian is represented by the Lithothamnion Limestone carbonate ramp that constitutes the uppermost carbonate unit of the Bolognano Formation. This ramp developed in the paleo Adriatic sea and it was characterised by a wide middle ramp environment in which coralline algae dominated carbonate production. This facies was associated with seagrass meadows colonizing the inner ramp. The outer ramp was characterized by bioturbated hemipelagic marl with planktonic foraminifera, pectinids and brachiopods in the aphotic zone. In this work we present facies and geochemical data providing evidence for an early, and repeated, onset of a restrictive environmental development, characterising and the Lithothamnion Limestone carbonate ramp. A stratigraphic section of ramp succession was measured in the eastern sector of Majella structure (Taranta Peligna), fourty bulk-rock samples were analysed for carbon isotopes then correlated with Mediterranean stable isotope record. Redox-sensitive elements (ICP-MS) was performed on twenty-five bulk rock samples. On these samples the Total Organic Carbon (TOC) was also measured using the Loss-On-Ignition (LOI) techniques. The foraminiferal content was analysed under a binocular microscope and classified for bio/chronostratigraphic attribution. The general negative carbon isotope trend recorded of the investigated section is interpreted as the record of the final stage of the Late Miocene Carbon Shift. Trends in the redox-sensitive elements are indicative of an evident decrease in bottom-water oxygen content and coinciding with the drowning of Lithothamnion Limestone carbonate ramp. The drowning coincides with the occurrence of Globorotalia nicolae (MMi 13b zone), when a conspicuous terrigenous input marked by a spike of Al and TOC content was recorded in the investigated succession.

Decoding seafloor and paleoclimate conditions from the paleo-Adriatic domain during early Messinian (Majella, Apennines, Italy)

The hydrodynamic behavior of karst aquifers is usually complex due to the high degree of heterogeneity and anisotropy of their geologic and hydrogeologic properties. Among karstified rocks, metamorphic carbonate rocks (e.g marble and meta-dolostone) are characterized by very low porosity and permeability, but their hydraulic properties can be altered by geologic processes, and significant aquifers can develop into these rocks eventually. However, the functioning of metamorphic karst aquifers is still poorly known. This contribution presents the hydrological monitoring of three of the main karst springs of the Apuan Alps (Italy). This mountain chain is characterized by extensive metamorphosed carbonate outcrops in which karst aquifers have developed. Pollaccia, Renara and Equi springs were equipped with multi parametric sensors for water level and discharge (L, Q), temperature (T), and electrical conductivity (EC). Their hydrographs and chemographs were compared with precipitation time series collected by the meteorological stations to investigate the response of the karst systems to infiltration and to infer their structure. The mean discharge for Pollaccia, Renara and Equi springs were respectively about 900, 200 and 800 l/s, their EC varied between 130 and 300 µS/cm, whereas T ranged between 7.8 and 10.6 °C. Water discharge, T, and EC response to infiltration was quick and impulsive with lag times of few hours. EC and T trends were complex for all the three springs, but dilution was the prevalent hydrodynamic response to precipitation observed during the monitoring. Piston-flow phenomena were scarce and limited to particular conditions. No delay between discharge increments and EC and T responses occurred. These observations suggest that the springs are fed by dominant conduit systems in which water flows only in few, enlarged conduits, with limited fracture storage. Piston-flow phenomena could be related to the presence of secondary flow networks that are connected with the main flow pathways only in specific conditions and/or to the flushing of limited volumes of water stored in the aquifers. Monitoring results suggest that the functioning of meta-carbonate aquifers in the Apuan Alps is controlled by several factors such as the low degree of fracturing of marbles, the local structural arrangement, and the primary porosity of the karstified rocks. As a consequence, storage is limited and flow velocity is high, preventing sustained water-rock interactions.

Monitoring karst aquifers hydrodynamics in metamorphic carbonates: the example of the Apuan Alps, Italy

The present geomorphology of the Volturno river delta and related strandplains is largely a product of an intricate long-term relationships between geological evolution and human impacts. In order to assess the main drivers of the changed landscape in the last 150 years, a multidisciplinary study was carried out by combining historical and geological data. A 150 year cartographic sources were acquired, georeferenced and managed into a GIS environment. Some 1800 well log stratigraphic data were acquired and interpreted to reconstruct the stratigraphic architecture of the plain. Historical analysis has produced documentary evidence of the geomorphological evolution of the area since the end of the XVII century, when, during the Spanish vice-kingdom, it was subjected to major land reclamation. More than 500 km of canals were built in the coastal area. The development of agriculture and farming on reclaimed land promoted urbanization and increasing landscape fragmentation. The peak was attained between the 1960s and the 1990s, when landscape pattern structure increased in complexity with major alterations of alluvial channels and of the deltaic environment, and retreat of the coastline. Land use maps were reconstructed for the 1957 and 2012. The overgrowth of the urban areas to the sea, coupled with intensification of agricultural and tourism activities, resulted in the loss of high quality ecosystems such as the humid coastal setting, the lacustrine/marshy back-dune area and, in most cases, also the beach-dune system. The negative sedimentary balance resulting from the reclamation works on the river courses, together with the interventions along the Volturno river basin, resulted in an accelerated and severe coastal erosion. Coastline displacement was calculated at 7 time points, showing timing and causes of trends and rates of variation. The anthropic impacts were compared with the subsidence trends previously assessed. The lack of an unequivocal correlation of the latter with agricultural land use and zootechnical farm location indicates that these human activities do not exert a significant impact on regional subsidence rates. On the contrary, a net overlay of the subsiding areas with the geological architecture was recognized and in particular with the areal distribution and thickness of deposits such as clayey silts, clays and peats. From geotechnical point of view, these soils can be classified as fine-grained soil (mostly clayey) with poor mechanical properties (high compressibility and low strength). Moreover, the inclusion of significant amount of peat and organic matter clearly reflects high values for the coefficient of secondary compression. The subsidence rates, coupled with the sea level rise due to climatic changes, increase the vulnerability of the coast to erosion, flooding and storm surge and aquifer salinization.

The changing geomorphology of the Volturno delta and coast (northern Campania, Italy): human influence and geological architecture

A large Neogenic "Calcari a Lucina" deposit - i.e. hydrocarbons-rich cold seep carbonate -, reaching 40 m of thickness and several tens of meters of extension, crops out in the Crotone Basin (South Italy). It is composed of authigenic carbonate forming a facies referable to the conduits of gas/fluid, crosscutting early carbonate-cemented bioclastic and siliciclastic sediments definable as pavement facies. Conduits are commonly characterized by the accretion of meters thick thinly laminated and banded calcite and formed by the alternation of dark micritic laminae and clear crystalline layers. The micritic laminae are characterized by an autochthonous microbial peloidal to dendrolitic fabric, incorporating coprolites and planktonic foraminifera. In contrast the crystalline layers are characterized by microspar laminae and centimeters thick sparry crusts composed of prismatic zoned calcite crystals. The pavement facies is typified by foraminiferal bioturbated mudstone/wackestone gradually passing to mixed arenites as the increasing of the siliciclastic grains composed of quartz, plagioclase, phyllosilicates, aphanitic lithic grains, phaneritic rock fragments, and heavy minerals, all immersed into a micritic carbonate matrix, and indicating both sedimentary and crystalline basement source. The foraminiferal assemblage, characterized by almost exclusively by planktonic forms, and the relative proportion of sandy/silty grains, indicate a deep-water setting with occasional siliciclastic coarser sedimentary flows. A common chemosynthetic macrofauna composed of often articulated and in life-position Lucinids, Mytilids and Vesicomids bivalves, associated to tubeworms and gastropods, is commonly present into such sediments. The deposits of the pavement facies are commonly brecciated, possibly because the overpressure conditions established by the gas/fluid injection, and the displacive growth of the conduit deposits that crosscut the sediments, suggesting a very early cementation of the micritic matrix. Clasts of breccias are also later lined by primary fibrous to acicular isopachous to fan-shaped calcite cement. The high diversity of the heavy minerals in the mixed arenite deposits together with the presence of unstable (green amphibole) and moderately stable (epidote, garnet, sillimanite) heavy detrital species, indicates a burial depth comprised between 600 m and 2000 m during which a late diagenetic phase occurred. A pervasive neomorphic recrystallization of the carbonate grains and the precipitation of mosaic equant calcite cements, filling the remnant voids, took place during this phase.

Neogene seepage carbonate deposition in the Crotone Basin (South Italy), preliminary results

The increasing effects of anthropogenic carbon dioxide (CO2) emissions on climate change pressure the scientific community to provide accurate predictions of the future consequences of these variations. The oceans and marine organisms are strongly affected by climate and CO2atm, but they also produce pivotal feedback on climate. Thus, studying the marine carbon cycle is crucial to understand the drivers regulating the past, present, and future evolution of climate. Among marine biota, coccolithophores, a group of calcifying marine phytoplankton, play a key role in the ocean carbon cycle at various timescales providing pivotal information on the oceans’ capacity towards CO2 buffering. They are also particularly sensitive to environmental variations making them excellent climate proxies. In this study, experimental cultures of the species Helicosphaera carteri cultivated in turbidostats under CO2-controlled conditions were compared to the fossil coccolithophore assemblage at the International Ocean Discovery Program (IODP) Site U1501 (South China Sea). The combination of paleontological and culture-derived data can improve predictions of the state of biodiversity in the future under varying climate change scenarios. Helicosphaera carteri cultures were grown under 425 ppm CO2, a level consistent with the best-case scenario predicted by the Intergovernmental Panel on Climate Change (IPCC), the Representative Concentration Pathway (RCP) 2.6 (IPCC, 2014). The selected time interval for studying the fossil coccolithophore assemblage belongs to Marine Isotope Stage 5 (130-70 kyr), a geological interval considered as an analogue for modern warming. Through the study of the fossil record, we identified significant changes to the coccolithophore community during the warmest substages of MIS5, i.e. MIS5e. Site U1501 recorded a significant peak in coccolithophore absolute abundance related to increased productivity during MIS5e, and consequently, the highest coccolith-derived carbonate contribution to bulk calcium carbonate of the last 300 kyr. Data from cultures indicated the resilience of H. carteri towards high CO2 through the maintenance of well-preserved coccoliths. However, the growth rate, despite being constant, was slightly lower than the control culture, indicating a decreased contribution to calcite production/export under high CO2 levels. The results suggest coccolithophores may play an important, but shifting role in carbon sequestration in a warmer world. Further, this comparison contributes to improving our understanding of the potential effects of anthropogenic climate change on oceanic primary producers like coccolithophores.

Living and Fossil Coccolithophores: a tool to understand past and future climate changes

The Cenomanian–Turonian Oceanic Anoxic Event 2 (OAE-2) represents a major perturbation of the global carbon cycle associated with the extensive deposition of organic carbon-rich deposits (black shales) in the oceanic basins, worldwide. Numerous studies have suggested that enhanced volcanic activity at mid-oceanic ridges and large igneous province (LIP) eruptions may have acted as potential trigger mechanisms of this event. These phenomena caused excess CO2 degassing and a consequent dramatic temperature increase in the oceans and atmosphere. Although the geochemical, sedimentological and paleontological changes throughout the OAE-2 are well-known in basinal deposits, the shallow- water carbonate counterpart is still poorly investigated. The OAE-2, however, strongly impacted both deep and shallow-water ecosystems. The limited information on the expression of the OAE-2 in carbonate platforms represents a critical gap in our understanding of ecological responses to abrupt paleoenvironmental/paleoclimatic changes in the mid-Cretaceous, given that shallow shelves accounted for a significant part of the global ocean biological productivity and carbonate production. In this work we present new high-resolution geochemical and sedimentological data across the OAE-2, based on bivalve shells and bulk rock material from a well exposed upper Cenomanian – lower Turonian section, in the carbonate successions of the Friuli Carbonate Platform (FCP) cropping out in the Karst area, near the city of Gorizia. Biostratigraphy and carbon-isotope stratigraphy were used to establish a precise stratigraphic dating and for high resolution correlations with coeval shallow-water and reference open-ocean sections. Sr-isotope data, Hg concentration and other geochemical proxies have been used to highlight possible evidence of volcanic activity and changes in weathering and to evaluate paleoenvironmental conditions on the FCP during the OAE-2. Results highlight that, during the event, the FCP underwent major biotic and geochemical changes that these fluctuations can be compared to those occurring in coeval carbonate platforms of the Tethys during the OAE-2. 

First evidence of the Oceanic Anoxic Event -2 in the shallow-water carbonates of the Friuli Carbonate Platform: geochemical and sedimentological data

Here we present an integrated calcareous plankton and geochemical record from the Tethyan Terche and Madeago sections (NE Italy), deposited in a middle-lower bathyal setting. These sections record a negative Carbon Isotope Excursion corresponding to Eocene Thermal Maximum 2 (ETM2, ~54 Ma). Our planktic foraminiferal and calcareous nannofossil records show significant, though temporary, changes in both sections across this event. No significant dissolution occurred that could have affected the assemblages. Warm index surface-dweller Acarinina increased while of the deeper-dweller chiloguembelinids and subbotinids declined in abundance. A test reduction of up to 50% compared to pre-event sizes for both surface- and deeper dwellers planktic foraminiferal is particularly marked at Madeago. While symbiont bleaching can reduce growth, both symbiont and asymbiotic planktic foraminifers were affected at the same scale in our sections at the ETM2, and hence not a likely cause of the size reduction. The enhanced surface remineralization of organic matter due to warming may have reduced the food input at the thermocline, thus contracting the deeper ecological niches. The calcareous nannofossil assemblages provide evidence of increased surface water eutrophy during the ETM2. The increase in small placoliths Toweius and Ericsonia may indicate that dwarfism also affected nannofossil assemblages, though to a lesser degree. We thus hypothesize that the ETM2 perturbation impacted the entire upper water column possibly changing stratification and niche spaces. To establish whether the observed dwarfism was related to environmental stressors which are not commonly linked to the ETM2 climatic perturbation, we quantified the Hg (ppb), TOC (wt%) and Hg/TOC (ppb/wt%) geochemical proxies through our sections. Results show an increase in Hg in both sections at the base of the ETM2. We attribute this increase to coeval submarine igneous events that might have introduced biolimiting metals, which changed plankton productivity and possibly affected test size. However, we cannot exclude reworking of the metal because we record an increase in sedimentation rate and nannofossil rework at the ETM2. We suggest that the plankton dwarfism, here documented for the first time across the ETM2, could be the result of the coupled effect of increase in biolimiting metals and changes in the physicochemical structure of the upper water column.

Evidence of Tethyan calcareous plankton dwarfism across the ETM2

The genus Xenophora comprises species of marine gastropods, known from the Cretaceous and still living today, which have the ability to form their shells agglutinating objects with different origins, from other shells to bio- or lithoclasts. Different agglutination potentials are shown by species of Xenophora, from species lacking attachments to others completely covered, as the case of the Mediterranean Xenophora crispa (König, 1825). Shell sections of fossil (Early Pleistocene, Arda and Stirone Rivers, Italy) and recent specimens (Mediterranean Sea, Spain) of X. crispa were here analyzed at the Scanning Electron Microscope (SEM) and powders, collected from different parts of the shell, at X-Ray Diffraction (XRD), in order to characterize in detail the microstructure and the mechanisms, function and behaviour of the agglutination in the same species through time, in this case over about 2 millions of years. Also, as the Arda and Stirone River sections were deposited during the Early Pleistocene, this research allows to examine if and how these parameters varied during a climate change. Indeed, the Early Pleistocene was a time interval characterized by several climatic oscillations linked to glacial/interglacial cycles and the Mediterranean area was strongly affected by these climatic changes showing in marine environment a progressive climatic cooling. This study shows that the functional purpose of the agglutination in X. crispa may be related to a snowshoe strategy to successfully colonize muddy substrates, coupled with tactile and olfactory camouflage. Indeed, this species secretes in the columella and peripheral edge of both fossil and recent specimens a less dense and a more organic rich calcitic fabric, possibly to lighten the shell thickest parts in order not to sink in soft sediments and to facilitate the shell raising from the substrate to create a protected feeding area. This behaviour and the shell microstructure seem to have been maintained by X. crispa over 2 My time span, thus allowing to suppose that this species did not suffer the climatic cooling of the Early Pleistocene.

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Phytochemical, Physicochemical and GC-MS Screening of Dyes Extracted from Tagetes Erecta and Tithonia Diversifolia

Synthetic seismic forward modeling as a tool to assess the seismic signature of carbonate-bearing fault zones

Role of Early Jurassic rift architecture in the dispersal of calciturbidites, as revealed by geological mapping in Central and Northern Apennines

Using multi-proxy thermal maturity datasets to validate deformation styles from the Adjara-Trialeti fold-and-thrust belt to the Greater Caucasus (Georgia)A

Decoding seafloor and paleoclimate conditions from the paleo-Adriatic domain during early Messinian (Majella, Apennines, Italy)

Monitoring karst aquifers hydrodynamics in metamorphic carbonates: the example of the Apuan Alps, Italy

The changing geomorphology of the Volturno delta and coast (northern Campania, Italy): human influence and geological architecture

Neogene seepage carbonate deposition in the Crotone Basin (South Italy), preliminary results

Living and Fossil Coccolithophores: a tool to understand past and future climate changes

First evidence of the Oceanic Anoxic Event -2 in the shallow-water carbonates of the Friuli Carbonate Platform: geochemical and sedimentological data

Evidence of Tethyan calcareous plankton dwarfism across the ETM2

From the Early Pleistocene to the Recent: how is Xenophora crispa biomineralization varied?

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