Polycyclic aromatic hydrocarbons (PAHs) in late Eocene to early Pleistocene mudstones of the Sylhet succession,NE Bengal Basin,Bangladesh: Implications for source and paleoclimate conditions during Himalayan uplift

Distribution and possible sources of polycyclic aromatic hydrocarbons (PAHs) have been investigated in 23 late Eocene to early Pleistocene mudstones from the Sylhet succession of the northeastern Bengal Basin, Bangladesh. Paleoclimatic conditions in the southern Himalaya region throughout the Himalayan uplift were reconstructed, based on combustion derived PAHs and aromatic land plant derived biomarkers. Phenanthrene, fluoranthene (Fla), pyrene (Py), benz[a]anthracene (BaAn), chrysene/triphenylene (Chry + Tpn), benzofluoranthenes (Bflas), benzo[e]pyrene (BePy), benzo[a]pyrene (BaPy), perylene (Pery), indeno[1,2,3-cd]pyrene (InPy), benzo[ghi]perylene (BghiP), coronene (Cor) and retene (Ret) were the identified PAHs. Fla/(Fla + Py) ratios > 0.5 and InPy/(InPy + BghiP) > 0.2 from almost all Sylhet samples suggest occurrence of natural wildfires. Low contents of BaAn and BaPy indicate decomposition by long exposure to sunlight before sedimentation, or early diagenetic weathering. Increased Cor, InPy and BghiP contents suggest occurrence of larger, high temperature wildfires. Correlation coefficients of the PAHs and p-values for statistical hypothesis testing showed that the positive and negative correlations within the PAHs may be indicative of high or low temperatures in wildfires. Fungi derived Pery showed negative correlations with Py (r = −0.67, p = 4.6 × 10⁻⁴) and Fla (r = −0.56, p = 5.0 × 10⁻³), but not with Cor, Bflas, InPy and BghiP. Based on the correlation coefficients for all PAHs and their p-values, five statistical groups ([Py, Fla], [Cor, Bflas, InPy, BghiP], [BaAn, Chry + Tpn, BaPy], [Pery] and [Ret]) were recognized. These groups are probably correlated with origins and depositional processes. According to the results, the Sylhet succession was deposited in three differing paleoclimatic regimes: (1) First phase (late Eocene to early Miocene, early to middle stage of Himalayan uplift): High contents of combustion derived PAHs (Fla, Py and BePy), significant gymnosperm derived Ret, and low Pery abundances in the Jaintia and Barail groups indicate arid climatic conditions. Although wildfires could often occur, 5- or 6-ring combustion PAHs (Cor, InPy and BghiP) contents are low, suggesting that the wildfires were relatively low temperature. (2) Second phase (middle to late Miocene: middle to late stage of Himalayan uplift): Combustion derived PAHs and fungi derived Pery were dominant in the Surma Group. The climate was arid to humid and seasonal, with a dry season giving conditions suitable for combustion. Abundant Fla, Bflas, BePy, Cor, InPy and BghiP imply high temperatures in large wildfires. However, frequency of the wildfires decreased because of wet climate. (3) Third phase (late Miocene to Pleistocene: late stage of Himalayan uplift): Moderate to high Pery contents and low Fla, Py and BePy abundances in the Tipam and Dupitila groups indicate establishment of more humid climate. InPy, BghiP, Cor, Bflas and BaPy were predominant. Intensified humid and seasonal climate arising from the Himalayan monsoon decreased the incidence and frequency of general wildfires, but increased the ratio of large to small wildfires.     

A 60-million-year Cenozoic history of western Amazonian ecosystems in Contamana,eastern Peru

We provide a synopsis of ~ 60 million years of life history in Neotropical lowlands, based on a comprehensive survey of the Cenozoic deposits along the Quebrada Cachiyacu near Contamana in Peruvian Amazonia. The 34 fossil-bearing localities identified have yielded a diversity of fossil remains, including vertebrates, mollusks, arthropods, plant fossils, and microorganisms, ranging from the early Paleocene to the late Miocene–?Pliocene (> 20 successive levels). This Cenozoic series includes the base of the Huchpayacu Formation (Fm.; early Paleocene; lacustrine/fluvial environments; charophyte-dominated assemblage), the Pozo Fm. (middle + ?late Eocene; marine then freshwater environments; most diversified biomes), and complete sections for the Chambira Fm. (late Oligocene–late early Miocene; freshwater environments; vertebrate-dominated faunas), the Pebas Fm. (late early to early late Miocene; freshwater environments with an increasing marine influence; excellent fossil record), and Ipururo Fm. (late Miocene–?Pliocene; fully fluvial environments; virtually no fossils preserved). At least 485 fossil species are recognized in the Contamana area (~ 250 ‘plants’, ~ 212 animals, and 23 foraminifera). Based on taxonomic lists from each stratigraphic interval, high-level taxonomic diversity remained fairly constant throughout the middle Eocene–Miocene interval (8-12 classes), ordinal diversity fluctuated to a greater degree, and family/species diversity generally declined, with a drastic drop in the early Miocene. The Paleocene–?Pliocene fossil assemblages from Contamana attest at least to four biogeographic histories inherited from (i) Mesozoic Gondwanan times, (ii) the Panamerican realm prior to (iii) the time of South America’s Cenozoic “splendid isolation”, and (iv) Neotropical ecosystems in the Americas. No direct evidence of any North American terrestrial immigrant has yet been recognized in the Miocene record at Contamana.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Organic geochemistry and depositional environment of the Aptian bituminous limestone in the Kale Gümüşhane area (NE-Turkey): An example of lacustrine deposits on the platform carbonate sequence

The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average T_max value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The T_max values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C₂₆–C₃₀) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C₂₉ is the dominant sterane, with C₂₉ > C₂₇ > C₂₈. The bituminous limestone samples have low C₂₂/C₂₁ ratios, high C₂₄/C₂₃ tricyclic terpane ratios and very low C₃₁R/C₃₀ hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.     

Temporal–spatial distribution and tectonic setting of porphyry copper deposits in Iran: Constraints from zircon U–Pb and molybdenite Re–Os geochronology

Porphyry copper deposits (PCDs) in Iran are dominantly distributed in Arasbaran (NW Iran), the middle segment of the Urumieh–Dokhtar Magmatic Arc (UDMA), and Kerman (central SE Iran), with minor occurrences in eastern Iran and the Makran arc. This paper provides a temporal–spatial and geodynamic framework of the Iranian porphyry Cu (Mo–Au) systems, based on geochronologic data obtained from zircon U–Pb and molybdenite Re–Os dating of host porphyritic rocks and molybdenites in 15 major PCDs. The dating results define a long metallogenic duration (39–6 Ma), and suggest a long history of tectonic evolution from the accretionary orogeny related to early Cenozoic closure of the Neo-Tethys Ocean to subsequent collisional orogeny for the Iranian porphyry copper systems.The oldest porphyry mineralization occurred in the eastern part of Iran after the closure of a branch of the Neo-Tethyan (Sistan) Ocean between the Lut and Afghan blocks in the late Eocene (39–37 Ma). This was followed by mineralization in the Kerman porphyry copper belt over a time interval of about 20 m.y., where two metallogenic epochs have been recognized, including late Oligocene (29–27 Ma) and Miocene (18–6 Ma). The Bondar-e-Hanza deposit formed in the late Oligocene, while and the remaining dated deposits belong to Miocene epoch. According to the deposits' characteristics and their ages, the Miocene epoch can be divided into early, middle, and late stages. The Darreh Zar, Bakh Khoshk, Chah Firouzeh and Sar Kuh deposits formed during the early–middle Miocene. The largest porphyry deposits occur in the middle stage during the middle Miocene (14–11 Ma) and include the Sar Cheshmeh, Meiduk, Dar Alu and Now Chun deposits. These deposits were formed during crustal thickening, uplift, and rapid exhumation of the belt. The final stage of porphyry mineralization occurred during the late Miocene (9–6 Ma), and formed the Iju, Kerver, Kuh Panj and Abdar deposits.There were two porphyry mineralization stages in the Arasbaran porphyry copper belt in NW Iran, including an older late Oligocene (29–27 Ma) and a younger early Miocene (22–20 Ma) events. The Haft Cheshmeh deposit belongs to the older stage, and the world-class Sungun and Masjed Daghi deposits formed during the early Miocene.In the middle segment of the UDMA (Saveh–Yazd porphyry copper belt), PCDs formed during middle Miocene time (17–15 Ma). The geochronological results reveal that the porphyry mineralization moved from the northwest to southeast of UDMA over the time.Our dating results, combined with the possible late Eocene–Oligocene timing for collision between the Arabian and Iranian plates, support a model for Iranian PCD formation by partial melting of previously subduction-modified lithosphere in a post-subduction and post-collisional tectonic setting.     

Metallogeny,structural evolution,post-mineral cover distribution and exploration in concealed areas of the northern Chilean Andes

Mineral exploration of prospective areas concealed by extensive post-mineralization cover is growing, being very complex and expensive. The projection of rich and giant Paleocene to early Oligocene porphyry-Cu-Mo belts in northernmost Chilean Andes (17.5–19.5°S) has major exploration potential, but only a few minor deposits have been reported to date, due to the fact that the area is largely covered by post-mineral strata. We integrate the Cenozoic stratigraphic, structural and metallogenic evolution of this sector, in order to identify the most promising regions related to lesser post-mineral cover and the projection of different metallogenic belts. The Paleocene to early Eocene metallogenic belt extends along the Precordillera, with ca. 30 km wide, and includes porphyry-Cu prospects and small Cu (±Mo-Au-Ag) vein and breccia-pipe deposits. Geochronological data indicate an age of 55.5 Ma for an intrusion related to one deposit and ages from 69.5 to 54.5 Ma for hydrothermal alteration in one porphyry-Cu prospect and largest known Cu deposits. The middle Eocene to early Oligocene porphyry belt, in the Western Cordillera farther east, is associated with 46–44 Ma intrusions. It is estimated to be 40-km wide, but is largely concealed by thick post-mineral cover. The youngest Miocene to early Pliocene metallogenic belt, also in the Western Cordillera, is well-exposed and includes Au-Ag epithermal and polymetallic veins and manto-type deposits.The Oligocene-Holocene cover consists of a succession of continental sedimentary and volcanic rocks that overall increase in thickness from 0 to 5000 m, from west to east. These strata are subhorizontal in the west and folded-faulted towards the east. Miocene gentle anticlines and monocline flexures extend along strike for 30–60 km in the Precordillera and were generated by propagation of high-angle east-dipping blind reverse faults with at least 300–900 m of Oligocene bedrock offset. The thickness of cover exceeds 2000 m in the eastern Central Depression, whereas it is generally less than 1000 m in the Precordillera along the Paleocene to early Eocene porphyry-Cu belt and it can reach locally up to 5000 m in the Western Cordillera, above the middle Eocene to early Oligocene belt.In the studied Andean segment, the Miocene to early Pliocene metallogenic belt is superimposed on the Paleocene to Oligocene belts in a 40–50 km wide zone. This overlap may be explained by an accentuated migration of the magmatic front, from east to west, since ca. 25 Ma, as a consequence of subduction slab steepening after a period of magmatic lull and flat subduction from ca. 30–35 to 25 Ma. The identified areas of lesser cover thickness are prone to exploration for concealed deposits, especially along the projection of major porphyry-Cu-Mo belts.     

Environmental significance of mid- to late Holocene sapropels in Old Man Lake,Coorong coastal plain,South Australia: An isotopic,biomarker and palaeoecological perspective

The Holocene successions of numerous shallow lakes located along the Coorong coastal plain in South Australia attest to the impact of rising sea level and changing climate on their depositional environment. Old Man Lake is one of the smallest perennial alkaline lakes in the region. Its succession comprises a basal lagoonal sand rich in humic organic matter (OM) overlain by a 3.7 m thick upward shoaling lacustrine mudstone. The latter features three discrete sapropel units deposited between 3270 and 4910 cal yr BP, a time of increasing aridity throughout southeastern Australia. A core taken from the lake’s eastern margin yielded sedimentological, mineralogical, geochronological and micropaleontological data. Coring at five other sites across the lake provided sections of the humic and sapropelic facies (n = 20) for total organic carbon and Rock–Eval analysis; isotopic characterization of their micritic carbonate (δ¹³C_carb, δ¹⁸O_carb) and co-existing OM (δ¹³C_org); and GC–MS and GC–irMS analysis of their free aliphatic hydrocarbons. For each ‘sapropel event’ high productivity of diatoms and green algae was the principal driver of the accumulation and preservation of OM in such high concentrations. The precursor algal blooms were likely triggered by the influx of fresh water following winter rainfall. The combination of kerogen hydrogen index and δ¹³C_carb–δ¹³C_org, previously employed to track secular changes in algal productivity and organic preservation, proved useful in identifying synchronous geographic differences in these processes across the lake. Highly branched isoprenoids (HBI: C_25:1 ≫ C_20:0) are prominent components of the aliphatic hydrocarbons in the sapropels, confirming the significant contribution of diatoms to their OM. The C isotopic signatures of the principal C_25:1 HBI isomer and the co-occurring C₂₃–C₃₁ odd carbon numbered n-alkanes further document the non-uniformity of biomass preservation within and between the three sapropel units. The evidence from this study suggests that seasonal algal blooms and meromixis, although not necessarily an anoxic hypoliminion, were required for sapropel formation in the Holocene lakes of the Coorong region. Higher resolution sampling, dating and comparative analysis (microfossil, biomarker and isotopic) of these sapropels is required to clarify their potential significance as palaeoclimate proxies.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Organic matter distribution in the modern sediments of the Pearl River Estuary

We determined biomarker concentrations and distributions for surface sediments from 54 sites in the Pearl River Estuary, China. We focus on a suite of four biomarker-based indicators for relative terrestrial to marine organic matter (OM) source: the branched-isoprenoid tetraether (BIT) index, the ratio of high/low molecular weight n-alcohols [(ΣC_26–34/(ΣC₁₆₊₁₈ + ΣC_26–34)], an analogous ratio for n-fatty acids and the ΣC₂₉-steroids/(ΣC₂₉-steroids + brassicasterol) ratio. All four exhibit the same terrestrial to marine transition seen in previous bulk δ¹³C studies, but with an abrupt decrease in the relative terrestrial contribution across the delta front to pro-delta transition. Concentrations of terrestrially-derived biomarkers show no systematic decrease across the transition. Instead, the decrease in the proportion of terrestrial OM is due to a decrease in the sedimentation rate and associated terrestrial OM burial across the delta toe. This suggests that diagenetic controls on the fate of terrestrial OM, such as increased biodegradation where sedimentation rate is low, are subordinate to sedimentological processes. Biomarker-derived temperature values are cooler than expected for the lower Pearl River catchment, suggesting that the dominant component of the terrestrial OM is derived from the cooler upland regions of the catchment. The dominance of input from more distal terrain with greater topographic relief is evidence for the importance of geomorphological control on terrigenous OM transport. Collectively, the results demonstrate the importance of sedimentological processes in the supply, deposition and transport of terrestrial OM.     

Calibrating n-alkane Sphagnum proxies in sub-Arctic Scandinavia

Moss covered, high latitude wetlands hold large amounts of terrestrial organic matter (OM), which may be vulnerable to expected climate warming. Molecular analysis of fluvially transported material from these regions can distinguish between different sources of terrestrial OM. Sphagnum moss may represent one of the major sources. This study aimed to quantitatively establish a molecular proxy for identifying Sphagnum-derived OM from high latitude peatlands in the sub-Arctic coastal ocean. We collected and analyzed Sphagnum species throughout northern Sweden and Finland. Results show that the C₂₅/(C₂₅ + C₂₉) n-alkane ratio is most suitable for terrestrial OM source apportionment in these coastal regions since, compared to other n-alkane Sphagnum proxies, it shows (i) the least variation between species, (ii) the most constant values for different latitudinal regimes and (iii) the largest dynamic range to the higher plant end member in two-source mixing models. Application of the proxy to surface sediments and suspended particulate matter in the sub-Arctic northern Baltic Sea shows that 68–103% of the terrestrial OM fraction is derived from Sphagnum-rich peatland. We recommend that future studies on terrestrial OM fluxes into (sub-)Arctic regions should apply the C₂₅/(C₂₅ + C₂₉) proxy to improve insight into the contribution of Sphagnum-derived terrestrial OM from climate-vulnerable, high latitude wetlands.     

Physils and organic matter-base palaeoenvironmental records of the K/Pg boundary transition from the late Cretaceous-early Palaeogene succession of the Um-Sohryngkew River section of Meghalaya,India

A continuous, shallow marine succession of the Um-Sohryngkew River section is distinct as it contains late Maastrichtian-early Danian planktonic foraminiferal zones and the K/Pg boundary, although K/Pg transition events remain inconclusive. Physils divide entire succession in to lower, middle and upper sub-divisions and represent anomalous values of redox-sensitive elements (δCe, La/Yb and Gd/Yb) in biozone CF3. Organic matter when analyzed show TOC and C spikes in biozone CF3. Illite thermometry also revealed sudden increase in the palaeo-temperature (>140 °C) for yellowish brown 1–2 mm thick organic rich clay layer in biozone CF3. Interestingly, conspicuous increase in the short chain n-alkanes and fatty acids is observed in the biozone CF3, although, long chain n-alkanes (C₂₇–C₃₃) derived from terrestrial plants show low abundance throughout the succession.High amount of combustion derived fluoranthene, pyrene, chrysene, benzo(a) anthracene PAH compounds found in the biozone CF3 are analogous to those reported from the K/T boundary sections of Stevns Klint, Gubbio, Woodside Creek and Arroyo el Mimbral. The pyrolitic signatures of these organic macro-molecules reflect global fire, caused distress to biota (during the deposition of biozone CF3 layer) which is coincidental with the well documented Ce anomaly layer, but, preceded by planktonic foraminiferal change in biozone P0 and PGE anomaly bearing layer in the biozone CF2. These organic macro-molecules reflect global fire, induced by the heat supplied by the late Cretaceous Abor and/or Deccan extrusions perhaps linked with the K/T transition events as later initiated prior to the K/Pg boundary, however, the main episode of Deccan volcanic activity occurred ∼300 ky earlier or at the K/Pg boundary itself. The deposition of 1–2 mm thick, yellowish brown, smooth (with conchoidal fracture) pyrite nodules and micro-spherules bearing organic rich clay layer marked with the decrease in the carbonate content (2.43%) that lies at the contact between the silty mudstone and grey calcareous shale located in the biozone CF3 of this succession coincides with the first appearance of Pseudoguembelina hariaensis representing age of 66.83–65.45 Ma is also related to the India’s collision with the Eurasia and Burma andextrusion of Abor volcanic.These events also endorse succeeding events such as anomalous concentration of platinum group of elements and concentration of spherules during biozone CF2, which are other end Cretaceous events before the advent of the K/Pg boundary.     

Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems

Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C₁₇, n-C₁₉, n-C₂₁, n-C₂₃ and n-C₂₅ alkanes, algae (Rhodophyta, Chlorophyta) produced n-C₁₅ and n-C₁₇ and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C₂₅, n-C₂₇, n-C₂₉, n-C₃₁ and n-C₃₃. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C₂₇ + C₂₉ + C₃₁/C₁₅ + C₁₇ + C₁₉; terrestrial to aquatic ratio) and the P_aq (C₂₃ + C₂₅/C₂₃ + C₂₅ + C₂₉ + C₃₁; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.     

The first record of Eocene tuff in a Paleogene rift basin near Nantou,Western Foothills,central Taiwan

Microfossils and a U–Pb age dating on zircon grains in the tuff beds exposed in the axial part of the Tsukeng anticline along the Pinglin River in the Western Foothills near Nantou, central Taiwan, show an occurrence of the Eocene volcanics unconformably beneath the uppermost part of the Latest Oligocene Wuchihshan Formation. This is the first discovery of the Eocene tuff exposed in the Western Foothills.The proposed Miocene “Tsukeng Formation” and “Takeng Formation” of Ho et al. (1956) named for sequences exposed in the Nantou area, Western Foothills, have to be abandoned and the standard Oligocene–Miocene lithostratigraphy used commonly in the Western Foothills of northern Taiwan is properly applicable in central Taiwan. The thick pink–brown–green colored volcanics unconformably beneath the uppermost Wuchihshan Formation is named for the first time as the Pinglin Tuff which contains Late Middle Eocene calcareous nannofossils (Zone NP16) consistent with a U–Pb age dating (38.8 ± 1 Ma) on zircon grains in the tuff. The Pinglin Tuff is overlying the Middle Eocene Chungliao Formation which contains indigenous larger foraminifera Discocyclina dispansa ex. interc. sella-dispansa and calcareous nannofossils of Zones NP14–15. The Middle Eocene Pinglin Tuff and Chungliao Formation represent the Paleogene syn-rift sequence unconformably overlain by the Latest Oligocene–Miocene post-rift sequence. This is the first document with conclusive paleontological data and age dating showing an occurrence of Paleogene marine rift basin exposed in the Western Foothills. This study also confirms similar Tertiary basin architecture between the Taiwan Strait–Pearl River Mouth Basin in the NE South China Sea and the Western Foothills onland central Taiwan.     

Glacial–interglacial productivity and environmental changes in Lake Biwa,Japan: A sediment core study of organic carbon,chlorins and biomarkers

Temporal changes in paleoproductivity of Lake Biwa (Japan) over the past 32 kyr have been studied by analyzing bulk organic carbon and photosynthetic pigments (chlorins) in the BIW95-5 core. Primary productivity was estimated on the assumption of C/N_org values of 8 for autochthonous organic matter (OM) and 25 for allochthonous OM and using an equation developed for the marine environment. The estimate indicates that primary productivity ranges from 50 to 90 g C m^?2 yr^?1 in the Holocene, while it is ～60 g C m^?2 yr^?1 on average in the last glacial. Pheophytin a and pheophorbide a are the major chlorins. A downcore profile of chlorin concentration normalized to autochthonous organic carbon (OC) shows a decreasing trend. Chlorin productivity was corrected by removal of the effect of post-burial chlorin degradation. The temporal profile of chlorin productivity thereby obtained resembles that from autochthonous OC.The difference in primary productivity between the Holocene and the glacial for the lake is markedly smaller than that for Lake Baikal situated in the boreal zone. This difference between the two lakes is probably caused by the difference in their climatic conditions, such as temperature and precipitation. Precipitation at Lake Biwa is relatively large during the glacial and the Holocene because of the continuous influence of the East Asian monsoon. Lake Baikal precipitation is generally small as a result of control by the continental (Siberia) climate regime. In addition, a significant difference in productivity between the glacial and the Holocene for Lake Baikal may be essentially controlled by the hydrodynamic systems in the lake.Lake Biwa terrigenous OM input events occurred at least five times over the period 11–32 kyr BP, suggesting enhanced monsoon activity. Molecular examination of the layer with a large input of terrigenous OM during the Younger Dryas indicates that concentrations of terrigenous biomarkers such as n-C₂₇–C₃₁ alkanes, lignin phenols, cutin acids, ω-hydroxy acids and C₂₉ sterols are high, suggesting that soil OM with peat-like material entered the lake as a result of flooding. An enhanced sedimentation rate in the last 3000 years might have been partially caused by agricultural activity around the lake.     

Provenance of the Eocene Soebi Blanco formation,Bonaire, Leeward Antilles: Correlations with post-Eocene tectonic evolution of northern South America

Middle to upper Eocene fluvial strata in the island of Bonaire contain detrital components that were tracked to Precambrian to Triassic massifs in northern Colombia and Venezuela. These detrital components confirm previous hypothesis suggesting that Bonaire and the Leeward Antilles were attached to South American basement massifs (SABM). These are composed of different fragmented South American blocks (Paraguana, Falcon, Maracaibo, Guajira, Perija, and Santa Marta) representing an Eocene, right-laterally displaced tectonic piercing point along the southern Caribbean plate margin. U–Pb LA-ICP-MS from the metamorphic boulders of the Soebi Blanco Formation in Bonaire yield Grenvillian peaks ages (1000–1200 Ma), while detrital zircons recovered from the sandy matrix of the conglomerates contain populations with peaks of 1000 Ma–1200 Ma, 750–950 Ma, and 200–300 Ma. These populations match with geochronological data reported for the northern South American massifs. Thermochronological results from the metamorphic clasts yield Paleocene–middle Eocene ages (65–50 Ma) that confirm a regional-scale cooling event in this time. These data imply a land connection between the SABM and the Leeward Antilles in late Eocene times, followed by a significant strike slip right-lateral displacement and transtensional basin opening starting in latest Eocene times. The succession of Eocene tectonic events recorded by the Soebi Blanco Formation and adjacent basins is a major tracer of the oblique convergence of the Caribbean plate against the South American margin.     

Long-lived,stationary magmatism and pulsed porphyry systems during Tethyan subduction to post-collision evolution in the southernmost Lesser Caucasus,Armenia and Nakhitchevan

The composite Meghri–Ordubad and Bargushat plutons of the Zangezur–Ordubad region in the southernmost Lesser Caucasus consist of successive Eocene to Pliocene magmatic pulses, and host two stages of porphyry Cu–Mo deposits. New high-precision TIMS U–Pb zircon ages confirm the magmatic sequence recognized by previous Rb–Sr isochron and whole-rock K–Ar dating. A 44.03 ± 0.02 Ma-old granite and a 48.99 ± 0.07 Ma-old granodiorite belong to an initial Eocene magmatic pulse, which is coeval with the first stage of porphyry Cu–Mo formation at Agarak, Hanqasar, Aygedzor and Dastakert. A subsequent Oligocene magmatic pulse was constrained by U–Pb zircon ages at 31.82 ± 0.02 Ma and 33.49 ± 0.02 Ma for a monzonite and a gabbro, and a late Miocene porphyritic granodioritic and granitic pulse yielded ages between 22.46 ± 0.02 Ma and 22.22 ± 0.01 Ma, respectively. The Oligo-Miocene magmatic evolution broadly coincides with the second porphyry-Cu–Mo ore deposit stage, including the major Kadjaran deposit at 26–27 Ma.Primitive mantle-normalized spider diagrams with negative Nb, Ta and Ti anomalies support a subduction-like nature for all Cenozoic magmatic rocks. Eocene magmatic rocks have a normal arc, calc-alkaline to high-K calc-alkaline composition, early Oligocene magmatic rocks a high-K calc-alkaline to shoshonitic composition, and late Oligocene to Mio-Pliocene rocks are adakitic and have a calc-alkaline to high-K calc-alkaline composition. Radiogenic isotopes reveal a mantle-dominated magmatic source, with the mantle component becoming more predominant during the Neogene. Trace element ratio and concentration patterns (Dy/Yb, Sr/Y, La/Yb, Eu/Eu*, Y contents) correlate with the age of the magmatic rocks. They reveal combined amphibole and plagioclase fractionation during the Eocene and the early Oligocene, and amphibole fractionation in the absence of plagioclase during the late Oligocene and the Mio-Pliocene, consistent with Eocene to Pliocene progressive thickening of the crust or increasing pressure of magma differentiation. Characteristic trace element and isotope systematics (Ba vs. Nb/Y, Th/Yb vs. Ba/La, ²⁰⁶Pb/²⁰⁴Pb vs. Th/Nb, Th/Nb vs. δ¹⁸O, REE) indicate that Eocene magmatism was dominated by fluid-mobile components, whereas Oligocene and Mio-Pliocene magmatism was dominated by a depleted mantle, compositionally modified by subducted sediments.A two-stage magmatic and metallogenic evolution is proposed for the Zangezur–Ordubad region. Eocene normal arc, calc-alkaline to high-K calc-alkaline magmatism was coeval with extensive Eocene magmatism in Iran attributed to Neotethys subduction. Eocene subduction resulted in the emplacement of small tonnage porphyry Cu–Mo deposits. Subsequent Oligocene and Miocene high-K calc-alkaline and shoshonitic to adakitic magmatism, and the second porphyry Cu–Mo deposit stage coincided with Arabia–Eurasia collision to post-collision tectonics. Magmatism and ore formation are linked to asthenospheric upwelling along translithospheric, transpressional regional faults between the Gondwana-derived South Armenian block and the Eurasian margin, resulting in decompression melting of lithospheric mantle, metasomatised by sediment components added to the mantle during the previous Eocene subduction event.     

FTIR microspectroscopy of Ediacaran phosphatized microfossils from the Doushantuo Formation,Weng'an,South China

Phosphatized microfossils from ca. 580 Ma from the Doushantuo Formation in the Weng'an region of South China were analyzed by Fourier transform infrared (FTIR) microspectroscopy for their chemical characterization. Two morpho-types of phosphatized embryo-like fossils (Megasphaera and Megaclonophycus) were analyzed, together with algal fossils. Transmission IR spectra of the microfossils have absorption bands of around 2960 cm^− 1 and 2925 cm^− 1, indicating the presence of aliphatic hydrocarbon (anti-symmetric aliphatic CH₃ and aliphatic CH₂), and have an additional band of around 1595 cm^− 1, probably derived from aromatic moieties (aromatic CC). In addition, IR microscopic mapping shows that aliphatic hydrocarbon and aromatics are distributed inside the embryo-like fossils. The embryo-like fossils appear to show three types of CH₃/CH₂ peak height ratios (R_3/2) and aromatic CC/CH₂ peak height ratios (R_CC/2 values): (1) high-R_3/2/low-R_CC/2 type (R_3/2 = ~ 0.2–1.0 and R_CC/2 ~ 0–2), (2) low-R_3/2/medium-R_CC/2 type (R_3/2 = ~ 0.2–0.6 and R_CC/2 = ~ 1–4); and (3) low-R_3/2/high-R_CC/2 type (R_3/2 = ~ 0.2–0.6 and R_CC/2 ~ 1–8). All three types are contained in both Megasphaera and Megaclonophycus. Raman spectra for the carbonaceous matter within the rock sample show a similar degree of thermal alteration, indicating that the organics were embedded in situ prior to thermal maturation. The IR spectroscopic differences might reflect differences in original organic compositions of microorganisms, and/or immediate post-mortem alteration. This suggests that the origins of phosphatized embryo-like fossils are more diverse than was previously recognized on the basis of their morphology. A comparison of R_3/2 and R_CC/2 values in the embryo-like fossils with those of the algal fossils and the extant microorganisms indicates the possible interpretation that some of the embryo-like fossils belong to animal embryo, others are algae, but none of them originate from bacteria.     

Petrography,mineralogy and geochemistry of the Late Eocene oolitic ironstones of the Jebel Ank,Southern Tunisian Atlas

The oolitic ironstones ore deposit of Jebel Ank (central Tunisia), is a simply folded stratiform ore body of about 2.5–8 m thickness located in the upper part of the epicontinental Souar Formation (Late Eocene) and is covered by the continental Segui Formation (Mio-Pliocene). The deposit contains about 20 Mt of ore with an average grade of 50% Fe. Generally, oolitic iron deposition occurs in shallow water lagoonal environments. The Jebel Ank deposit lies between two regional disconformities (Late Eocene and Miocene), and is evidence of a transitional stage at the end of regional regression before renewed transgression. The footwall of the oolitic iron ore-bearing bed consists of a fine-grained sandstone bed (10–20 cm-thick) pinching out laterally westward into green clays. The hanging wall is composed of thin-bedded limestone and clay alternations (2–3.5 m-thick).Iron occurs in the form of cryptocrystalline goethite with limited Al-Fe substitution. The goethite contains around 48% Fe, 5% Al and up to 1.5% P. Jarosite, alunite and manganese minerals (cryptomelane, psilomelane and manjiorite) are supergene secondary minerals, probably related to descending surface fluids. These manganese minerals occur as accessory minerals with the goethite and are most abundant at the lowermost part of the succession showing varied morphologies (local cement, space filling and free centimeter sized nodules). Fe-oolites in the deposit are similar to those documented in many other oolitic ironstone deposits. The dominant Fe-oolite type (>90%) has a concentrically laminated cortex with no nucleus. The nuclei of the oolites that do have a nucleus are most commonly detrital quartz grains.Major elements in high grade samples (Fe₂O₃ > 65%) vary within a limited range and show higher concentrations of SiO₂ (average 7.85%) and Al₂O₃ (average 5.1%), with minor TiO₂, MnO, MgO, Na₂O, K₂O, and SO₃ (less than 1%). PAAS-normalized trace elements of bulk samples and Fe-oolite generally show similar behavior, both are enriched in V, Co, Ni, Mo, As, Zn, and Y and are depleted in Cu, Rb, Zr, Nb, Ba, and Hf. Anomalous V, Cr, Ni, Zn, and REE-Y are correlated with goethite. PAAS-normalized REE-Y patterns of both bulk samples and Fe-oolite show slight HREE enrichment, positive Ce with negative Y anomalies.The mineralogy (goethite and cryptomelane) along with the geochemistry (Si vs. Al; As + Cu + Mo + Pb + V + Zn vs. Ni + Co binary plots; Zn–Ni–Co triangular diagram, REE-Y content and patterns and Ce/Ce¹ vs. Nd and Ce/Ce¹ vs. Y_N/Ho_N binary plots) of the studied oolitic ironstone are congruent with a hydrogenetic type. While two possible sources of iron for Jebel Ank ironstone can be proposed: (i) submarine weathering of glauconite-rich sandstone and (ii) detrital iron from adjacent continental hinterland, the later is the more plausible source of iron, based on paleogeographic setting, the occurrence of fine sandstone underlying the iron level, occurrence of Mn-ores in the lower part of the Fe-ores succession, high phosphorous, zinc, ∑REE-Y concentrations and Y/Ho ratios, and low La/Ce ratios.     

The role of slump scars in slope channel initiation: A case study from the Miocene Jatiluhur Formation in the Bogor Trough,West Java

This paper investigates slope channel initiation by seabed irregularities that were initially formed by slump scars in the lower to middle Jatiluhur Formation, part of the middle- to late Miocene successions in the Bogor Trough, West Java. This Miocene succession is up to 1000 m thick in the study area, and is interpreted as a prograding slope–shelf system that formed during a period of falling- and lowstand stages in relative sea level. The lower part of the formation is a siltstone-dominated siliciclastic succession, containing slump deposits, slump-scar-fill deposits, and minor channel-fill deposits, which formed in slope and shelf-margin environments. In contrast, the middle part, which gradationally overlies the lower part, is characterized by shallow-marine carbonates.The slump-scars-fill deposits have an overall lenticular geometry, and are 140–480 m wide and 0.4–1.6 m thick. Some have distinct erosional bases, which cut into the underlying siltstones, in association with medium- to coarse-grained sandstones with lateral-accretion surfaces and tractional structures common in channel-fill deposits. The incident link of slump-scar-fill deposits and channel-fill deposits in the prograding slope–shelf succession of the lower to middle Jatiluhur Formation suggests that some slump scars formed incipient seabed irregularities that may have played an important role in the development of slope channels. The present study provides one example of the various potential mechanisms that can result in channel formation in a slope setting.     

Tropical northeast Africa in the middle–late Eocene: Paleomagnetism of the marine-mammals sites and basalts in the Fayum province,Egypt

The mid-late Eocene “Valley of Whales” in the Fayum province of Egypt contains hundreds of marine-mammals’ skeletons. Given its paleontological importance, we carried out a paleomagnetic study of the fossil-bearing formations. A sequence of basalts directly overlying the upper Eocene rocks in three distant clusters within a 25 km-long NW–SE graben in the southwestern part of the area was also studied. Thermal demagnetization of three-axis IRM was used to identify and eliminate sites dominated by hematite and/or goethite as potential remanence carriers. Progressive thermal demagnetization of the NRM isolated a characteristic NNE–SSW dual-polarity direction with a shallow inclination that passes both tilt and reversal tests. The mean tilt-corrected direction of the sedimentary formations is D/I = 16°/30° (k = 50, α₉₅ = 3°) yielding a paleomagnetic pole at 70°N/159°E. The anisotropy of magnetic susceptibility (AMS) indicated that the observed inclinations were free from inclination shallowing, as did the nearly identical characteristic remanence of the overlying basalt flows (with a tilt-corrected reversed-polarity direction of D/I = 198°/−28° (k = 38, α₉₅ = 7°) and a pole at 68°N/158°E). The new paleopoles place the Fayum province at a lower paleolatitude (15–17°N) than today (29.5°N), and point to the possible prevalence of tropical climate in northeast Africa during mid-late Eocene times. This tropical position is nearly identical to the paleolatitudes extrapolated from the mean of 36 coeval poles rotated from the other major cratons and from Africa itself. The declinations show a minor easterly deviation from those predicted by extrapolation from other continents. This is interpreted as due to a small clockwise rotation internal to NE Africa, possibly related to Red Sea/Gulf of Suez rifting after the late Eocene. The alternative explanation that the geomagnetic field had a non-zonal non-dipole field contribution is not favored.