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Article

Pre-Messinian Deposits of the Mediterranean Ridge: Biostratigraphic and Geochemical Evidence from the Olimpi Mud Volcano Field

1
Faculty of Geology and Geoenvironment, School of Science, National and Kapodistrian University of Athens, University Campus, 15784 Zografou, Greece
2
Hellenic Centre for Marine Research, Institute of Oceanography, 46.7 km Athens-Sounio Ave., 19013 Anavyssos, Greece
3
School of Geology, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
4
Institute of Petroleum Research (IPR)—FORTH, University Campus, 73100 Chania, Greece
*
Author to whom correspondence should be addressed.
Water 2021, 13(10), 1367; https://doi.org/10.3390/w13101367
Submission received: 13 March 2021 / Revised: 8 May 2021 / Accepted: 10 May 2021 / Published: 14 May 2021
(This article belongs to the Special Issue Coastal and Continental Shelf Dynamics in a Changing Climate)

Abstract

:
This study presents the results derived from micropaleontological and organic geochemical analyses of mud breccia samples obtained (through gravity coring) from five mud volcanoes (Gelendzhik, Heraklion, Moscow, Milano, Leipzig) located at the Olimpi mud volcano field on the Mediterranean Ridge accretionary complex. A thorough calcareous nannofossil semi-quantitative analysis was performed to determine the biostratigraphic assignment of the deep-seated source strata. Mudstone/shale clasts of different stratigraphic levels were identified and assigned to the Miocene nannofossil biozones CNM10, CNM8–9, CNM7, CNM6–7, and Oligocene CNO4/CNO5. A single mudstone clast from the Gelendzhik plateau, assigned to the biozone CNM10, demonstrated unique micropaleontological and geochemical characteristics, suggesting a sapropelic origin. Subsequently, the total organic carbon (TOC) content and thermal maturity of the collected mud breccias was evaluated using the Rock-Eval pyrolysis technique, and their oil and gas potential was estimated. The pyrolyzed sediments were both organic rich and organic poor (TOC >0.5% or <0.5%, respectively), with their organic matter showing characteristics of the type III kerogen that consists of adequate hydrogen to be gas generative, but insufficient hydrogen to be oil prone. However, the organic matter of the late Serravallian (CNM10) sapropelic mudstone was found to consist of a mixed type II/III kerogen, implying an oil-prone source rock.

1. Introduction and Geotectonic Setting

Mud volcanoes (MVs) are very common structures on the eastern Mediterranean seafloor, distributed in areas under a compressional tectonic regime. In total, more than 250 MVs have been identified on the Mediterranean ridge (MR), while such structures are absent throughout the neighboring tectonically inactive Hellenic backstop, even though extensional stresses may prevail in places. MVs are considered as the most important pathways for the release of overpressure caused primarily by tectonic movements and secondarily by the production of diagenetic fluids (biogenic and/or thermogenic) within deep-seated sediments.
Many studies have been carried out during the past decades in order to determine the MVs’ spatial distribution in the eastern Mediterranean basin (Figure 1) (e.g., [1,2,3,4,5]), their sedimentological and geochemical characteristics [6,7,8,9,10], and their possible relation to gas hydrates and gas seeps [11,12,13,14,15].
Based on Mediterranean Sea studies, the sediments extruded during the eruptive activity of MVs comprise mixtures of a poorly sorted clayey, silty, and sandy matrix along with angular to round coarser material (i.e., pebbles, cobbles, or even larger clasts), which usually do not share the same stratigraphic origin. The established term for these sediments is “mud breccia”. Cita et al. [17] were the first authors to use the previous term aiming to describe the material expelled from the Prometheus MV, which consists of a grey clay- and silt-sized matrix supporting centimeter-sized sub-rounded clasts of semi-indurated sediment [18].
The Olimpi mud volcano field (OMVF) is located on the central-northern MR (Figure 1) and includes several mud domes/complexes. The MR is a relatively deep (~1700–2000 m) and a wide ridge on the bed of the eastern Mediterranean Sea, running along an area extending from Calabria, south of Crete Island, to the southwest edge of the Turkish coast, and from there, eastwards south of Cyprus Island. The MR is being uplifted by compressional stresses, triggered by the collision and subsequent subduction of the African plate beneath the Eurasian, Aegean, and Anatolian plates. Hence, the MR is actually the accretionary wedge/prism of this subduction zone, while the marine region offshore of southern Crete is considered as a forearc basin (e.g., [19,20]. The compressional tectonic regime developed in the MR consists of the latest event of the cyclic tectono-metamorphic process that took place during the migration of the Hellenic orogenic belt towards the most external (southern) units [19,21]. A thick continental crust developed because of the stacking of the Cretan nappe piles (e.g., Mani/Plattenkalk, Arna/Phyllites-Quartzites, Gavrovo, Pindos) during the Oligocene–early Miocene under a N-S trending compressional deformation [22].
During the Miocene–Pliocene, the lithospheric plate convergence zone and, subsequently, the tectonic compression migrated southwards to the Mediterranean region offshore of southern Crete and offshore of southern Peloponnese [23]. As a result, the compression in the Mediterranean basin led to the onset of the MR development. At the same time, Crete and Peloponnese, which previously experienced compressional stresses, were subjected to a N-S trending extensional tectonic regime. In the Miocene–early Pliocene, crustal extension in Crete caused the uplifting of the lower nappes [22,24], and sedimentary basins were developed onshore and offshore (backstop area) Crete and Peloponnese.
The mud volcanism is most probably related to backthrusting processes along the northern boundary of the accretionary wedge, near the Hellenic backstop region [25]. The ongoing (since Miocene–Pliocene) tectonic compressional deformation in the MR has been considered as the triggering process for the development of MVs since the early Pleistocene. For example, the first eruptive activity of the Napoli MV was estimated between 1.25 and 1.5 Ma, while the first eruption of the Milano MV was estimated at 1.75 Ma [6,7].
The sediments extruded onto the seafloor during the MV eruptions may originate from sub-salt formations of pre-Messinian age or from source beds of the Messinian age (e.g., [10]) and consist of a mixture of clasts of variable lithology and consolidation, supported by very stiff to very soft sandy mud matrix having clay as the dominant fraction (e.g., see Appendix A in Panagiotopoulos et al. [26]). In terms of petrology, most of the clasts of the mud breccia matrices are considered to be derived from the North African passive margin, except of various ophiolite-related lithoclasts that are probably derived from higher thrust sheets of Crete [25].
The scope of the present study was to perform micropaleontological and organic geochemical analyses on mud breccia deposits obtained from five MVs (Gelendzhik, Heraklion, Moscow, Milano, and Leipzig) of the OMVF using gravity coring, in order to shed light on the deep-seated sub-salt formations of the region, since there is lack of a deep-well drilling in this particular MR area. To the best of our knowledge, the only stratigraphy in the host sediment of the OMVF, albeit very shallow, is the one provided by Cita et al. [27] through a core analysis, which revealed that the occurrence of pelagic sequences of the Holocene to Middle Pleistocene are composed mainly of marl and sapropel, as well as tephra layers as minor, isochronous lithologies.

2. Materials and Methods

2.1. Sediment Collection and Sample Treatment

The sediment cores investigated in this work were collected from the crests of the relevant MVs (see Figure 2a for coring locations and core names) and initially examined by Panagiotopoulos et al. [26]. According to the previous study, the sampling locations were selected based on the intensity of the backscatter signal recorded during a swath bathymetry survey in the OMVF (Figure 2a–c) carried out by the R/V Aegaeo in 2016. The sediment sampling was performed using a gravity corer (Benthos Inc., Massachusetts, USA) with a 3-m-long core barrel (Benthos Inc., Massachusetts, USA). Because of the highly incohesive nature of the majority of the mud breccia deposits, the recovery length of the retrieved cores was generally incomplete (70–132 cm).
In the laboratory, 100–200 g of material was initially recovered from 14 mud breccia facies (see Figure 3 and [26]) and, then, clasts were carefully removed from the sediment matrix. In total, 42 samples (14 matrices and 28 clasts) were collected and described regarding their color (using the Munsell soil color chart), distinct features (e.g., fissilities), lithology (a representative example is displayed in Figure 4), and degree of consolidation (see Table A1, Table A2, Table A3, Table A4 and Table A5 in Appendix A). The degree of the sediment matrix consolidation was already determined by Panagiotopoulos et al. [26], while the consolidation degree of clasts was estimated by the present study using the empirical testing criteria referred to in Appendix A.
All samples were split in two equal halves. The first half was completely homogenized using a mortar and pestle and an amount of at least 100 mg per sample was subjected to Rock-Eval pyrolysis, while the second half was used to produce smear slides for the microscopical study of the calcareous nannofossil content, according to standard techniques [28,29].

2.2. Micropaleontology and Biostratigraphy

Concerning the calcareous nannofossil analysis, a semi-quantitative determination was conducted in up to 300 fields of view per slide in randomly distributed longitudinal traverses using a Leica DMLSP (Leica Microsystems GmbH, Wetzlar, Germany) optical polarizing light microscope at a 1250× magnification. The traverses represented both low- and high-density material content in an effort to make accurate nannofossil determinations and trace even the rarest species. The semi-quantitative abundances of the taxa encountered were recorded as follows: A, abundant: ≥1 specimen/1 field of view; C, common: ≥1 specimen/10 fields of view; F, few: 1 specimen/10–50 fields of view; R, rare: 1 specimen/>50 fields of view.
Τhe zonal assignment follows the biostratigraphic scheme of Agnini et al. [30], which incorporates the biochronologic information from Βackman et al. [31] and is correlated to the Martini [32] biozones (see Table 1).
It should be noted that sample preparation restrictions, due to the nature of the examined sediment (i.e., minute clasts within a consolidated sediment matrix), could result in the contamination of the nannofossil assemblages and organic matter content. Hence, the grinding and homogenization process of the matrix and minor clasts could artificially produce a sample characterized by various organic matter types and diverse nannofossil assemblages. Further, the occurrence of clasts containing organic matter and nannofossils of dissimilar stratigraphic origin could be explained by the presence of an amount of residual matrix that was not sufficiently scraped off from the surface of the clasts during the sample preparation, resulting in its amalgamation with the clast.

2.3. Organic Geochemical Analysis

The samples, after being pulverized and dried at 40 °C, were subjected to the Rock-Eval pyrolysis technique [33,34,35] in the Institute of Petroleum Research (IPR)—FORTH, using a Delsi Rock-Eval VI system. The determined parameters are presented in Table A1, Table A2, Table A3, Table A4 and Table A5 of Appendix A.
Briefly, during the Rock-Eval pyrolysis the rock sample is heated in an inert (nitrogen) atmosphere. Hydrocarbons already present in the sample are volatized at 300 °C and recorded as the S1 peak. As the analysis proceeds at higher temperatures (up to 850 °C), hydrocarbons generated from the kerogen are recorded as the S2 peak (see Figure A1 in Appendix A for representative well-defined S2 peaks), which is an indicator of thermal maturity. Carbon dioxide and carbon monoxide produced during the pyrolysis are also recorded (S3 peak). Subsequently, the residual carbon is determined during oxidation of the sample (S4 peak). Considering the experimental data, the Tmax, total organic carbon (TOC), mineral carbon (MinC) content, hydrogen index (HI = 100 × S2 × TOC−1), and oxygen index (OI = 100 × S3 × TOC−1) are calculated based on Emeis and Kvenvolden [36].
The HI and OI parameters are used to characterize the origin of the organic matter. Marine organisms and algae, in general, are composed of lipid- and protein-rich organic matter, where the ratio of H to C is higher than in the carbohydrate-rich constituents of land plants. HI may reach up to 600 mg g−1 in geological samples. OI is correlated with the ratio of O to C, which is high for polysacharride-rich remains of land plants and inert organic material (residual organic matter) encountered as background in marine sediments. OI values do not usually exceed 240 mg g−1.

3. Results

3.1. General Lithological Description and Dating of Samples

The 28 examined clasts were classified as mudstones, shales, carbonate mudstones, sandstone (sample LEV9GC 67–69 clast 2), and carbonate interlaminated sandstone/mudstone (sample LEV9GC 98–100 clast 1). Mudstones, however, dominated the clast lithology. For further details, see Table A1, Table A2, Table A3, Table A4 and Table A5 in Appendix A.
The14 examined sediment matrices were mixtures of clay, silt, and sand and can be classified as sandy mud. A detailed description of the mud matrices of the cored sediments in the OMVF has already been provided by Panagiotopoulos et al. [26].
Concerning the biostratigraphic dating accomplished through the calcareous nannofossil analysis (Table 1 and Table A6, Table A7, Table A8, Table A9, Table A10, Table A11, Table A12, Table A13, Table A14, Table A15, Table A16, Table A17, Table A18, Table A19, Table A20, Table A21, Table A22, Table A23, Table A24, Table A25, Table A26, Table A27, Table A28, Table A29, Table A30, Table A31, Table A32, Table A33, Table A34, Table A35, Table A36, Table A37, Table A38, Table A39, Table A40, Table A41, Table A42, Table A43, Table A44, Table A45, Table A46 and Table A47 in Appendix A), most of the clast samples were assigned to the early-middle Miocene (CNM6–7, CNM7, CNM8–9. and CNM10 biozones [30]). However, for the first time, Oligocene clasts (see Figure 5 and Table 1) were also identified in the broader Olimpi/Prometheus 2 area.
The rest of the clasts could not be accurately or reliably dated (see Table A2, Table A3, Table A4 and Table A5 in Appendix A) because of: (i) the significant reworking and/or mixing observed in the sediment samples; these clasts were labeled as “mixed Oligocene–Miocene”; and (ii) the lack of nannofossil content or limited occurrence of specimens (probably reworked); these clasts were labeled as “undetermined”. The latter category also included the samples LEV3GC 65–67 clast 2 and LEV9GC 128–130 clast 1, due to insufficient sedimentary material for nannofossil biostratigraphic analysis.
Regarding the examined matrices, an age of mixed Oligocene–Miocene may be suggested for almost all samples, since characteristic species from completely different biozones were identified (see Table A6, Table A9, Table A11, Table A14, Table A17, Table A23, Table A26, Table A29, Table A30, Table A33, Table A36, Table A40, and Table A44 in Appendix A, as well as Figure 6). Only one sample (LEV3GC 2–5 matrix) appeared to be barren of nannofossils.

3.2. Organic Geochemical Analysis

The Rock-Eval analysis provides information about the richness, the quality, and the maturation level of the organic matter in sediments and rocks. Characteristic nomograms for the evaluation of the Rock-Eval experimental data are shown in Figure 7, Figure 8 and Figure 9, according to Espitalie et al. [33], Espitalie et al. [37], Hunt [38], and Jackson et al. [39]. Samples with OI values >240 mg g−1 (due to both matrix mineralogy and level of organic enrichment) and/or TOC values <0.3% are not shown in Figure 7 and Figure 8 because these data are considered of limited reliability for kerogen characterization.

3.2.1. Total Organic Carbon

The TOC values of the clasts fluctuated between 0.03% and 2.02%, while the TOC contents of the matrix samples varied between 0.25% and 0.94%. Two semi- to well-consolidated coarse-grained clasts from the Leipzig MV, i.e., one sandstone and one carbonate mudstone/sandstone (LEV9GC 67–69 clast 2 and LEV9GC 98–100 clast 1, respectively), exhibited very low values (0.03% and 0.26%, respectively), while one mudstone (LEV1GC 4–6 clast 1) from the Gelendzhik MV, dated as the middle Miocene (late Serravallian, CNM10), demonstrated the highest value.

3.2.2. Organic Matter Quality (Kerogen Type) and Thermal Maturation

Most of the data points associated with both clasts and matrices showed a distribution near the type III kerogen curve (Figure 7 and Figure 8). Nevertheless, the organic-rich mudstone (LEV1GC 4–6 clast 1) from the Gelendzhik MV plateau (see above) may be characterized as a mixed type II/III kerogen (Figure 7 and Figure 8).
In general, the analyzed samples were considered as “immature” for petroleum hydrocarbon generation, showing Tmax values lower than the oil window onset (Tmax of 435 °C) [33]. However, three clasts, i.e., the Miocene (CNM6–7) mudstone/carbonate mudstones LEV3GC 65–67 clast 1, LEV5GC 70–72 clast 1, and LEV9GC 67–69 clast 1, from the Heraklion, Moscow, and Leipzig MVs, respectively (see Table A2, Table A3, and Table A5 in Appendix A, as well as Figure 8), and one mixed Oligocene–Miocene matrix sample (LEV7GC 78–80) from the Milano MV (see Table A4 in Appendix A) were nearly “mature” (Tmax of 430–434 °C). In addition, based on Figure 9, the above-mentioned mudstone (LEV1GC 4–6 clast 1) from the Gelendzhik MV could be considered as a material of “good” hydrocarbon-generation potential.
Finally, the broad scattering of the data points in the HI vs. OI plot (Figure 7) indicates multiple sources for the organic matter of the investigated mud breccias.

3.2.3. Carbonates

The MinC contents of the pyrolyzed samples were used for the calculation of the carbonate contents by applying the equation of Jiang et al. [40]: Qcarbonates = 7.976 × MinC. According to the results (see Table A1, Table A2, Table A3, Table A4 and Table A5 in Appendix A), only four clasts contained Qcarbonates > 50% and, thus, they were characterized as carbonate mudstones.

4. Discussion

4.1. Stratigraphic Origin Evidence

It is considered that the clasts can lead to safer conclusions regarding their stratigraphic origin compared to the mud matrices, which are rather an irregular mixture of several stratigraphic layers during their upward movement through thick sections of sedimentary rocks. In contrast, the clasts reflect more reliably the characteristics of the source rocks, because they are the result of the high consolidation of sedimentary material in the deep-seated strata that have been removed and migrated to the seabed surface because of the tectonic overpressure (related with backthrusting) developed in the region. The variability in the macroscopic characteristics of the clasts (i.e., color, fissility, grain size; see Figure 4) suggests that the clasts do not share the same stratigraphic origin. This interpretation is further supported by the microscopic observations made during the nannofossil analysis.
Previous studies have suggested that the clasts from the broader Olimpi/Prometheus 2 area should be of Burdigalian–Langhian and early Serravallian age, containing reworked Oligocene, Eocene, and Cretaceous nannofossils [6,7,41,42,43]. In the present study, Burdigalian–Langhian mudstone/shale clasts (assigned to biozones CNM6–7; see Table 1) were common, while the latest Serravallian and Oligocene clasts were also identified. It is worth mentioning that the newly diagnosed Oligocene clasts from the OMVF include nannofossil assemblages, which are quite similar to the typical nanno-assemblages of the age-equivalent Gavrovo flysch (e.g., [44,45,46]).
The LEV1GC 4–6 clast 1 sample, a mudstone from the Gelendzhik MV (see Section 3.2.1), shows some interesting features regarding both its microscopic image and geochemical values: (i) it is characterized by a great abundance of both calcareous and siliceous microfossils, which indicates increased water column primary production (e.g., [47]) by the time of sediment deposition (CNM10—latest Serravallian age); and (ii) the Rock-Eval pyrolysis of this clast showed a high TOC value (~2%) together with a high HI and a relatively low OI (438 and 91 mg g−1, respectively; see Table A1 in Appendix A), which indicate low oxygen availability during the sediment deposition. Therefore, it is quite possible that anoxic/hypoxic conditions were triggered near the seafloor by the increased productivity in the euphotic zone together with enhanced organic matter preservation, resulting in the formation of deposits of sapropelic nature (e.g., [48,49,50]). Based on the previous interpretations, we believe that the LEV1GC 4–6 clast 1 sample originated from a sapropelic source rock.
The oldest known sapropels in the Mediterranean sedimentary sequences are considered to be of the Langhian age (~15.4 Ma) and can be found onshore northern Cyprus [51] as well as in the central part of the island, predominantly in marly successions (Kottafi Hill section, ranging up to CNM10 [52,53]). In addition, sapropel layers as old as the Langhian age (with the oldest layer assigned to the CNM7 biozone) were discovered offshore western Cyprus [54] during the leg 42A (site 375) of the Deep Sea Drilling Project (DSDP). In the latter study, a distinct sapropel was identified, whose characteristics are analogous to the LEV1GC 4–6 clast 1 sample regarding its age and organic content (~2%). Considering the fact that recent sapropels (Plio–Pleistocene and Holocene formations; e.g., [48,49,50,55]) are well studied and correlated across the Mediterranean basin, we suggest that the sapropel-like material of LEV1GC 4–6 clast 1 could originate from the equivalent deposits recorded in the sequences of the DSDP site 375.
Concerning the analyzed mud matrices, almost all samples were found to contain mixed assemblages consisting mostly of Miocene–Oligocene nannofossils together with older (reworked) species of Eocene and Cretaceous. The mixed assemblages in the mud matrices provide strong evidence that the investigated MVs are fed by multiple source rocks. However, one sample (LEV3GC 2–5 matrix) appeared to be barren of nannofossils (see Table A2 in Appendix A), emphasizing the great degree of heterogeneity in the mud breccia deposit. It can be suggested that the mixing of sediments took place at two stages: (i) an initial mixing of sediments coming from different sources occurred when they entered the MV’s feeder conduit and (ii) a further mixing occurred during the dynamic extrusion of the mudflows onto the seafloor.

4.2. Significance of the Reworked Nannofossil Species

Almost every examined clast included ~10% of reworked Miocene, Oligocene, Eocene, and Late- and Early-Cretaceous nannofossils, (see Table A7, Table A8, Table A10, Table A12, Table A15, Table A18, Table A19, Table A20, Table A21, Table A22, Table A24, Table A25, Table A28, Table A31, Table A32, Table A34, Table A37, Table A38, Table A41, Table A42, Table A43, Table A46, and Table A47 in Appendix A). These reworked specimens from older strata can provide valuable information concerning the stratigraphy and geological history of the MR.
In particular, it was observed that:
  • The middle Miocene (CNM7, CNM8–9 and CNM10) clasts embraced reworked nannofossils of the early-middle Miocene, Oligocene, Eocene, and Cretaceous;
  • The early-middle Miocene (CNM6–7) clasts included reworked nannofossils of the Oligocene, Eocene, and Cretaceous;
  • The Oligocene (CNO4/CNO5) clasts comprised reworked nannofossils of the Eocene and Cretaceous.
In addition, a remarkable observation was the absence of Paleocene species from all investigated clasts, which might be the result of severe thinning of Paleocene strata in the fold and thrust belt zone. Actually, the only indication that would support the existence of Paleocene material is the presence of Discoaster multiradiatus, whose first occurrence takes place at the base of CNP11 (NP9 biozone [32]).
The presence of reworked nannofossils in both Miocene and Oligocene assemblages of the analyzed clasts indicates the following: (i) subaerial/subsea exposure and erosion of Cretaceous and Eocene sequences during the Oligocene; (ii) subaerial/subsea exposure and erosion of the Oligocene, Eocene, and Cretaceous sequences during the early-middle Miocene; and (iii) subaerial/subsea exposure and erosion of the early-middle Miocene, Oligocene, Eocene, and Cretaceous sequences during the middle Miocene. It should be noted that intense sediment transport and redeposition is a common feature of the sedimentary processes in active forearc basins (e.g., formation of deep-sea flysch turbidites; see [56] and references therein).
However, it is not clear if the erosion and redeposition of the older sediments took place in subaerial or subsea conditions, even though a combination of both conditions would be more realistic. The subaerial exposure and erosion scenario can be supported by the high OI values calculated for most of the clasts after the Rock-Eval pyrolysis runs (see Table A1, Table A2, Table A3, Table A4 and Table A5 in Appendix A), which is a typical characteristic of the type III kerogen that indicates high terrestrial inputs [57]. The subsea erosion scenario, e.g., caused by intense turbidity current activity, is supported by the fact that the region southern of Crete is tectonically very active and experiences both compressional and extensional stresses (e.g., [21,22]). In such environments, steep slopes are formed and frequently fail due to seismic shaking, creating favorable conditions for the development of strong turbidity currents [56].

4.3. Organic Geochemistry Evidence

From a statistical point of view, the TOC content threshold for non-reservoir shale-type (source rock) sediments in oil provinces is considered the value of 0.5% [35]. Consequently, the source rock hydrocarbon-generative potential is considered as “poor” for TOC contents <0.5%, “fair” for values of 0.5–1%, “good” for values of 1–2%, and “very good” for values greater than 2% ([58]; see Table 2). Concerning the matrix samples, only four exceeded the TOC threshold of 0.5%, while the rest of them were considered as “poor” (see Table A1, Table A2, Table A3, Table A4 and Table A5 in Appendix A and Table 2). In contrast, the clast samples appeared to be richer in organic content; 12 of them appeared as “fair”, while the sapropelic mudstone clast (LEV1GC 4–6 clast 1) from the Gelendzhik MV plateau was classified as “very good” (TOC = 2.02%). Taking into account that the clasts can provide better evidence concerning the region’s deep stratigraphy, it can be concluded that ~46% of the randomly sampled clastic material originated from Miocene source rocks of “fair” and “very good” hydrocarbon-generating potential, buried ~2 km below the MR seafloor [26].
The suggested type III kerogen for the majority of analyzed samples (clasts and matrices) indicates a higher (terrestrial) plant contribution to the organic matter accumulation [57], which is in accordance with previous studies (e.g., [26,59]). Kerogen III is commonly considered as more favorable for gas enrichment than for oil generation [33]. Only the CNM10 LEV1GC 4–6 clast 1 sample, interpreted as being derived from a sapropelic formation, tended to approach the curve of the type II kerogen (see Figure 7). Kerogen II is primarily composed of marine organic materials (phytoplankton, zooplankton, and bacteria) together with allochthonous organic matter (originating, for example, from higher plants) [57] and is more prone to generating oil [33].
Based on Figure 8, all analyzed mud breccia samples were considered as “immature” to nearly “mature” for hydrocarbon-generation potential. Because the thermal condition for oil generation ranges from 100 to 150 °C [57], all cored sediments were subjected to temperatures lower than 100 °C. However, there is a possibility that four samples, i.e., LEV3GC 65–67 clast 1, LEV5GC 70–72 clast 1, LEV9GC 67–69 clast 1, and LEV7GC 78–80 matrix, which were characterized as nearly “mature” (see Section 3.2.2), were subjected to a heating close to 100 °C. Previous investigations have also led to a similar interpretation regarding the thermal maturity of clasts and matrix (e.g., [10,59], supporting the results of this study.
During the Rock-Eval pyrolysis performance, some samples demonstrated anomalous S2 signals. These anomalies concerned nine clasts (LEV1GC 4–6 clast 2, LEV1GC 18–20 clast 1, LEV1GC 65–67 clast 1, LEV5GC 10–12 clast 2, LEV5GC 40–42 clast 2, LEV5GC 123–125 clast 1, LEV5GC 123–125 clast 2, LEV7GC 40–43 clast 1, and LEV9GC 67–69 clast 2) and two matrix samples (LEV1GC 65–67 and LEV3GC 2–5), and appeared as bimodal S2 peaks (Figure 10a–d), probably indicating mixtures of organic matter from dissimilar stratigraphic horizons, from contrasting environments (terrestrial and marine), or of different thermal maturity. For this reason, the Tmax values estimated from the peaks of the S2 profiles of these samples were considered as highly uncertain; according to Yang and Horsfield [60], numerous factors can artificially modify the Tmax values and influence the maturity judgments. Nevertheless, the moderate to major reworking of the nannofossil assemblages of most of the above-mentioned clasts supports the interpretation of the organic matter mixing.

5. Conclusions

This study provides important information concerning the (pre-Messinian) sub-salt sediments of the eastern Mediterranean basin, south of Crete, which is an underexplored marine region lacking deep exploratory wells.
A biostratigraphic dating of mud breccia deposits (including clasts and mud matrices) from the Olimpi mud volcano field, based on a meticulous calcareous nannofossil analysis, led, for the first time, to the determination of one Oligocene (CNO4/CNO5) mudstone clast, two Oligocene (the assemblage mostly indicating the CNO3-CNO4/CNO5 biozones) mudstone/shale clasts, and four Serravallian (CNM10) mudstone clasts, with the rest of the analyzed sediments being assigned to the biozones CNM6–7, CNM7, and CNM8–9. Previous studies have dated analogous sediments from the broader Olimpi/Prometheus 2 area as Burdigalian–Langhian and early Serravallian. Almost all examined samples included Miocene, Oligocene, Eocene, and Cretaceous reworked nannofossils.
Both clasts and matrices of the cored mud breccias were subjected to Rock-Eval pyrolysis in order to evaluate the sediments’ source rock potential for hydrocarbon generation. For this evaluation, the total organic carbon (TOC) values, kerogen type, and thermal maturation were determined. The results showed (i) the distribution of the majority of the data points associated with the pyrolyzed sediments close to the type III kerogen curve, (ii) organic-rich (TOC >0.5%) and organic-poor sediments (TOC <0.5%), and (iii) “immature” (Tmax <434 °C) to nearly “mature” (Tmax of 430–434 °C) material.
On the other hand, the pyrolysis results remarkably revealed one CNM10 mudstone clast from the Gelendzhik MV plateau with a high TOC content (~2%) and composed of organic matter of a mixed type II/III kerogen (oil prone). In addition, the high hydrogen index and relatively low oxygen index of the previous clast together with its enhanced calcareous and siliceous microfossil content provide good evidence that the source of this material is a sapropelic rock.
Finally, we believe that the data provided by the current investigation can be significant for the oil and gas exploration of the wider study area (offshore southern Crete), since they shed light on the occurrence and stratigraphic position of hydrocarbon source rocks, although they are estimated to be below the thermal condition for oil generation. Because the Mediterranean Ridge accretionary complex is a highly-tectonized region, it is reasonable to assume that the lateral extension of the determined Miocene source rocks might potentially occur deeper in the stratigraphic column of the broader Olimpi mud volcano area, thus reaching the oil/gas window maturities.

Author Contributions

Conceptualization, A.N., M.V.T. and A.G.; methodology, M.V.T., G.R., N.P., A.G., I.H. and A.N.; validation, M.V.T., A.N., I.P., G.R., N.P., I.H. and A.G.; investigation, M.V.T., A.N., I.P., G.R. and A.G.; data curation, A.N., M.V.T., N.P. and I.P.; writing—original draft preparation, A.N., M.V.T., I.P., G.R. and A.G.; writing—review and editing, A.N., M.V.T., I.P. and N.P.; visualization, A.N., M.V.T., I.P., N.P. and G.R.; supervision, M.V.T., A.G. and G.R. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the General Secretariat for Research and Technology of Greece within the framework of the Programming Agreements with the Hellenic Research Centers for the period 2014–2016.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in Appendix A.

Acknowledgments

The technical support provided by the captain and crew of the R/V Aegaeo is highly acknowledged. This work has been accomplished in the framework of the Interdisciplinary Postgraduate Study Program “Palaeontology-Geobiology”.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

The information derived from the macroscopic examination and biostratigraphic and geochemical analyses of the collected mud breccia samples is presented in the Table A1, Table A2, Table A3, Table A4 and Table A5 provided below. This information includes:
  • Sampling intervals and sample types (matrix or clast);
  • Percentages of nannofossils in the images captured by the Leica DMLSP optical polarizing light microscope, dating of sediments and rock types;
  • Macroscopic observations such as consolidation degree of samples, sediment color, fissility occurrence, and characteristic sound during samples’ homogenization that is indicative of quartz presence;
  • Parameters measured during each Rock-Eval pyrolysis run such as S1, S2, and S3 peaks;
  • Parameters calculated from the Rock-Eval experimental data such as Tmax, HΙ, and OI, and TOC, MinC, and carbonate contents.
The consolidation degree of the matrix intervals has already been described by Panagiotopoulos et al. [26]. The consolidation degree of the investigated clasts was determined using an empirical method, following the criteria described below:
  • Soft: the rock can be broken between fingers;
  • Soft to semi-consolidated: the rock can be broken between fingers and a hard object (e.g., mortar or table surface) with normal effort;
  • Semi-consolidated: the rock can be broken between fingers and a hard object (e.g., mortar or table surface) with a lot of effort;
  • Semi- to well-consolidated: the rock can be broken between pestle and mortar with normal effort;
  • Well-consolidated: the rock can be broken between pestle and mortar with a lot of effort.
All nannofossil assemblages identified during the present study together with their semi-quantitative determination are displayed in the Table A6, Table A7, Table A8, Table A9, Table A10, Table A11, Table A12, Table A13, Table A14, Table A15, Table A16, Table A17, Table A18, Table A19, Table A20, Table A21, Table A22, Table A23, Table A24, Table A25, Table A26, Table A27, Table A28, Table A29, Table A30, Table A31, Table A32, Table A33, Table A34, Table A35, Table A36, Table A37, Table A38, Table A39, Table A40, Table A41, Table A42, Table A43, Table A44, Table A45, Table A46 and Table A47 provided below. Note that the counted specimens are expressed vs. the number of fields of view (see Section 2.2 for details).
Finally, Figure A1 illustrates representative Rock-Eval pyrograms showing typical unimodal and almost symmetric S2 curves.
Table A1. Gelendzhik MV (LEV1GC core).
Table A1. Gelendzhik MV (LEV1GC core).
Core
Interval
(cm)
Samp. TypeNannofossils
(%)
DatingRock TypeConsolid. DegreeColorRemarkOI
mg g−1
HI
mg g−1
Tmax
°C
TOC
%
MinC
%
S1
mg g−1
S2
mg g−1
S3
mg g−1
Carbonate
%
4–6matrix30mixed; mostly
Oligocene–Miocene
sandy mudsoftgreenish grey (10GY5/1)quartz sound228.0939.334210.891.850.010.352.0314.76
4–6clast 170–80CNM10mudstonesoftpale yellow (5Y8/3) 91.09437.624132.024.660.398.841.8437.17
4–6clast 210CNM10mudstonesemi-wellvery dark grey
(N3/)
331.15114.75?0.610.350.010.72.022.79
18–20matrix30mixed; mostly
Oligocene–Miocene
sandy mudfirmgreenish grey (10GY5/1)quartz sound366.0458.494260.531.240.010.311.949.89
18–20clast 150CNM8–9mudstonesemigreenish grey (5GY6/1) 95.38155.38?0.650.3601.010.622.87
65–67matrix30mixed; mostly
Oligocene–Miocene
sandy mudfirmdark greenish grey (10GY4/1) 431.9187.23?0.471.010.020.412.038.06
65–67clast 1<10CNM10mudstonesemigrey
(N5/)
354116?0.50.80.020.581.776.38
Table A2. Heraklion MV (LEV3GC core).
Table A2. Heraklion MV (LEV3GC core).
Core
Interval
(cm)
Samp. TypeNannofossils
(%)
DatingRock TypeConsolid. DegreeColorRemarkOI
mg g−1
HI
mg g−1
Tmax
°C
TOC
%
MinC
%
S1
mg g−1
S2
mg g−1
S3
mg g−1
Carbonate%
2–5matrixalmost barrenundeterminedsandy mudvery softdark greenish grey (10GY4/1)quartz sound32200?0.250.0600.50.080.48
25–27matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffgreenish grey (7.5GY5/1)quartz sound138.334.044180.942.80.010.321.322.33
65–67clast 130–40CNM6–7mudstonesoftpale yellow (5Y8/3) 126.8131.964340.975.040.011.281.2340.2
65–67clast 2?undeterminedmudstonesoftlight grey (N7/) 142.6741.334160.754.5900.311.0736.61
Table A3. Moscow MV (LEV5GC core).
Table A3. Moscow MV (LEV5GC core).
Core
Interval
(cm)
Samp. TypeNannofossils
(%)
DatingRock TypeConsolid. DegreeColorRemarkOI
mg g−1
HI
mg g−1
Tmax
°C
TOC
%
MinC
%
S1
mg g−1
S2
mg g−1
S3
mg g−1
Carbonate
%
10–12matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffgreenish grey (7.5GY5/1)quartz sound529.4135.294260.342.6800.121.821.38
10–12clast 1~10mainly CNO3-
CNO4/CNO5
shalesemigreenish grey (5GY6/1)sub-parallel fissility516.6758.334190.362.4600.211.8619.62
10–12clast 2~30mixed; mostly
Oligocene–Miocene
mudstonesemidark grey (N4/) 481.82145.45?0.110.180.010.160.531.44
40–42clast 170–80CNO4/CNO5mudstonesoft-semipale yellow (5Y8/3) 465.7921.054270.386.0400.081.7748.18
40–42clast 2~10mixed; mostly
Oligocene–Miocene
mudstonesemi-wellvery dark grey
(N3/)
373.68100?0.190.2600.190.712.07
70–72clast 130–40CNM6–7carbonate mudstonesemigrey
(N6/)
230.592204330.856.710.021.871.9653.52
100–102matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffgreenish grey (10GY5/1)quartz sound490.9157.584240.331.9300.191.6215.39
100–102clast 1≤10mainly CNO3-
CNO4/CNO5
mudstonesemidark grey (N4/) 287.564.584260.480.4300.311.383.43
100–102clast 220–30CNM10mudstonesemi-wellgrey
(N6/)
195.8391.674230.241.1600.220.479.25
123–125matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffgreenish grey (10GY5/1)quartz sound497.1468.574270.351.930.010.241.7415.39
123–125clast 1almost barrenundeterminedmudstonesemidark greyish brown (10YR4/2) 249.1261.4?0.570.220.020.351.421.75
123–125clast 230CNM7carbonate mudstonesemi-wellpale yellow (5Y8/3) 539.1317.39?0.238.230.010.041.2465.64
Table A4. Milano MV (LEV7GC core).
Table A4. Milano MV (LEV7GC core).
Core
Interval
(cm)
Samp. TypeNannofossils
(%)
DatingRock TypeConsolid. DegreeColorRemarkOI
mg g−1
HI
mg g−1
Tmax
°C
TOC
%
MinC
%
S1
mg g−1
S2
mg g−1
S3
mg g−1
Carbonate
%
12–14matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery softgreenish grey (10GY5/1)quartz sound473.1758.544270.411.640.010.241.9413.08
40–43matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery softgreenish grey (10GY5/1)quartz sound446.9467.354270.491.670.010.331.9413.32
40–43clast 1<10CNM8–9shalewelldark greyish brown (10YR4/2)parallel fissility270.4988.52?0.610.40.010.541.653.19
40–43clast 220–30CNM8–9mudstonesemigreenish grey (5GY6/1) 554.1737.53990.482.290.010.182.6618.27
78–80matrix30mixed; mostly
Oligocene–Miocene
sandy mudsoftdark greenish grey (10GY4/1)quartz sound380.4365.224320.461.720.010.31.7513.72
78–80clast 1<5CNM8–9mudstonesemi-welldark grey (N4/1) 265.7142.864270.351.4600.150.9311.64
78–80clast 2almost barrenundeterminedmudstonesemigreenish grey (5GY6/1) 477.2752.274130.440.620.010.232.14.95
Table A5. Leipzig MV (LEV9GC core).
Table A5. Leipzig MV (LEV9GC core).
Core Interval
(cm)
Samp. TypeNannofossils
(%)
DatingRock TypeConsolid. DegreeColorRemarkOI
mg g−1
HI
mg g−1
Tmax
°C
TOC
%
MinC
%
S1
mg g−1
S2
mg g−1
S3
mg g−1
Carbonate
%
10–13matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery softgreenish grey (10GY5/1)quartz sound224.6252.314280.651.520.010.341.4612.12
10–13clast 1≤10CNM8–9mudstonewellvery dark grey
(N3/)
189.9393.224270.590.610.010.551.124.87
67–69clast 1<10CNM6–7mudstonesoftgrey
(N/6)
76.1276.124340.670.370.010.510.512.95
67–69clast 2almost barrenundeterminedsandstonesemi-wellgreyish green (5G5/2) 200100?0.030.0300.030.060.24
98–100matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffdark greenish grey (10GY4/1)quartz sound168.7556.254270.481.5800.270.8112.6
98–100clast 1~10mixed; mostly
Oligocene–Miocene
carbonate mudstone/
sandstone
semi-welllight grey (N7/)/dark grey (N4/)interbedding, quartz sound207.6942.314240.269.3500.110.5474.58
98–100clast 230–40CNM6–7mudstonesemi-wellgrey
(N/6)
127.5963.224240.873.5800.551.1128.55
98–100clast 350–60CNM8–9shalewellGrey
(N/6)
sub-parallel fissility291.6794.444230.366.0900.341.0548.57
128–130matrix30mixed; mostly
Oligocene–Miocene
sandy mudvery stiffdark greenish grey (10GY4/1)quartz sound155.161.224220.491.6300.30.7613
128–130clast 1?undeterminedshalesemi-wellreddish brown (2.5YR4/4)sub-parallel fissility321.6251.354270.370.9300.191.197.42
128–130clast 220–30CNM7carbonate mudstonesemipale yellow (5Y8/3) 2201304280.47.2300.520.8857.67
128–130clast 3~5CNM8–9mudstonesemilight grey (N7/) 73.33644260.750.2600.480.552.07
Table A6. Gelendzhik MV.
Table A6. Gelendzhik MV.
LEV1GC 4–6 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 7
Calcidiscus macintyrei X 7
Discoaster quinqueramus X1
Discoaster variabilis X 4
Helicosphaera carteri X 6
Reticulofenestra pseudoumbilicus X 9
Umbilicosphaera jafari X1
Umbilicosphaera rotula X 7
Sphenolithus disbelemnos X1
Sphenolithus tintinnabulum X1
Sphenolithus neoabies X 5
Paleogene
Micrantholithus sp. X1
Reticulofenestra bisecta X 9
Long-range Paleogene–Neogene
Coccolithus pelagicusX 24
Coronocyclus mesostenos X2
Cyclicargolithus floridanusX 20
Discoaster sp. X 8
Pontosphaera multipora X1
Rhabdosphaera sp. X3
small reticulofenestroidsX 29
Sphenolithus moriformis X 6
Helicosphaera mediterranea X2
Helicosphaera sp. X 6
Sphenolithus sp. X3
Other
Siliceous microfossils X2
Table A7. Gelendzhik MV.
Table A7. Gelendzhik MV.
LEV1GC 4–6 Clast 1
Biozone: CNM10
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporusX 30
Calcidiscus macintyrei X1
Discoaster formosus X3
Discoaster braarudii X3
Discoaster kugleri X2
Discoaster variabilis X3
Helicosphaera carteri X2
Umbilicosphaera rotula X2
Long-range Paleogene–Neogene
Coccolithus pelagicus X3
Discoaster sp.X 13
small reticulofenestroidsX 10
Sphenolithus moriformis X1
Other
Siliceous microfossilsX 20
Table A8. Gelendzhik MV.
Table A8. Gelendzhik MV.
LEV1GC 4–6 Clast 2
Biozone: CNM10
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X1
Calcidiscus macintyrei X2
Coccolithus miopelagicus X2
Discoaster apetalus X1
Discoaster assymetricus X1
Discoaster exilis X1
Discoaster kugleri X2
Discoaster ulnatus X1
Discoaster variabilis X 8
Helicosphaera carteri X 5
Reticulofenestra pseudoumbilicusX 32
Sphenolithus disbelemnos X1
Sphenolithus dissimilis X2
Umbilicosphaera foliosa X 5
Umbilicosphaera rotula X1
Paleogene
Reticulofenestra bisectaX 10
Reticulofenestra hillae X1
Sphenolithus predistentus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 21
Coronocyclus nitscens X1
Cyclicargolithus floridanus X3
Discoaster deflandrei X1
Discoaster sp.X 23
Pontosphaera multipora X3
Reticulofenestra perplexa X2
small reticulofenestroidsX 16
Sphenolithus moriformisX 11
Table A9. Gelendzhik MV.
Table A9. Gelendzhik MV.
LEV1GC 18–20 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 5
Calcidiscus macintyrei X3
Discoaster apetalus X1
Discoaster calcaris X1
Discoaster variabilis X 6
Gephyrocapsa <3 μm X1
Helicosphaera carteri X 9
Helicosphaera selli X1
Reticulofenestra pseudoumbilicusX 10
Sphenolithus abies X1
Sphenolithus heteromorphus X1
Umbilicosphaera foliosa X2
Umbilicosphaera jafari X2
Paleogene
Cyclicargolithus abisectus X1
Discoaster saipanensis X1
Discoaster spinescens X1
Micrantholithus sp. X1
Reticulofenestra hillae X1
Reticulofenestra bisecta X 5
Long-range Paleogene–Neogene
Coccolithus pelagicusX 29
Coronocyclus nitescens X1
Cyclicargolithus floridanusX 28
Discoaster sp.X 18
Pontosphaera multipora X1
Pontosphaera sp. X3
Rhabdosphaera sp. X1
small reticulofenestroidsX 19
Sphenolithus moriformis X3
Table A10. Gelendzhik MV.
Table A10. Gelendzhik MV.
LEV1GC 18–20 Clast 1
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 4
Calcidiscus macintyreiX 12
Discoaster variabilis X 5
Helicosphaera carteri X 5
Helicosphaera walbersdorfensis X 5
Reticulofenestra pseudoumbilicusX 13
Sphenolithus abies X 4
Sphenolithus heteromorphus X1
Umbilicosphaera rotula X 4
Paleogene
Calcidiscus gerrardii X1
Micrantholithus sp. X1
Reticulofenestra hillae X1
Reticulofenestra reticulata X1
Reticulofenestra bisecta X2
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X 4
Coccolithus pelagicusX 22
Coronocyclus nitescens X1
Cyclicargolithus floridanus X1
Discoaster sp. X 7
Helicosphaera intermedia X1
Helicosphaera mediterranea X1
Pontosphaera multipora X2
Pontosphaera sp. X3
Reticulofenestra perplexaX 20
Rhabdosphaera sp. X2
small reticulofenestroidsX 25
Sphenolithus moriformis X 6
Cretaceous
Zeugrhabdotus sp. X1
Table A11. Gelendzhik MV.
Table A11. Gelendzhik MV.
LEV1GC 65–67 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X2
Calcidiscus macintyrei X3
Discoaster braarudii X2
Discoaster cauliflorus X1
Discoaster decorus X2
Discoaster exilis X3
Discoaster variabilis X 9
Helicosphaera carteri X 9
Helicosphaera walbersdorfensis X1
Helicosphaera wallichi X3
Reticulofenestra pseudoumbilicusX 17
Sphenolithus heteromorphus X1
Umbilicosphaera jafari X 6
Umbilicosphaera rotula X2
Helicosphaera etholonga X1
Paleogene
Discoaster barbadiensis X1
Reticulofenestra hillae X2
Reticulofenestra bisecta X 5
Long-range Paleogene–Neogene
Coccolithus pelagicusX 13
Coronocyclus mesostenos X 8
Cyclicargolithus floridanusX 11
Discoaster sp. X 6
Pontosphaera discopora X1
Pontosphaera multipora X 8
Pontosphaera sp. X1
Reticulofenestra perplexa X3
Rhabdosphaera sp. X2
small reticulofenestroidsX 13
Sphenolithus moriformis X 9
Table A12. Gelendzhik MV.
Table A12. Gelendzhik MV.
LEV1GC 65–67 Clast 1
Biozone: CNM10
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X4
Discoaster braarudii X4
Discoaster decorus X2
Discoaster kugleri X1
Discoaster variabilis X 4
Gephyrocapsa <3 μm X1
Helicosphaera carteriX 10
Helicosphaera dissimilis X1
Helicosphaera selli X1
Reticulofenestra pseudoumbilicusX 22
Sphenolithus delphix X1
Sphenolithus heteromorphus X1
Sphenolithus neoabies X1
Umbilicosphaera jafari X2
Umbilicosphaera rotula X2
Paleogene
Discoaster barbadiensis
Helicosphaera recta X1
Reticulofenestra hillae X3
Reticulofenestra bisecta X3
Long-range Paleogene–Neogene
Coccolithus pelagicusX 16
Coronocyclus mesostenos X3
Cyclicargolithus floridanus X 5
Discoaster deflandrei X1
Pontosphaera multipora X2
Pontosphaera sp. X3
Reticulofenestra perplexa X2
Rhabdosphaera sp. X2
small reticulofenestroidsX 32
Sphenolithus moriformis X1
Table A13. Heraklion MV.
Table A13. Heraklion MV.
LEV3GC 2–5 Matrix
Biozone: undetermined
Table A14. Heraklion MV.
Table A14. Heraklion MV.
LEV3GC 25–27 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 4
Coccolithus miopelagicus X 4
Discoaster variabilis X2
Helicosphaera carteri X 3
Reticulofenestra pseudoumbilicus X 4
Sphenolithus abies X1
Sphenolithus cometa X3
Sphenolithus heteromorphusX 10
Umbilicosphaera rotula X1
Paleogene
Reticulofenestra bisecta X2
Reticulofenestra lockeri X2
Sphenolithus predistentus X1
Long-range Paleogene–Neogene
Coronocyclus mesostenos X1
Discoaster sp. X2
Sphenolithus truaxii X2
Helicosphaera sp. X 8
small reticulofenestroidsX 10
Reticulofenestra perplexaX 11
Sphenolithus moriformisX 11
Cyclicargolithus floridanusX 21
Coccolithus pelagicusX 34
Cretaceous
undetermined Cretaceous sp. X1
Table A15. Heraklion MV.
Table A15. Heraklion MV.
LEV3GC 65–67 Clast 1
Biozone: CNM6–7
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X2
Calcidiscus macintyrei X3
Calcidiscus premacintyrei X1
Discoaster variabilis X 8
Gephyrocapsa <3 μm X1
Helicosphaera ampliamperta X 5
Helicosphaera carteriX 16
Helicosphaera walbersdorfensis X6
Sphenolithus dissimilis X2
Sphenolithus heteromorphus X 5
Umbilicosphaera foliosa X1
Umbilicosphaera jafari X 9
Umbilicosphaera rotula X 6
Paleogene
Discoaster barbadiensis X1
Reticulofenestra lockeri X1
Reticulofenestra bisecta X2
Sphenolithus predistentus X2
Long-range Paleogene–Neogene
Coccolithus pelagicusX 61
Coronocyclus mesostenos X1
Cyclicargolithus floridanusX 15
Discoaster deflandrei X 12
Discoaster sp.X 35
Helicosphaera intermedia X 7
Pontosphaera sp. X2
small reticulofenestroidsX 25
Sphenolithus moriformisX 13
Cretaceous
undetermined Cretaceous sp. X1
Eiffellithus turriseiffelii X1
Table A16. Heraklion MV.
Table A16. Heraklion MV.
LEV3GC 65–67 Clast 2
Biozone: undetermined
Table A17. Moscow MV.
Table A17. Moscow MV.
LEV5GC 10–12 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X 4
Calcidiscus premacintyrei X1
Coccolithus miopelagicus X1
Discoaster variabilis X1
Gephyrocapsa <3 μm X2
Helicosphaera carteri X3
Helicosphaera orientalis X2
Pseudoemiliania lacunosa X2
Reticulofenestra pseudoumbilicus X 9
Sphenolithus heteromorphus X2
Syracosphaera pulchra X1
Umbilicosphaera jafari X 4
Umbilicosphaera rotula X1
Paleogene
Chiasmolithus sp. X1
Coccolithus formosus X3
Cyclicargolithus abisectus X3
Discoaster barbadiensis X1
Discoaster multiradiatus X1
Helicosphaera recta X1
Reticulofenestra lockeri X1
Reticulofenestra hillae X1
Reticulofenestra stavensis X1
Sphenolithus ciperoensis X1
Sphenolithus distentus X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 11
Coronocyclus mesostenos X3
Cyclicargolithus floridanus X 5
Discoaster deflandrei X1
Discoaster sp. X 5
Helicosphaera intermedia X1
Pontosphaera multipora X1
Pontosphaera sp. X2
Reticulofenestra perplexa X 4
small reticulofenestroids X3
Sphenolithus moriformis X 4
Cretaceous
undetermined Cretaceous sp. X1
Table A18. Moscow MV.
Table A18. Moscow MV.
LEV5GC 10–12 Clast 1
Mainly CNO3-CNO4/CNO5
SpeciesACFRSpecimens Counted
Neogene
Coccolithus miopelagicus X1
Discoaster discissus X1
Discoaster durioi X1
Discoaster exiis X3
Gephyrocapsa <3 μm X1
Helicosphaera carteri X 4
Sphenolithus abies X3
Paleogene
Coccolithus formosus X3
Discoaster barbadiensis X1
Discoaster multiradiatus X1
Discoaster nodifer X1
Helicosphaera compacta X2
Helicosphaera recta X2
Reticulofenestra lockeri X 7
Reticulofenestra bisecta X 4
Reticulofenestra reticulata X2
Sphenolithus distentus X 8
Sphenolithus obtusus X1
Sphenolithus peartiae X1
Sphenolithus predistentus X2
Zygrhablithus bijugatus X 4
Long-range Paleogene–Neogene
Coccolithus pelagicus X 10
Coronocyclus mesostenos X1
Cyclicargolithus floridanusX 71
Discoaster deflandrei X 9
Discoaster leroyi X1
Discoaster sp. X 8
Helicosphaera intermedia X1
Helicosphaera mediterranea X3
Pontosphaera multipora X3
Pontosphaera sp. X1
Sphenolithus moriformis X 7
small reticulofenestroids X 11
Cretaceous
Arkhangelskiales sp. X3
Broinsonia parca X1
undetermined Cretaceous sp. X3
Diazomatolithus lehmanii X1
Eiffelithus sp. X2
Zeugrhabdotus X2
Table A19. Moscow MV.
Table A19. Moscow MV.
LEV5GC 10–12 Clast 2
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 5
Calcidiscus macintyrei X 5
Coccolithus miopelagicus X1
Discoaster kugleri X1
Discoaster variabilis X1
Discoater durioi X1
Gephyrocapsa <3 μm X3
Helicosphaera carteri X 6
Helicosphaera orientalis X1
Helicosphaera selli X1
Helicosphaera stalis X2
Pontosphaera japonica X1
Pseudoemiliania lacunosa X2
Reticulofenestra pseudoumbilicus X 7
Rhabdosphaera? sp. X 3
Sphenolithus abies X 3
Sphenolithus belemnos X1
Sphenolithus dissimilis X1
Sphenolithus heteromorphus X 6
Syracosphaera pulchra X1
Umbilicosphaera foliosa X3
Umbilicosphaera jafari X 7
Umbilicosphaera rotula X1
Umbilicosphaera sibogae X1
Paleogene
Coccolithus formosus X2
Cyclicargolithus abisectus X 5
Discoaster multiradiatus X1
Helicosphaera compacta X2
Reticulofenestra lockeri X 4
Reticulofenestra bisecta X 9
Reticulofenestra hillae X1
Sphenolithus capricornatus X1
Sphenolithus ciperoensis X2
Sphenolithus distentus X3
Sphenolithus predistentus X1
Sphenolithus umbrellus X2
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 15
Coronocyclus mesostenos X 6
Coronocyclus nitescens X1
Cyclicargolithus floridanusX 26
Discoaster deflandrei X 5
Discoaster salomoni X2
Discoaster sp. X3
Helicosphaera intermedia X 5
Helicosphaera mediterranea X 3
Helicosphaera sp. X1
Pontosphaera multipora X1
Pontosphaera sp. X2
Sphenolithus moriformis X3
small reticulofenestroidsX 26
Table A20. Moscow MV.
Table A20. Moscow MV.
LEV5GC 40–42 Clast 1
Biozone: CNO4/CNO5
SpeciesACFRSpecimens Counted
Paleogene
Coccolithus eopelagicus X2
Cyclicargolithus abisectus X2
Discoaster barbadiensis X1
Helicosphaera obliqua X1
Helicosphaera recta X2
Reticulofenestra lockeri X1
Reticulofenestra bisecta X 5
Sphenolithus ciperoensis X 4
Sphenolithus distentus X2
Sphenolithus predistentus X1
Zygrhablithus bijugatus X 6
Long-range Paleogene–Neogene
Braarudosphaera bigelowi X1
Coccolithus pelagicusX 29
Coronocyclus mesostenos X 5
Coronocyclus nitescens X3
Cyclicargolithus floridanusX 81
Discoaster deflandrei X 11
Discoaster sp. X 3
Helicosphaera euphratis X2
Helicosphaera intermedia X3
Helicosphaera leesiae X2
Helicosphaera mediterranea X2
Pontosphaera japonica X 6
Rhabdosphaera? sp. X 4
Sphenolithus conicus X 4
Sphenolithus moriformisX 20
Cretaceous
Broinsonia parca X1
Eiffelithus sp. X1
Rhagodiscus infinitus X1
Table A21. Moscow MV.
Table A21. Moscow MV.
LEV5GC 40–42 Clast 2
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X3
Coccolithus miopelagicus X1
Helicosphaera carteri X 4
Helicosphaera princei X1
Helicosphaera stalis X1
Reticulofenestra pseudoumbilicus X2
Rhabdosphaera? sp. X2
Sphenolithus dissimilis X1
Sphenolithus heteromorphus X2
Sphenolithus tintinnabulum X1
Umbilicosphaera jafari X 5
Umbilicosphaera rotula X3
Paleogene
Calcidiscus gerrardii X1
Coccolithus crassus? X1
Coccolithus formosus X 7
Cyclicargolithus abisectus X2
Cyclicargolithus parvus X1
Discoaster wemmelensis X1
Helicosphaera leesiae X1
Helicosphaera recta X1
Reticulofenestra daviesii X1
Reticulofenestra lockeri X1
Reticulofenestra bisecta X 5
Sphenolithus ciperoensis X3
Sphenolithus distentus X2
Sphenolithus umbrellus X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 17
Coronocyclus mesostenos X3
Cyclicargolithus floridanusX 33
Discoaster deflandrei X3
Discoaster sp. X1
Pontosphaera sp. X1
small reticulofenestroidsX 17
Sphenolithus moriformis X 4
Table A22. Moscow MV.
Table A22. Moscow MV.
LEV5GC 70–72 Clast 1
Biozone: CNM6–7
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X1
Calcidiscus premacintyrei X3
Discoaster exilis X1
Helicosphaera ampliaperta X 6
Helicosphaera carteri X 5
Sphenolithus cometa X1
Sphenolithus dibelemnos X1
Sphenolithus heteromorphus X 5
Umbilicosphaera jafari X 4
Paleogene
Cyclicargolithus abisetus X2
Discoaster barbadiensis X1
Reticulofenestra lockeri X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 12
Coronocyclus mesostenos X4
Cyclicargolithus floridanusX 19
Discoaster deflandrei X 5
Discoaster sp. X8
Helicosphaera intermedia X4
Pontosphaera multipora X2
Pontosphaera sp. X1
Reticulofenestra perplexa X4
small reticulofenestroidsX 9
Sphenolithus moriformisX 15
Cretaceous
Dizomatolithus lehmanii X 1
Table A23. Moscow MV.
Table A23. Moscow MV.
LEV5GC 100–102 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X4
Calcidiscus macintyrei X3
Discoaster exilis X2
Gephyrocapsa <3 μm 1
Helicosphaera carteri X4
Reticulofenestra pseudoumbilicusX 18
Schyphosphaera intermedia X1
Sphenolithus cometa X2
Sphenolithus heteromorphus X4
Umbilicosphaera jafari X2
Umbilicosphaera rotula X2
Paleogene
Discoaster multiradiatus X1
Discoaster nodifer X1
Sphenolithus ciperoensis X2
Sphenolithus distentus X1
Sphenolithus predistentus X2
Zygrhablithus bijugatus X2
Long-range Paleogene–Neogene
Coccolithus pelagicusX 18
Coronocyclus mesostenos X2
Cyclicargolithus floridanusX 17
Discoaster deflandrei X3
Discoaster sp. X 5
Sphenolithus moriformis X 6
Cretaceous
Diazomatolithus lehmanii X1
Table A24. Moscow MV.
Table A24. Moscow MV.
LEV5GC 100–102 Clast 1
Mainly CNO3-CNO4/CNO5
SpeciesACFRSpecimens Counted
Neogene
Coccolithus miopelagicus X1
Discoaster kugleri X2
Reticulofenestra pseudoumbilicus X3
Umbilicosphaera jafari X3
Paleogene
Coccolithus formosus X 8
Reticulofenestra lockeri X2
Reticulofenestra reticulata X1
Reticulofenestra stavensis X 5
Sphenolithus distentus X 8
Sphenolithus peartiae X3
Umbilicosphaera detecta X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 22
Coronocyclus nitescens X2
Cyclicargolithus floridanusX 66
Discoaster deflandrei X2
Helicosphaera euphratis X1
Helicosphaera intermedia X3
Helicosphaera leesiae X1
Helicosphaera sp. X1
Pontosphaera multipora X1
small reticulofenestroidsX 13
Sphenolithus moriformisX 20
Cretaceous
undetermined Cretaceous sp. X2
Zeugrhabdotus sp. X1
Table A25. Moscow MV.
Table A25. Moscow MV.
LEV5GC 100–102 Clast 2
Biozone: CNM10
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X1
Calcidiscus macintyrei X2
Coccolithus miopelagicus X2
Discoaster kugleri X2
Discoaster variabilis X2
Gephyrocapsa <3 μm X2
Helicosphaera ampliaperta X3
Helicosphaera carteri X 10
Pseudoemiliania lacunosa? X2
Reticulofenestra pseudoumbilicusX 12
Sphenolithus heteromorphus X 4
Umbilicosphaera foliosa X2
Umbilicosphaera jafari X2
Umbilicosphaera rotula X1
Paleogene
Cyclicargolithus abisectus X2
Discoaster nodifer X1
Reticulofenestra lockeri X1
Reticulofenestra bisecta X 4
Sphenolithus ciperoensis X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 38
Cyclicargolithus floridanusX 36
Discoaster deflandrei X1
Discoaster sp. X1
Helicosphaera intermedia X2
Helicosphaera mediterranea X1
small reticulofenestroidsX 12
Sphenolithus moriformisX 13
Cretaceous
Diazomatolithus lehmanii X2
Eiffelithus sp. X1
other
Siliceous microfossils X2
Table A26. Moscow MV.
Table A26. Moscow MV.
LEV5GC 123–125 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X2
Calcidiscus macintyrei X2
Discoaster kugleri X1
Gephyrocapsa <3 μm X2
Helicosphaera carteri X 6
Reticulofenestra pseudoumbilicus X 9
Sphenolithus heteromorphus X3
Umbilicosphaera jafari X 4
Umbilicosphaera rotula X2
Paleogene
Reticulofenestra bisecta X1
Sphenolithus ciperoensis X1
Sphenolithus distentus X2
Sphenolithus predistentus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 16
Cyclicargolithus floridanusX 11
Discoaster deflandrei X2
Discoaster sp. X2
Helicosphaera leesiae X1
Reticulofenestra perplexa X 5
Sphenolithus moriformis X 8
Sphenolithus sp. X1
Cretaceous
undetermined Cretaceous sp. X1
Diazomatolithus lehmanii X2
Table A27. Moscow MV.
Table A27. Moscow MV.
LEV5GC 123–125 Clast 1
Biozone: undetermined
Table A28. Moscow MV.
Table A28. Moscow MV.
LEV5GC 123–125 Clast 2
Biozone: CNM7
SpeciesACFRSpecimens Counted
Neogene
Coccolithus miopelagicus X2
Helicosphaera carteri X 10
Sphenolithus heteromorphusX 27
Paleogene
Reticulofenestra bisecta X2
Long-range Paleogene–Neogene
Coccolithus pelagicusX 21
Cyclicargolithus floridanusX 16
Discoaster deflandrei X1
Discoaster sp. X 4
Helicosphaera intermedia X1
Micrantholithus sp. X1
Pontosphaera sp. X 4
Reticulofenestra perplexaX 30
small reticulofenestroids X 10
Sphenolithus moriformisX 15
Table A29. Milano MV.
Table A29. Milano MV.
LEV7GC 12–14 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X1
Calcidiscus macintyrei X 4
Coccolithus miopelagicus X1
Discoaster discissus X1
Discoaster durioi X1
Discoaster variabilis X1
Gephyrocapsa <3 μm X2
Helicosphaera carteri X 4
Pseudoemiliania lacunosa X2
Reticulofenestra pseudoumbilicusX 24
Sphenolithus heteromorphus X1
Umbilicosphaera jafari X 2
Umbilicosphaera rotula X1
Paleogene
Discoaster barbadiensis X3
Sphenolithus umbrellus X2
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X1
Coccolithus pelagicusX 8
Cyclicargolithus floridanusX 11
Discoaster deflandrei X3
Discoaster sp. X1
Helicosphaera intermedia X1
Pontosphaera multipora X2
Pontosphaera sp. X3
Reticulofenestra perplexa X 6
small reticulofenestroids X 10
Sphenolithus moriformis X 3
Cretaceous
Arkhangelskiella sp. X2
undetermined Cretaceous sp. X1
Rhagodiscus sp. X1
Table A30. Milano MV.
Table A30. Milano MV.
LEV7GC 40–43 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Pleistocene
Gephyrocapsa oceanica X2
Neogene
Calcidiscus macintyrei X 4
Coccolithus miopelagicus X1
Discoaster asymmetricus X1
Gephyrocapsa <3 μm X1
Helicosphaera carteri X 7
Helicosphaera princei X1
Helicosphaera stalis X1
Pseudoemiliania lacunosa X2
Reticulofenestra pseudoumbilicusX 40
Sphenolithus disbelemnos X2
Sphenolithus heteromorphus X 3
Umbilicosphaera jafari X 6
Paleogene
Cyclicargolithus abisetus X2
Discoaster barbadiensis X1
Reticulofenestra bisecta X1
Reticulofenestra lockeri X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X1
Coccolithus pelagicusX 15
Coronocyclus mesostenos X
Cyclicargolithus floridanus X 4
Discoaster deflandrei X
Discoaster sp. X 4
Helicosphaera mediterranea X1
Pontosphaera multipora X1
Pontosphaera sp. X 2
Reticulofenestra perplexa X2
Sphenolithus moriformis X 3
Cretaceous
undetermined Cretaceous sp. X1
Dizomatolithus lehmanii X 3
Eiffellithus turriseiffelii X1
Rhagodiscus sp. X1
Table A31. Milano MV.
Table A31. Milano MV.
LEV7GC 40–43 Clast 1
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X 6
Calcidiscus macintyreiX 12
Discoaster variabilis X 6
Helicosphaera carteri X 9
Helicosphaera walbersdorfensis X 5
Reticulofenestra pseudoumbilicusX 15
Sphenolithus abies X 4
Umbilicosphaera rotula X 4
Paleogene
Reticulofenestra hillae X3
Reticulofenestra reticulata X1
Reticulofenestra bisecta X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X 4
Coccolithus pelagicusX 19
Cyclicargolithus floridanus X1
Discoaster sp. X 8
Helicosphaera intermedia X1
Helicosphaera mediterranea X2
Pontosphaera multipora X2
Pontosphaera sp. X4
Reticulofenestra perplexaX 15
Rhabdosphaera sp. X2
small reticulofenestroidsX 18
Sphenolithus moriformis X 8
Cretaceous
Zeugrhabdotus sp. X1
undetermined Cretaceous sp. X1
Table A32. Milano MV.
Table A32. Milano MV.
LEV7GC 40–43 Clast 2
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X2
Cryptococcolithus sp. X1
Discoaster variabilis X1
Gephyrocapsa <3 μm X1
Helicosphaera carteriX 15
Helicosphaera stalis X1
Helicosphaera walbersdorfensis Χ 6
Reticulofenestra pseudoumbilicusX 39
Sphenolithus abies X2
Sphenolithus heteromorphus X1
Umbilicosphaera foliosa X1
Umbilicosphaera jafariX 20
Paleogene
Cruciplacolithus sp. X1
Reticulofenestra bisecta X1
Sphenolithus ciperoensis X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 15
Coronocyclus mesostenos X 8
Cyclicargolithus floridanusX 10
Helicosphaera intermedia X1
Pontosphaera multipora X1
Pontosphaera sp. X 5
small reticulofenestroidsX 28
Sphenolithus moriformis X 4
Table A33. Milano MV.
Table A33. Milano MV.
LEV7GC 78–80 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X1
Helicosphaera carteri X2
Reticulofenestra pseudoumbilicusX 48
Sphenolithus disbelemnos X2
Sphenolithus heteromorphus X 4
Umbilicosphaera jafari X 6
Umbilicosphaera rotula X 3
Paleogene
Discoaster barbadiensis X1
Sphenolithus distentus X1
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X1
Coccolithus pelagicusX 21
Cyclicargolithus floridanusX 19
Discoaster sp. X 5
Pontosphaera multipora X1
Pontosphaera sp. X2
Reticulofenestra perplexa X 3
small reticulofenestroidsX 10
Sphenolithus calyculus X1
Sphenolithus moriformis X 5
Table A34. Milano MV.
Table A34. Milano MV.
LEV7GC 78–80 Clast 1
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X3
Coccolithus miopelagicus X2
Helicosphaera carteri X2
Reticulofenestra pseudoumbilicusX 14
Sphenolithus abies X1
Sphenolithus disbelemnos X2
Sphenolithus heteromorphus X2
Umbilicosphaera foliosa X 4
Umbilicosphaera jafari X 2
Umbilicosphaera rotaria X1
Umbilicosphaera rotula X2
Paleogene
Discoaster barbadiensis X1
Reticulofenestra bisecta X3
Reticulofenestra lockeri X3
Long-range Paleogene–Neogene
Coccolithus pelagicusX 12
Coronocyclus mesostenos X 3
Cyclicargolithus floridanus X 6
Pontosphaera sp. X1
small reticulofenestroids X 48
Sphenolithus moriformis X 8
Table A35. Milano MV.
Table A35. Milano MV.
LEV7GC 78–80 Clast 2
Biozone: undetermined
Table A36. Leipzig MV.
Table A36. Leipzig MV.
LEV9GC 10–13 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X3
Helicosphaera carteri X2
Reticulofenestra pseudoumbilicusX 19
Sphenolithus heteromorphus X1
Umbilicosphaera jafari X1
Umbilicosphaera rotula X1
Paleogene
Discoaster saipanensis X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 14
Cyclicargolithus floridanus X 9
Discoaster deflandrei X2
Discoaster sp. X 5
Helicosphaera intermedia X1
Reticulofenestra perplexa X2
Sphenolithus moriformis X 5
Coronocyclus mesostenos X2
Cretaceous
undetermined Cretaceous sp. X2
Table A37. Leipzig MV.
Table A37. Leipzig MV.
LEV9GC 10–13 Clast 1
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X1
Calcidiscus macintyrei X 2
Helicosphaera carteri X 8
Helicosphaera princei X1
Helicosphaera stalis X1
Helicosphaera walbersdorfensis X 2
Reticulofenestra pseudoumbilicusX 25
Rhabdosphaera sp. X1
Sphenolithus abies X1
Sphenolithus cometa X1
Sphenolithus disbelemnos X2
Sphenolithus heteromorphus X2
Umbilicosphaera jafari X 4
Umbilicosphaera rotula X1
Paleogene
Coccolithus fomosus X1
Cyclicargolithus abisectus X1
Sphenolithus ciperoensis X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 37
Cyclicargolithus floridanusX 18
Discoaster deflandrei X3
Discoaster sp. X 3
Helicosphaera intermedia X2
Helicosphaera mediterranea X2
Helicosphaera sp. X3
Pontosphaera sp. X
Reticulofenestra perplexa X 9
small reticulofenestroidsX 3
Sphenolithus moriformis X 6
Cretaceous
undetermined Cretaceous sp. X1
Dizomatolithus lehmanii X2
Table A38. Leipzig MV.
Table A38. Leipzig MV.
LEV9GC 67–69 Clast 1
Biozone: CNM6–7
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X1
Calcidiscus premacintyrei X1
Discoaster exilis X1
Helicosphaera ampliaperta X 5
Helicosphaera carteri X 4
Helicosphaera princei X1
Sphenolithus cometa X2
Sphenolithus dibelemnos X1
Sphenolithus heteromorphus X 3
Umbilicosphaera jafari X 3
Paleogene
Cyclicargolithus abisetus X2
Discoaster barbadiensis X1
Reticulofenestra bisecta X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 10
Coronocyclus mesostenos X2
Cyclicargolithus floridanusX 24
Discoaster deflandrei X 4
Discoaster sp. X11
Helicosphaera intermedia X4
Helicosphaera mediterranea X1
Pontosphaera multipora X1
Pontosphaera sp. X1
Reticulofenestra perplexa X3
small reticulofenestroidsX 10
Sphenolithus moriformisX 11
Sphenolithus sp. X1
Cretaceous
Dizomatolithus lehmanii X 4
Table A39. Leipzig MV.
Table A39. Leipzig MV.
LEV9GC 67–69 Clast 2
Biozone: undetermined
Table A40. Leipzig MV.
Table A40. Leipzig MV.
LEV9GC 98–100 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X2
Helicosphaera carteri X 4
Reticulofenestra pseudoumbilicusX 17
Sphenolithus heteromorphus X2
Umbilicosphaera jafari X3
Paleogene
Cyclicargolithus abisetus X1
Discoaster multiradiatus X1
Reticulofenestra hillae X2
Long-range Paleogene–Neogene
Braarudosphaera bigelowii X1
Coccolithus pelagicusX 11
Coronocyclus mesostenos X1
Coronocyclus nitescens X1
Cyclicargolithus floridanus X 5
Discoaster deflandrei X1
Discoaster sp. X 5
Micrantholithus sp. X1
Pontosphaera multipora X1
Pontosphaera sp. X2
Reticulofenestra perplexa X2
Cretaceous
Dizomatolithus lehmanii X1
Table A41. Leipzig MV.
Table A41. Leipzig MV.
LEV9GC 98–100 Clast 1
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus premacintyrei X2
Coccolithus miopelagicus X1
Cryptococcolithus sp. X1
Reticulofenestra pseudoumbilicus X1
Umbilicosphaera roluta X1
Paleogene
Cyclicargolithus abisetus X 4
Helicosphaera compacta X 2
Helicosphaera recta X1
Reticulofenestra bisecta X 1
Reticulofenestra erbae X2
Reticulofenestra hillae X2
Reticulofenestra lockeri X2
Sphenolithus distentus X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 13
Coronocyclus mesostenos X2
Coronocyclus nitescens X2
Cyclicargolithus floridanusX 82
Discoaster deflandrei X 4
Discoaster sp. X1
Helicosphaera intermedia X 7
Helicosphaera sp. X 5
Pontosphaera sp. X2
Reticulofenestra perplexa X2
small reticulofenestroids X 10
Sphenolithus moriformisX 9
Cretaceous
undetermined Cretaceous sp. X2
Dizomatolithus lehmanii X 4
Table A42. Leipzig MV.
Table A42. Leipzig MV.
LEV9GC 98–100 Clast 2
Biozone: CNM6–7
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus premacintyrei X2
Helicosphaera carteri X 7
Helicosphaera walbersdorfensis X 2
small reticulofenestroidsX 9
Sphenolithus heteromorphusX 12
Umbilicosphaera jafariX 22
Umbilicosphaera rotula X 8
Helicosphaera vedderi X1
Discoaster variabilis X1
Discoaster petaliformis X1
Helicosphaera waltans X 2
Helicosphaera ampliaperta X 2
Coccolithus miopelagicus X5
Paleogene
Cyclicargolithus abisectus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 31
Cyclicargolithus floridanusX 11
Discoaster sp. X 3
Helicosphaera intermedia X1
Helicosphaera sp. X 10
Pontosphaera sp. X 3
Reticulofenestra perplexa X 3
Sphenolithus moriformis X 6
Table A43. Leipzig MV.
Table A43. Leipzig MV.
LEV9GC 98–100 Clast 3
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X 8
Coccolithus miopelagicus X2
Discoaster formosus X1
Helicosphaera carteri X7
Reticulofenestra pseudoumbilicusX 31
Rhabdosphaera sp. X2
Umbilicosphaera jafari X 5
Umbilicosphaera rotula X1
Paleogene
Cyclicargolithus abisetus X1
Reticulofenestra daivesi X1
Sphenolithus ciperoensis X1
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 28
Cyclicargolithus floridanus X 6
Discoaster deflandrei X2
Discoaster sp. X 5
Helicosphaera intermedia X2
Pontosphaera multipora X3
Pontosphaera sp. X 3
Reticulofenestra perplexaX 17
Sphenolithus moriformisX 15
Cretaceous
Eiffellithus sp. X1
Watznaueria barnesiae X2
Table A44. Leipzig MV.
Table A44. Leipzig MV.
LEV9GC 128–130 Matrix
Mixed; Mostly Oligocene–Miocene
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus macintyrei X1
Calcidiscus premacintyrei X1
Discoaster exilis X1
Discoaster ulnatus X1
Helicosphaera carteri X 6
Helicosphaera walbersdorfensis X2
Reticulofenestra pseudoumbilicus X 8
Sphenolithus abies X1
Sphenolithus cometa X1
Sphenolithus heteromorphus X1
Umbilicosphaera jafari X 6
Paleogene
Coccolithus formosus X1
Cyclicargolithus abisetus X1
Discoaster tanii X1
Reticulofenestra bisecta X1
Reticulofenestra hillae X1
Reticulofenestra lockeri X1
Sphenolithus delphix X1
Sphenolithus distentus X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 12
Coronocyclus mesostenos X1
Cyclicargolithus floridanusX 16
Discoaster deflandrei X1
Discoaster sp. X1
Helicosphaera intermedia X1
Pontosphaera multipora X1
Reticulofenestra perplexa X3
Sphenolithus moriformis X3
Cretaceous
Eiffelithus sp. X1
undetermined Cretaceous sp. X3
Watznaueria barnesiae X3
Watznaueria ovata X1
Table A45. Leipzig MV.
Table A45. Leipzig MV.
LEV9GC 128–130 Clast 1
Biozone: undetermined
Table A46. Leipzig MV.
Table A46. Leipzig MV.
LEV9GC 128–130 Clast 2
Biozone: CNM7
SpeciesACFRSpecimens Counted
Neogene
Coccolithus miopelagicus X 7
Helicosphaera carteri X 5
Reticulofenestra pseudoumbilicus X1
Sphenolithus heteromorphusX 14
Umbilicosphaera jafari X 6
Umbilicosphaera rotula X2
Paleogene
Discoaster barbadiensis X1
Long-range Paleogene–Neogene
Coccolithus pelagicusX 45
Coronocyclus nitescens X1
Cyclicargolithus floridanusX 35
Discoaster deflandrei X2
Discoaster sp. X 5
Helicosphaera intermedia X3
Micrantholithus sp. X 4
Pontosphaera sp. X 8
Reticulofenestra perplexa X3
small reticulofenestroids X 4
Sphenolithus moriformis X 6
Cretaceous
Watznaueria barnesiae X2
Table A47. Leipzig MV.
Table A47. Leipzig MV.
LEV9GC 128–130 Clast 3
Biozone: CNM8–9
SpeciesACFRSpecimens Counted
Neogene
Calcidiscus leptoporus X1
Discoaster bolli X1
Discoaster formosus X1
Discoaster variabilis X1
Helicosphaera carteri X 8
Reticulofenestra pseudoumbilicusX 28
Sphenolithus dissimilis X1
Umbilicosphaera foliosa X2
Umbilicosphaera jafari X3
Paleogene
Zygrhablithus bijugatus X1
Long-range Paleogene–Neogene
Coccolithus pelagicus X 6
Cyclicargolithus floridanus X2
Discoaster sp. X3
Pontosphaera multipora X2
Pontosphaera sp. X1
Reticulofenestra perplexa X1
Sphenolithus moriformis X 4
Cretaceous
Dizomatolithus lehmanii X2
Figure A1. Distinct unimodal S2 peaks in the Rock-Eval pyrograms of samples from: (a) the Gelendzhik MV, (b) the Heraklion MV, (c) the Moscow MV, (d) the Milano MV, and (e) the Leipzig MV.
Figure A1. Distinct unimodal S2 peaks in the Rock-Eval pyrograms of samples from: (a) the Gelendzhik MV, (b) the Heraklion MV, (c) the Moscow MV, (d) the Milano MV, and (e) the Leipzig MV.
Water 13 01367 g0a1

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Figure 1. Spatial distribution of the mud volcanoes (see the yellow bullets) in the eastern Mediterranean basin. The thick dashed lines indicate the northern and southern boundaries of the central Mediterranean Ridge, while the red arrow indicates the approximate location of the Olimpi mud volcano field. Modified from Mascle et al. [5]; see [16] for the explanation of the additional information shown on the map.
Figure 1. Spatial distribution of the mud volcanoes (see the yellow bullets) in the eastern Mediterranean basin. The thick dashed lines indicate the northern and southern boundaries of the central Mediterranean Ridge, while the red arrow indicates the approximate location of the Olimpi mud volcano field. Modified from Mascle et al. [5]; see [16] for the explanation of the additional information shown on the map.
Water 13 01367 g001
Figure 2. (a) Bathymetric digital terrain model of the Olimpi mud volcano field (grid interval: 50 m; ellipsoid: WGS84; projection: UTM35N; reference datum: mean sea level) and sediment coring locations (the core labels appear in white color). (b) Seabed reflectivity in the Olimpi mud volcano field (grid interval of 50 m), with the yellow-colored patches representing strong backscatter signal. (c) Location of the Olimpi mud volcano field (inset map). From Panagiotopoulos et al. [26].
Figure 2. (a) Bathymetric digital terrain model of the Olimpi mud volcano field (grid interval: 50 m; ellipsoid: WGS84; projection: UTM35N; reference datum: mean sea level) and sediment coring locations (the core labels appear in white color). (b) Seabed reflectivity in the Olimpi mud volcano field (grid interval of 50 m), with the yellow-colored patches representing strong backscatter signal. (c) Location of the Olimpi mud volcano field (inset map). From Panagiotopoulos et al. [26].
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Figure 3. Images of the gravity cores recovered from the five MVs, showing the coring depth below seafloor (bsf) and the various mud breccia facies. The red arrows indicate the sampling core intervals. Modified from Panagiotopoulos et al. [26]. For a detailed description of the cored sediments see Panagiotopoulos et al. [26].
Figure 3. Images of the gravity cores recovered from the five MVs, showing the coring depth below seafloor (bsf) and the various mud breccia facies. The red arrows indicate the sampling core intervals. Modified from Panagiotopoulos et al. [26]. For a detailed description of the cored sediments see Panagiotopoulos et al. [26].
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Figure 4. Image of a representative mud breccia facies from the Olimpi mud volcano field (LEV5GC core from the Moscow MV).
Figure 4. Image of a representative mud breccia facies from the Olimpi mud volcano field (LEV5GC core from the Moscow MV).
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Figure 5. Example of an age-diagnostic assemblage list showing the relative abundances of the nannofossil species in the total assemblage of the LEV5GC 40–42 clast 1 sample. The coexistence of Sphenolithus distentus and Sphenolithus predistentus (their microscopic image appears at the right) and Sphenolithus ciperoensis defines the CNO4/CNO5 biozone. The identified Cretaceous species along with some Paleogene (pre-Oligocene) species are considered as reworked.
Figure 5. Example of an age-diagnostic assemblage list showing the relative abundances of the nannofossil species in the total assemblage of the LEV5GC 40–42 clast 1 sample. The coexistence of Sphenolithus distentus and Sphenolithus predistentus (their microscopic image appears at the right) and Sphenolithus ciperoensis defines the CNO4/CNO5 biozone. The identified Cretaceous species along with some Paleogene (pre-Oligocene) species are considered as reworked.
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Figure 6. Left: Example of a non-age-diagnostic assemblage list showing the relative abundances of the nannofossil species in the total assemblage of the LEV5GC 10–12 matrix sample. Right: Microscopic image of the sample indicating considerable reworking due to the concomitant occurrence of the Calcidiscus premacintyrei (Miocene) and Discoaster barbadiensis (Eocene) species. Almost all matrix samples displayed analogous microscopic images.
Figure 6. Left: Example of a non-age-diagnostic assemblage list showing the relative abundances of the nannofossil species in the total assemblage of the LEV5GC 10–12 matrix sample. Right: Microscopic image of the sample indicating considerable reworking due to the concomitant occurrence of the Calcidiscus premacintyrei (Miocene) and Discoaster barbadiensis (Eocene) species. Almost all matrix samples displayed analogous microscopic images.
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Figure 7. Modified van Krevelen diagram presenting the results of the Rock-Eval pyrolysis. One mudstone clast (LEV1GC 4–6 clast 1) dated as middle Miocene (CNM10 biozone) demonstrates different geochemical characteristics from the rest of the samples.
Figure 7. Modified van Krevelen diagram presenting the results of the Rock-Eval pyrolysis. One mudstone clast (LEV1GC 4–6 clast 1) dated as middle Miocene (CNM10 biozone) demonstrates different geochemical characteristics from the rest of the samples.
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Figure 8. HI vs. Tmax plot showing, in parallel, the kerogen-type curves and maturity levels along with the upper- and lower-vitrinite reflectance thresholds (Ro) for oil generation. Note the distinct position of the sample LEV1GC 4–6 clast 1 (CNM10 biozone), which approaches the type II kerogen curve.
Figure 8. HI vs. Tmax plot showing, in parallel, the kerogen-type curves and maturity levels along with the upper- and lower-vitrinite reflectance thresholds (Ro) for oil generation. Note the distinct position of the sample LEV1GC 4–6 clast 1 (CNM10 biozone), which approaches the type II kerogen curve.
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Figure 9. (S1 + S2) vs. TOC plot indicating the potential of the source rocks for hydrocarbon generation.
Figure 9. (S1 + S2) vs. TOC plot indicating the potential of the source rocks for hydrocarbon generation.
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Figure 10. Distinct bimodal S2 peaks in the Rock-Eval pyrograms of samples from: (a) the Gelendzhik MV, (b) the Heraklion MV, (c) the Moscow MV, and (d) the Milano MV.
Figure 10. Distinct bimodal S2 peaks in the Rock-Eval pyrograms of samples from: (a) the Gelendzhik MV, (b) the Heraklion MV, (c) the Moscow MV, and (d) the Milano MV.
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Table 1. Biozones determined by the nannofossil study of the clast samples. The index species suggest the stratigraphic range of the samples, while the reworked species can provide valuable information about the basin’s evolution. The correlation with Martini [32] biozones appears in parentheses. (*) Miocene–Pliocene species associated with potential contamination caused by the upward migration of mud breccia.
Table 1. Biozones determined by the nannofossil study of the clast samples. The index species suggest the stratigraphic range of the samples, while the reworked species can provide valuable information about the basin’s evolution. The correlation with Martini [32] biozones appears in parentheses. (*) Miocene–Pliocene species associated with potential contamination caused by the upward migration of mud breccia.
Biostratigraphic SchemeIndex SpeciesMain Long-Range Species (or/and Reworked)ReworkedSamples
CNM10
(NN7)
D. kugleriC. pelagicus, C. floridanus, H. carteri, D. deflandrei, S. moriformisS. disbelemnos, S. dissimilis, H. ampliaperta, S. delphix, C. abisectus, D. nodifer, R. lockeri, R. bisecta, S. ciperoensis, R. hillae, S. predistentus, Z. bijugatus, H. recta, D. lehmanii, Eiffelithus sp. Also (*): P. lacunosa?, Gephyrocapsa sp. <3 μmLEV1GC 4–6 clast 1, LEV1GC 4–6 clast 2, LEV1GC 65–67 clast 1, LEV5GC 100–102 clast 2
CNM8–9 (NN6)R. pseudoumbilicus, C. macintyreiC. leptoporus, C. mesostenos, C. pelagicus, H. carteri, D. deflandrei, S. moriformisS. heteromorphus, S. cometa, S. disbelemnos, R. bisecta, S. ciperoensis, D. barbadiensis, R. lockeri, R. hillae, R. reticulata, Z. bijugatus, C. fomosus, C. abisetus, C. gerrardii, R. daivesi, D. lehmanii Zeugrhabdotus sp., Cruciplacolithus sp., Eiffellithus sp., W. barnesiae, undetermined Cretaceous sp. Also (*): P. lacunosa?, Gephyrocapsa <3 μm, S. abiesLEV1GC 18–20 clast 1, LEV7GC 40–43 clast 1, LEV7GC 40–43 clast 2 LEV7GC 78–80 clast 2, LEV9GC 10–13 clast 1, LEV9GC 98–100 clast 3, LEV9GC 128–130 clast 3
CNM7
(NN5)
S. heteromorphus, C. miopelagicusC. pelagicus, C. floridanus, D. deflandrei, S. moriformis, C. mesostenos, R. perplexaR. bisecta, D. barbadiensis, W. barnesiae, Micrantholithus sp.LEV5GC 123–125 clast 2, LEV9GC 128–130 clast 2
CNM6–7 (NN4)S. heteromorphus, Helicosphaera ampliapertaC. pelagicus, C. floridanus, D. deflandrei, S. moriformis, C. mesostenos, R. perplexaS. cometa, S. dibelemnos, C. abisetus, R. bisecta, S. predistentus, D. barbadiensis, R. lockeri, D. lehmanii, undetermined Cretaceous sp., E. turriseiffeliiLEV3GC 65–67 clast 1, LEV5GC 70–72 clast 1, LEV9GC 67–69 clast 1, LEV9GC 98–100 clast 2
CNO4/CNO5 (NP24)S. distentus, S. predistentus, S. ciperoensisC. pelagicus, C. floridanus, D. deflandrei, S. moriformis, C. mesostenos, C. abisectus, R. bisecta, Z. bijugatusD. barbadiensis, C. eopelagicus, B. parca, Eiffelithus sp., R. infinitusLEV5GC 40–42 clast 1
Assemblage mainly featuring the CNO3-CNO4/CNO5 biozones (NP23-NP24)S. distentus, S. predistentus, S. peartiaeC. formosus, C. floridanus, D. deflandrei.C. formosus, D. multiradiatus, D. barbadiensis, Arkhangelskiales sp. Also (*): C. miopelagicus, D. kugleri, D. discissus, D. durioi, D. exilis, H. carteri, R. pseudoumbilicus, U. jafari, S. abiesLEV5GC 10–12 clast 1, LEV5GC 100–102 clast 1
Table 2. Source rock hydrocarbon-generation potential based on the TOC contents of the pyrolyzed sediment samples. Redrawn and modified from Peters [58].
Table 2. Source rock hydrocarbon-generation potential based on the TOC contents of the pyrolyzed sediment samples. Redrawn and modified from Peters [58].
Source Rock Generative PotentialTOC
% dw
Sample Type
Poor<0.510 matrices, 15 clasts
Fair0.5–14 matrices, 12 clasts
Good1–2
Very Good>21 clast
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Nikitas, A.; Triantaphyllou, M.V.; Rousakis, G.; Panagiotopoulos, I.; Pasadakis, N.; Hatzianestis, I.; Gogou, A. Pre-Messinian Deposits of the Mediterranean Ridge: Biostratigraphic and Geochemical Evidence from the Olimpi Mud Volcano Field. Water 2021, 13, 1367. https://doi.org/10.3390/w13101367

AMA Style

Nikitas A, Triantaphyllou MV, Rousakis G, Panagiotopoulos I, Pasadakis N, Hatzianestis I, Gogou A. Pre-Messinian Deposits of the Mediterranean Ridge: Biostratigraphic and Geochemical Evidence from the Olimpi Mud Volcano Field. Water. 2021; 13(10):1367. https://doi.org/10.3390/w13101367

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Nikitas, Anastasios, Maria V. Triantaphyllou, Grigoris Rousakis, Ioannis Panagiotopoulos, Nikolaos Pasadakis, Ioannis Hatzianestis, and Alexandra Gogou. 2021. "Pre-Messinian Deposits of the Mediterranean Ridge: Biostratigraphic and Geochemical Evidence from the Olimpi Mud Volcano Field" Water 13, no. 10: 1367. https://doi.org/10.3390/w13101367

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