Neoglacial (<3000 years) till and flutes at Saskatchewan Glacier,Canadian Rocky Mountains,formed by subglacial deformation of a soft bed

Understanding the processes that deposit till below modern glaciers provides fundamental information for interpreting ancient subglacial deposits. A process‐deposit‐landform model is developed for the till bed of Saskatchewan Glacier in the Canadian Rocky Mountains. The glacier is predominantly hard bedded in its upper reaches and flows through a deep valley carved into resistant Palaeozoic carbonates but the ice margin rests on a thick (<6 m) soft bed of silt‐rich deformation till that has been exposed as the glacier retreats from its Little Ice Age limit reached in 1854. In situ tree stumps rooted in a palaeosol under the till are dated between ca 2900 and 2700 yr bp and record initial glacier expansion during the Neoglacial. Sedimentological and stratigraphic observations underscore the importance of subglacial deformation of glaciofluvial outwash deposited in front of the advancing glacier and mixing with glaciolacustrine carbonate‐rich silt to form a soft bed. The exposed till plain has a rolling drumlinoid topography inherited from overridden end moraines and is corrugated by more than 400 longitudinal flute ridges which record deformation of the soft bed and fall into three genetically related types: those developed in propagating incipient cavities in the lee of large subglacial boulders embedded in deformation till, and those lacking any originating boulder and formed by pressing of wet till up into radial crevasses under stagnant ice. A third type consists of U‐shaped flutes akin to barchan dunes; these wrap around large boulders at the downglacier ends of longitudinal scours formed by the bulldozing of boulders by the ice front during brief winter readvances across soft till. Pervasive subglacial deformation during glacier expansion was probably facilitated by large boulders rotating within the soft bed (‘glacioturbation’).     

Punctuated environmental change along the Holocene (<6 ka) bank margin of south-west Exuma Sound, Bahamas

Characteristics of environmental change along the Holocene (<6 ka BP) bank margin of south‐west Exuma Sound, Bahamas, are defined by comparing mineral, isotope and lithologic stratigraphic patterns in deep‐water (1081 m) slope strata in ODP Hole 631A (Exuma Sound) with proximal (≈6 km) shoal‐water and insular geology of the Lee Stocking Island (LSI) region. After platform submergence, a bank‐top transition from non‐skeletal‐ to skeletal‐dominated deposition occurred in the LSI region by ≈3·8 ka, and is recorded in the adjacent slope sediments by a contemporaneous change in the abundance of transported allochems. The transition at Site 631 is punctuated by an anomalous shift in foraminiferal δ¹³C (–1‰) and δ¹⁸O (–3‰), which may represent a period of climate change that established a brackish coastal zone at least 6 km wide, coincident (≈3·8–4 ka) with bank‐top erosion and pedogenesis. Non‐skeletal allochems reappeared in Hole 631A sediments as the dominant transported allochem type by ≈2·4 ka, then again over the last several hundred years, and are contemporaneous with periods of increased platform‐margin circulation in the LSI region. Such rejuvenation of platform circulation may have resulted from rapid relative rises in sea level, superimposed on the net gradual post‐glacial rise. At Site 631, a prominent (25%) decline in aragonite abundance occurred during the period from 2·4 ka to the last few hundred years, and coincided with an increase in magnesian calcite and skeletal debris, and a positive shift in foraminiferal δ¹⁸O values. These patterns lend support to the hypothesis that, during this period, the LSI margin was barred by skeletal shoals, allowing bank‐top trapping of aragonite and hypersaline water, with increased coastal salinity (resulting from reflux of hypersaline waters through the shoals) and/or cooled coastal waters (caused by reduced exchange of warmed bank‐derived water relative to wind‐generated upwelling). Along the Exuma slope, a diagenetic overprint may further enhance the recent decline in aragonite accumulation. Integration of Holocene deep‐water slope and bank‐top stratigraphies along the bank margin of south‐west Exuma Sound reveals a pattern of punctuated environmental change superimposed on longer term development of interglacial conditions.     

Milankovitch cyclicity in Purbeck peritidal limestones of the Prebetic (Berriasian, southern Spain)

Peritidal carbonate rocks (Purbeck facies) of the uppermost Portlandian to Berriasian in the type section of the Sierra del Pozo Formation in the Prebetic Zone, southern Spain, are divisible into 141 shallowing upward cycles averaging 2 m in thickness. The subtidal facies in these cycles consist of micritic or marly limestones with dasycladacean algae and lituolids; the intertidal facies are micritic limestones containing birdseyes and miliolids; the supratidal facies comprise laminated algal limestones, the tops of which display desiccation cracks and rhizocretions, or more locally palaeosols, calcretes, or palaeokarst surfaces. A statistical study, using power spectra of the Fast Fourier Transform, demonstrates that the periodicity of these cycles is in the Milankovitch frequency band. Most sedimentary cycles correspond to the obliquity cycles; eccentricity and precession cycles have also been recognized. Using a Fischer plot, third-order tectono-eustatic cycles are recognized, which can be correlated with the eustatic curve of the Exxon chart. The shallowing upward sequences are characterized by a distinctive pattern of geochemical parameters. Carbon and oxygen isotopic (δ¹³C and δ¹⁸O) variations, calcium and magnesium carbonate contents and the abundance of organic matter and trace elements (Mn and Sr) all have predictable patterns of distribution within the sequences. The Sr content of the subtidal facies is relatively high whereas the δ¹³C and δ¹⁸O ratios are quite low; in the intertidal facies the Sr and Mn levels fall concomitantly with a rise in δ¹³C and δ¹⁸O. The highest δ¹³C and δ¹⁸O values occur in the lower part of the supratidal facies, whereas in the upper part of δ values and Sr contents drop sharply. Cyclic variations in evaporation and in meteoric water influence, determined from oxygen isotopic composition, reveal that the cyclicity of the beds containing the most limestones (supratidal) and those with the most marls (subtidal) is related to climatic changes. The coldest periods are those represented by supratidal deposits, when the sea level was at its lowest. During the warmest periods, when the overall sea level was higher, subtidal deposits accumulated in the region. A genetic model is proposed, according to which the asymmetrical sedimentary cycles occur in response to glacio-eustatic changes with a periodicity similar to that of Plio-Pleistocene sea-level variations, but with a much lower range due to the smaller extent of polar ice caps during the Early Cretaceous. The glacio-eustatic changes involved a rapid sea-level rise and a slow sea-level fall.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Facies mosaic and diagenetic patterns of the early Devonian (Late Pragian–Early Emsian) microbialite‐dominated carbonate sequences,Qasr Member,Jauf Formation,Saudi Arabia

The Al‐Jawf area of northern Saudi Arabia provides spectacular outcrops of Early Devonian carbonate bioherms in the Wadi Murayr and Dumat Al‐Jandal areas. These carbonate bioherms belong to the Qasr Member of the Late Pragian–Early Emsian Jauf Formation (~405 Ma) and are surrounded by a bioclastic carbonate succession. The Qasr Member is the first major carbonate unit of the Palaeozoic succession in Saudi Arabia that mainly consists of microbialite carbonates and metazoan reefs exhibiting distinct mound features. These bioherm complexes and their associated carbonate facies are pervasively dolomitized. Stratigraphic, petrographic and geochemical analyses were conducted to determine the facies distribution and interpret their depositional and diagenetic processes. A total of 11 facies are identified from a range of depositional environments within a carbonate platform system, ranging from tidal flats, lagoon, shoal, patch reefs to reef front. The main diagenetic processes are carbonate cementation and dolomitization. Dolomitization occurred as both fabric preserved (mostly in grain‐dominated facies) and fabric destructive (mud‐dominated facies). The microbialites and coralline sponges facies show poor reservoir with visual porosity less than 5%, but this succession may have a potential to serve as a good source for the underlying and overlying facies. Ooid and peloidal grainstone facies show fair to good visual porosity that locally exceeds 10% with intergranular porosity as the dominant type. However, in the most studied samples, vuggy and intraparticle porosities are observed as the dominant type. Copyright © 2015 John Wiley & Sons, Ltd.     

Sedimentological proof and dating of the Early Holocene volcanic eruption of Ulmener Maar (Vulkaneifel,Germany)

A minerogeniclayer occurs in early postglacial organic sediments from five maar lakes (West Eifel Volcanic Field, Germany). The mineralogy and stratigraphic position of this tephra suggests that it is related to the youngest German volcano, Ulmener Maar, nearby. Radiocarbon dating of wood from the base of the Ulmener Maar Tephra at two locations provide ages in agreement with an accelerator mass spectrometer ¹⁴C date for the minerogenic layer from sediments of Lake Holzmaar situated 13 km south-west of Ulmener Maar. The mean radiocarbon age is 9 560 years BP. Dating by varve chronology provides an age of 10017 years VT (varve time in years before 1950) or 10 895 years corrected VT. Based on palynology the Ulmener Maar Tephra was deposited at the end of the Preboreal. High values of natural remnant magnetization intensity, typical of pyroclastic material, confirm that this minerogenic layer differs in composition from other clastic deposits of the sedimentary record. Geochemical analyses reveal increased values of total trace elements for the Laacher See Tephra and Ulmener Maar Tephra. An isopach map based on thickness variations of the Ulmener Maar Tephra at five investigated maar lakes indicates that the tephra was mainly transported to the south west.     

Holocene evolution of the Triftje- and the Oberseegletscher (Swiss Alps) constrained with <Superscript>10</Superscript>Be exposure and radiocarbon dating

To develop a more precise understanding of Alpine glacier fluctuations during the Holocene, the glacier forefields of the Triftjegletscher and the Oberseegletscher east of Zermatt in the Valais Alps, Switzerland, were investigated. A multidisciplinary approach of detailed geological and geomorphological field mapping combined with ¹⁰Be exposure and radiocarbon dating was applied. A total of twelve samples of boulders and bedrock were taken from both Little Ice Age (LIA) landforms, as documented by the Dufour map published in 1862, and from landforms outside of the LIA. The resulting ¹⁰Be ages range between 12590 ± 350 a and 420 ± 170 a. A piece of wood found embedded in the Little Ice Age moraine gave radiocarbon ages that range between 293 cal years BP up to modern (356–63 cal years before 2013). Based on these results, four tentative steps of the Holocene evolution could be distinguished. An early Holocene stage, which documents the decay of the Egesen stadial glaciers when the first parts of the study area became ice free. This was followed by a phase with no evidence of glacier advance. Then in the late Holocene, the glaciers advanced (at least) twice. An advance around 1200 a, as shown by several moraine ages, coincides with the Göschenen II cold phase. A more extensive readvance occurred during the LIA as shown on the historical maps and underpinned by one ¹⁰Be exposure age and the radiocarbon age. This later advance destroyed or overprinted the earlier landforms in most parts of the area.     

Ecology and fluvial dynamics of an Early Holocene medium‐sized European lowland river valley (Upper Scheldt,northern Belgium)

The fluvial environment of Early Holocene small‐ to middle‐sized lowland rivers in northwest Europe is mostly unstudied due to a lack of preserved and accessible deposits. A rescue excavation in the Scheldt valley in northern Belgium offered the opportunity to study a Boreal alluvial succession in detail. The results of palaeoecological and sedimentological analyses (diatoms, pollen, botanical macro‐remains, molluscs, grain size) characterize the biotic and physical environment in the middle reach of this medium‐sized river system. Although the Early Holocene in the Scheldt Basin has often been portrayed as a period of fluvial stability with marshy conditions and diffuse discharge, this study showed evidence of point bar formation by a small, low‐energy meandering river between ~9.5 and ~8.8 cal. ka BP. The point bar was at least temporarily vegetated and shows a shift from herbaceous riparian vegetation to an open willow‐dominated alluvial forest. This evidence points to a more open vegetation and a more energetic environment than traditionally described for rivers of this size and age. A link to the 9.3 ka BP cooling event is suggested and possible reasons for the scarcity of records of this type of deposits are discussed.     

Pedogenetic and diagenetic fabrics in the Upper Proterozoic Sarnyëré formation (Gourma, Mali)

Several diagenetic fabrics are described in the uppermost member of the Sarnyéré formation, an Upper Proterozoic dolomite (700-600 Ma). Micronodular micrite, microsparite showing nodulisation processes, orbicular crusts and oncoids are thought to be due to the pedogenetic alteration of an algal (Porostromata) boundstone. Further evolution in a vadose zone creates a network of cavities which are later filled by “cave stromatolites”, micropopcorn micrite and multilayered cements. A rhythmical repetition of facies evidences a polyphased pedogenetic history, leading to a 30 m thick highly complex section. Such numerous and diversified structures are rarely preserved, especially in Proterozoic rocks, but each of them have equivalents in recent examples of caliche soil profiles.     

Classifying chalk microtextures: Sedimentary versus diagenetic origin (Cenomanian–Santonian,Paris Basin,France)

Microtexture describes the type of particles and their arrangement in matrix samples at scanning electron microscopy scale. Although a microtexture classification exists for micritic limestone, it cannot be directly applied to chalk. This study therefore proposes a classification of chalk microtextures and discusses the origin of microtexture variability. Chalk was sampled at thirteen spatio‐temporal locations along the coastline of northern France (Cenomanian–Santonian). Four criteria are defined to describe, characterize and determine chalk matrix microtexture: (i) mineralogical content; (ii) biogenic fraction; (iii) micritic fraction; and (iv) cement fraction. From these criteria, two major groups are defined: Pure Chalk Microtexture Group, with seven classes, and Impure Chalk Microtexture Group, divided into two subgroups: Argillaceous Microtexture with four classes and Siliceous Microtexture with two classes. Microtexture variability is related both to initial sedimentation and to diagenesis. Sedimentological conditions (for example, climate and distance from shore) affect chalk composition (carbonate content and type of insoluble particles), thus influencing microtexture. Changes in Pure Chalk Microtexture are the result of increasing diagenetic intensity. This classification can also be used to characterize the microtexture of subsurface chalk reservoirs. Reservoir quality depends on the petrophysical and mechanical properties of reservoir rocks, which can be better understood by exploring their sedimentary and diagenetic history, revealed by the study of chalk microtexture variability.     

Occurrence of Contrasting skarn formations in dolomites of the Traversella deposit (Ivrea,Italy)

Metasomatic columns hosted in dolomitic marbles in the thermal aureole of the Traversella monzodiorite (Ivrea, Italy) differ by their mineralogy and/or mineral composition. Three groups have been distinguished. In group A, the first zone always contains forsterite-calcite and the second zone contains clinopyroxene. The last zone is made of wollastonite (A1), andradite-rich garnet (A 2) or grossular-rich garnet (A 3). In group B, tremolite instead of forsterite occurs in the first two zones. In group C columns, there are only two zones and clinohumite or chondrodite characterize the first zone.Field, petrographic and chemical data demonstrate that the occurrence of contrasted mineral zonations in the same protolith has not been induced by local heterogeneities in the dolomitic marbles. The presence of tremolite in group B instead of forsterite is due to the lower temperature prevailing in the external part of the contact aureole. Chemical data as well as - diagrams suggest that the columns in groups A and C were formed through the interaction of the dolomitic marbles with fluids with different _{Fe 2}O₃, _{Al 2 O 3} and _F. A fluid with low _{Al 2 O 3} and _{Fe 2}O₃ is assumed for the metasomatic column with wollastonite (A 1) and different Al₂O₃/Fe₂O₃ values in the fluid are responsible for the formation of columns A 2 and A 3. The stability of clinohumite or chondrodite in group C columns has been induced by a higher _F of the fluid than in the other groups. The presence during the prograde metasomatic stage of distinct fluids differing by their _{Al 2 O 3}/_{Fe 2}O₃ (columns A 2 and A 3) is likely to have been induced by variations in the source composition. Moreover, the low A1 and Fe content in column A 1 could be due to the reaction of the dolomitic marble with a fluid previously depleted in these components during percolation and reaction with the country rocks.As shown by isocon diagrams and Gresens's equation, skarn formation has locally induced both mass and volume change. The volume decreased in the wollastonite zone of A 1 (19%) and in the Fo-Cc zone of A2 (17%). Mass is always increased except in the wollastonite of A 1 where it is decreased. Mass balance of major elements has shown that Ca is likely to be a perfectly inert component and that Si is always strongly increased. Moreover, Fe is increased in A 2 and A 3 whereas Al is only increased in A 3. Mg is leached in the internal part of column Al.Quantification of chemical potential diagrams using different values of _{Al 2 O 3 Fe 2 O 3}, X _F and T suggests that the successive zones observed in all types of columns can be obtained along an increase of _{SiO 2} towards the inner zones. A simultaneous decrease in _MgO is inferred for group A columns.     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

A late Holocene paleoenvironmental reconstruction from Agua Caliente,southern Belize,linked to regional climate variability and cultural change at the Maya polity of Uxbenká

We report high-resolution macroscopic charcoal, pollen and sedimentological data for Agua Caliente, a freshwater lagoon located in southern Belize, and infer a late Holocene record of human land-use/climate interactions for the nearby prehistoric Maya center of Uxbenká. Land-use activities spanning the initial clearance of forests for agriculture through the drought-linked Maya collapse and continuing into the historic recolonization of the region are all reflected in the record. Human land alteration in association with swidden agriculture is evident early in the record during the Middle Preclassic starting ca. 2600 cal yr BP. Fire slowly tapered off during the Late and Terminal Classic, consistent with the gradual political demise and depopulation of the Uxbenká polity sometime between ca. 1150 and 950 cal yr BP, during a period of multiple droughts evident in a nearby speleothem record. Fire activity was at its lowest during the Maya Postclassic ca. 950–430 cal yr BP, but rose consistent with increasing recolonization of the region between ca. 430 cal yr BP and present. These data suggest that this environmental record provides both a proxy for 2800 years of cultural change, including colonization, growth, decline, and reorganization of regional populations, and an independent confirmation of recent paleoclimate reconstructions from the same region.     

Hyperspectral image analysis of different carbonate lithologies (limestone,karst and hydrothermal dolomites): the Pozalagua Quarry case study (Cantabria,North‐west Spain)

Ground‐based hyperspectral imaging combined with terrestrial lidar scanning is a novel technique for outcrop analysis, which has been applied to Early and Late Albian carbonates of the Pozalagua Quarry (Cantabrian Mountains, Spain). An image processing workflow has been developed for differentiating limestone from dolomite, providing additional sedimentary and diagenetic information, and the possibility to quantitatively delineate diagenetic phases in an accurate way. Spectral absorption signatures can be linked to specific sedimentary or diagenetic products, such as recent and palaeokarst, hydrothermal karst, (solution enlarged) fractures and different dolomite types. Some of the spectral signatures are related to iron, manganese, organic matter, clay and/or water content. Ground‐truthing accessible parts of the quarry showed that the classification based on hyperspectral image interpretation was very accurate. This technique opens the possibility for quantitative data evaluation on sedimentary and diagenetic features in inaccessible outcrops. This study demonstrates the potential of ground‐based imaging spectroscopy to provide information about the chemical–mineralogical distribution in outcrops, which could otherwise not be established using conventional field methods.     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Integrated stratigraphy and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar chronology of the Early to Middle Miocene Upper Freshwater Molasse in eastern Bavaria (Germany)

A detailed integrated stratigraphic study was carried out on middle Miocene fluvial successions of the Upper Freshwater Molasse (OSM) from the North Alpine Foreland Basin, in eastern Bavaria, Germany. The biostratigraphic investigations yielded six new localities thereby refining the OSM biostratigraphy for units C to E (sensu; Heissig, Actes du Congres BiochroM’97. Mem Trav EPHE, Inst Montpellier 21, 1997) and further improving biostratigraphic correlations between the different sections throughout eastern Bavaria. Radioisotopic ages of 14.55 ± 0.19 and 14.88 ± 0.11 Ma have been obtained for glass shards from the main bentonite horizon and the Ries impactite: two important stratigraphic marker beds used for confirming our magnetostratigraphic calibration to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). Paleomagnetic analysis was performed using alternating field (AF) and thermal (TH) demagnetization methods. The AF method revealed both normal and reverse polarities but proofs to yield unreliable ChRM directions for the Puttenhausen section. Using the biostratigraphic information and radioisotopic ages, the magnetostratigraphic records of the different sections are tentatively correlated to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). This correlation implies that the main bentonite horizon coincides to chron C5ADn, which is corroborated by its radioisotopic age of 14.55 Ma, whereas the new fossil locality Furth 460, belonging to OSM unit E, probably correlates to chron C5Bn.1r. The latter correlation agrees well with the Swiss Molasse locality Frohberg. Correlations of the older sections are not straightforward. The Brock horizon, which comprises limestone ejecta from the Ries impact, possibly correlates to C5ADr (14.581–14.784 Ma), implying that, although within error, the radioisotopic age of 14.88 ± 0.11 Ma is somewhat too old. The fossil localities in Puttenhausen, belonging to the older part of OSM unit C, probably coincide with chron C5Cn.2n or older, which is older than the correlations established for the Swiss Molasse. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

Chert spheroids of the Monterey Formation,California (USA): early‐diagenetic structures of bedded siliceous deposits

Chert spheroids are distinctive, early‐diagenetic features that occur in bedded siliceous deposits spanning the Phanerozoic. These features are distinct in structure and genesis from similar, concentrically banded ‘wood‐grain’ or ‘onion‐skin’ chert nodules from carbonate successions. In the Miocene Monterey Formation of California (USA), chert spheroids are irregular, concentrically banded nodules, which formed by a unique version of brittle differential compaction that results from the contrasting physical properties of chert and diatomite. During shortening, there is brittle fracture of diatomite around, and horizontally away from, the convex surface of strain‐resistant chert nodules. Unlike most older siliceous deposits, the Monterey Formation still preserves all stages of silica diagenesis, thus retaining textural, mineralogical and geochemical features key to unravelling the origin of chert spheroids and other enigmatic chert structures. Chert spheroids found in opal‐A diatomite form individual nodules composed of alternating bands of impure opal‐CT chert and pure opal‐CT or chalcedony. With increased burial diagenesis, surrounding diatomite transforms to bedded porcelanite or chert, and spheroids no longer form discrete nodules, yet still display characteristic concentric bands of pure and impure microcrystalline quartz and chalcedony. Petrographic observations show that the purer silica bands are composed of void‐filling cement that precipitated in curved dilational fractures, and do not reflect geochemical growth‐banding in the manner of Liesegang phenomena invoked to explain concentrically banded chert nodules in limestone. Chertification of bedded siliceous sediment can occur more shallowly (< 100 m) and rapidly (< 1 Myr) than the bulk silica phase transitions forming porcelanite or siliceous shale in the Monterey Formation and other hemipelagic/pelagic siliceous deposits. Early diagenesis is indicated by physical properties, deformational style and oxygen‐isotopic composition of chert spheroids. Early‐formed cherts formed by pore‐filling impregnation of the purest primary diatomaceous beds, along permeable fractures and in calcareous–siliceous strata.     

Regional studies of dolomites and their included fluids: recognizing multiple chemically distinct fluids during the complex diagenetic history of Lower Carboniferous (Mississippian) rocks of the Irish Zn-Pb ore field

This study provides a regional framework within which studies of ore-related dolomite and dolomite cements may be placed. Fluid inclusion data indicate the presence of three distinct fluids following early dolomitization: 1) a ubiquitous low-temperature, higher salinity fluid found in saddle dolomite; 2) a low-temperature, lower salinity fluid limited to sub-Waulsortian and Waulsortian carbonates; and 3) a higher temperature, lower salinity fluid found in Waulsortian and supra-Waulsortian rocks. Similar fluids have been reported in ore-associated minerals and postmineralization dolomite (Type 1) and in ore-stage carbonates and sphalerite (Types 2 and 3). The halogen geochemistry of included fluids indicates genesis from evaporated seawater. Type 1 fluids are enriched in chloride relative to bromide, reflecting a component of salinity derived via dissolution of halite or from dehydration of seawater. These data suggest that dolomitization and mineralization of Mississippian rocks in the Midlands requires both regionally extensive and localized fluid flow.     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.