Stable 18O and 13C isotope records of Viviparus diluvianus (Kunth, 1865) shells from Holsteinian (MIS 11) lakes of eastern Poland as palaeoenvironmental and palaeoclimatic proxies

The oxygen and carbon stable isotope composition of Viviparus diluvianus shells was determined in the palaeolakes of the Holsteinian interglacial (MIS 11) in eastern Poland: the Ortel Królewski, Hrud, Ossówka, Roskosz and Szymanowo lakes. The occurrence of V. diluvianus covers the Taxus zone, the so‐called intra‐interglacial cooling period (Pinus‐Larix zone), the climatic optimum (Carpinus‐Abies zone) and the post‐optimal period with an undefined pollen zone. The isotope record of V. diluvianus shells allowed palaeoclimate and palaeoenvironmental reconstructions. δ¹⁸O and δ¹³C vary from −8.7‰ in the post‐optimal period to −4.8‰ in the optimal period, and from −10.6‰ at the beginning of the Taxus zone to −4.2‰ at the climatic optimum, respectively. A positive correlation of the isotope curves indicates closed‐water bodies, and only at Roskosz was some occasional overflow inferred. Higher oxygen isotopes correspond to an increase in temperature and/or enhanced evaporation, which is well marked in the Carpinus‐Abies zone, whereas samples enriched in ¹³C are correlated with periods demonstrating a lower water level and higher productivity in the lakes. Episodes of lake shallowing and dense aquatic vegetation occurred in the Pinus‐Larix zone and during the climatic optimum. The isotope ratios for the climatic optimum significantly exceed those of the other periods, thus pointing to warmer conditions. An estimation of relative changes of average summer temperatures using the δ¹⁸O/temperature gradient yielded variation of 1–2 °C within the lakes. Absolute temperature reconstructions indicate the effects of specific local conditions. Hence, V. diluvianus shells offer a reliable proxy in qualitative studies of interglacial lake records.     

Implications for conifer glacial refugia and postglacial climatic variation in western Beringia from lake sediments of the Upper Indigirka basin

A c. 13 800 cal. a BP palynological record from Tschuch'ye Lake (eastern Yakutia), when combined with other palaeobotanical records from western Beringia, supports previous conclusions that Larix and Pinus pumila spread from multiple cryptic refugia during the Lateglacial period and middle Holocene, respectively. The antiquity and spatial distribution of Larix in many of these records suggest that full‐glacial landscapes probably had a small but important tree component. The Tschuch'ye record further indicates the absence of a Younger Dryas climatic reversal and is in accord with the preponderance of other data from western Beringia, which indicate warmer than present climates between c. 12 900 and 9100 cal. a BP. The subsequent spread of Pinus pumila, which has similar temperature requirements as Larix, denotes a shift to wetter but still warm climates during the middle Holocene, with palynological data suggesting optimal conditions in far western areas of western Beringia c. 7000–5000 cal. a BP. The postglacial occurrence of relatively warm/dry and warm/wet intervals is consistent with results of a regional climate‐model simulation that indicates warmer than present temperatures and decreased effective moisture at 11 000 cal. a BP and persistence of warm conditions but with greater moisture and longer growing season at 6000 cal. a BP.     

Influence of climate on the variability of snails of the genus Viviparus in deposits of the Holsteinian (Mazovian) Interglacial from Ortel Krolewski, eastern Poland

Sediments of palaeolakes located in eastern Poland represent the Holsteinian (Mazovian) Interglacial, which corresponds to the Marine Isotope Stage 11 (MIS 11). Some of these sediments are characterized by an extremely rich occurrence of mollusc shells. A total of 1795 specimens of the snail Viviparus diluvianus were measured from 5 samples collected from a succession of lake deposits at Ortel Krolewski. The sample from the lowermost part of the succession (2.5 m) represents the Picea-Alnus pollen zone of the Holsteinian Interglacial. Samples from 2.0, 1.5, 1.0m are related to the Taxus Zone. Samples collected from the uppermost part of the succession (0.5 m) correspond to the Pinus Zone representing the so-called intra-interglacial cooling. The population of V. diluvianus displays variability correlated with climatic changes. The population from the Taxus Zone is characterized by a higher content of mature forms compared to the earlier population from the Picea-Alnus Zone. Because the mature individuals are slimmer than the juvenile forms, their last whorl is relatively lower and the aperture relatively smaller. In populations from the Taxus Zone the mean slimness of the shell therefore increases, followed by a decrease in the mean relative height of the last whorl and the mean relative aperture height.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Late Quaternary palaeoecological and palaeoclimatological reconstruction in the Gutaiului Mountains,northwest Romania

Macrofossil, pollen, lithostratigraphy, mineral magnetic measurements (SIRM and magnetic susceptibility), loss‐on‐ignition, and AMS radiocarbon dating on sediments from two former crater lakes, situated at moderate altitudes in the Gutaiului Mountains of northwest Romania, allow reconstruction of Late Quaternary climate and environment. Shrubs and herbs with steppe and montane affinities along with stands of Betula and Pinus, colonised the surroundings of the sites prior to 14 700 cal. yr BP and the inferred climatic conditions were cold and dry. The gradual transition to open Pinus–Betula forests, slightly higher lake water temperatures, and higher lake productivity, indicate more stable environmental conditions between 14 700 and 14 100 cal. yr BP. This development was interrupted by cooler and drier climatic conditions between 14 100 and 13 800 cal. yr BP, as inferred from a reduction of open forests to patches, or stands, of Pinus, Betula, Larix, Salix and Populus. The expansion of a denser boreal forest, dominated by Picea, but including Pinus, Larix, Betula, Salix, and Ulmus started at 13 800 cal. yr BP, although the forest density seems to have been reduced between 13 400 and 13 200 cal. yr BP. Air temperature and moisture availability gradually increased, but a change towards drier conditions is seen at 13 400 cal. yr BP. A distinct decrease in temperature and humidity between 12 900 and 11 500 cal. yr BP led to a return of open vegetation, with patches of Betula, Larix, Salix, Pinus and Alnus and individuals of Picea. Macrofossils and pollen of aquatic plants indicate rising lake water temperatures and increased aquatic productivity already by ca. 11 800 cal. yr BP, 300 years earlier than documented by the terrestrial plant communities. At the onset of the Holocene, 11 500 cal. yr BP, forests dominated by Betula, Pinus and Larix expanded and were followed by dense Ulmus forests with Picea, Betula and Pinus at 11 250 cal. yr BP. Larix pollen was not found, but macrofossil evidence indicates that Larix was an important forest constituent at the onset of the Holocene. Moister conditions were followed by a dry period starting about 10 600 cal. yr BP, which was more pronounced between 8600 and 8200 cal. yr BP, as inferred from aquatic macrofossils. The maximum expansion of Tilia, Quercus, Fraxinus and Acer between 10 700 and 8600 cal. yr BP may reflect a more continental climate. A drier and/or cooler climate could have been responsible for the late expansion (10 300 cal. yr BP) and late maximum (9300 cal. yr BP) of Corylus. Increased water stress, and possibly cooler conditions around 8600 cal. yr BP, may have caused a reduction of Ulmus, Tilia, Quercus and Fraxinus. After 8200 cal. yr BP moisture increased and the forests included Picea, Tilia, Quercus and Fraxinus. Copyright © 2004 John Wiley & Sons, Ltd.     

Effects of Bioirrigation and Salinity on Arsenic Distributions in Ferruginous Concretions from Salt Marsh Sediment Cores (Southern Brazil)

Arsenic (As), iron (Fe), and manganese (Mn) contents were measured in sediment nodules and associated pore waters obtained from sediment cores collected from a salt marsh on Pólvora Island (southern Brazil). Sediment cores were obtained when brackish water dominated the estuary, at two different environments: an unvegetated mudflat colonized by crabs (Neohelice granulata), and a low intertidal stand vegetated by Spartina alterniflora. We determined the percentage of nodules in each depth interval of the cores, along with redox potential, and As, Fe, and Mn contents of the nodules. The mineralogy of the nodules was investigated, and results showed they are mainly composed by quartz, phyllosilicates, and amorphous Fe–Mn oxides/oxyhydroxides. Pore water results showed that bioturbation by local crabs supports oxygen penetration to depths of ca. 25 cm below the salt marsh surface, with lower Fe contents in pore water associated with the brackish period. However, S. alterniflora growth appears to have a greater impact on sediment geochemistry of Fe, Mn, and possibly As due to sulfate reduction and the associated decrease in pore water pH. Higher Fe concentrations were observed in the pore waters during the period of brackish water dominance, which also corresponded to the S. alterniflora growth season. The study demonstrates that differences in geochemical conditions (e.g., Fe content) that can develop in salt marsh sediments owing to different types of bioirrigation processes (i.e., bioirrigation driven by crabs versus that related to the growth of S. alterniflora) play important roles in the biogeochemical cycling of As.

     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

Larix during the Mid‐Pleniglacial (Greenland Interstadial 8) on Kotelny Island,northern Siberia

Needles, wood and pollen of Larix, recorded in a peat deposit from Kotelny Island, northern Siberia, indicate the local occurrence of larch around 38 000 cal. a BP, which is during the Middle Pleniglacial (Greenland Interstadial 8) of the Weichselian last glacial period. The pollen record, dominated by Cyperaceae, Poaceae, Betula, Alnus, Salix and Artemisia, indicates steppe‐tundra conditions with some shrubs and trees. The distribution of Larix species plays an important role in the reconstruction of climatic conditions during the Weichselian in Siberia. Nowadays Larix does not occur on Kotelny Island and in the present situation the temperature may not be the limiting factor for Larix, but instead the long, snowy winters and the moist tundra vegetation. Our data may contribute to a better understanding of Larix refugia and Weichselian climatic conditions in northern Siberia.     

Nb-Ta-Ti oxides fractionation in rare-metal granites: Kr��sno-Horn�� Slavkov ore district, Czech Republic

Nb-Ta-Ti-bearing oxide minerals (Nb-Ta-bearing rutile, columbite-group minerals) represent the most common Nb-Ta host in topaz-albite granites and related rocks from the Krásno-Horní Slavkov ore district. Tungsten-bearing columbite-(Fe), W-bearing ixiolite, wodginite and tapiolite-(Fe) are extremely rare in these rocks. Rutile contains significant levels of Ta (up to 37?wt.% Ta₂O₅) and Nb (up to 24?wt.% Nb₂O₅), with Ta/(Ta?+?Nb) ratio ranging from 0.04 to 0.61. Columbite-group minerals are represented mostly by columbite-(Fe) and rarely by columbite-(Mn), with Mn/(Mn?+?Fe) ratio ranging from 0.23 to 0.94. The exceptionally rare Fe-rich, W-bearing ixiolite occurs only as inclusions in Nb-Ta-bearing rutile from quartz-free alkali-feldspar syenites (Vysoky Kámen stock). Wodginite was found only in the topaz-albite microgranite of gneissic breccia matrix that occurs in the upper most part of the Hub topaz-albite granite stock. In wodginite, the Mn/(Mn?+?Fe) ratio is 0.42?C0.51, whereas the coexisting tapiolite-(Fe) has a distinctly lower Mn/(Mn?+?Fe) ratio close to 0.06.     

Evolution of a Holsteinian (MIS 11c) palaeolake based on a 12‐ka‐long diatom record from Dethlingen (northern Germany)

To provide insights into the long‐term evolution of aquatic ecosystems without human interference, we here evaluate a decadal‐ to centennial‐scale‐resolution diatom record spanning about 12 ka of the Holsteinian interglacial (Marine Isotope Stage 11c). Using a partially varved sediment core from the Dethlingen palaeolake (northern Germany), which has previously been studied for palynological and microfacies signals, we document the co‐evolution of the aquatic and surrounding terrestrial environment. The diatom record is dominated by the genera Stephanodiscus, Aulacoseira, Ulnaria and Fragilaria. Based on the diatom assemblages and physical sediment properties, the evolution of the Dethlingen palaeolake can be subdivided into three major phases. During the oldest phase (lasting ～1900 varve years), the lake was ～10–15 m deep and characterized by anoxic bottom‐water conditions and a high nutrient content. The following ～5600 years exhibited water depths >20 m, maximum diatom and Pediastrum productivity, and a peak in allochtonous nutrient input. During this phase, water‐column mixing became more vigorous, resulting in a breakdown of anoxia. The youngest lake phase (～4000–5000 years) was characterized by decreasing water depth, turbulent water conditions and decreased nutrient loading. Based on our palaeolimnological data, we conclude that the evolution of the Dethlingen palaeolake during the Holsteinian interglacial responded closely to (i) changes within the catchment area (as documented by vegetation and sedimentation) related to the transition from closed forests growing on nutrient‐rich soils (mesocratic forest phase) to open forests developing on poor soils (oligocratic forest phase), and (ii) short‐term climate variability as reflected in centennial‐scale climate perturbations.     

Early and Middle Pleistocene vegetation history of the Médoc region,southwest France

Pleistocene deposits, together with their pollen, plant macrofossil, foraminiferal, dinoflagellate and coleopteran remains, from five sites along the Atlantic coast of the Médoc Peninsula are described and discussed. Sediments making up the Négade Formation are shown to have been laid down under either estuarine or lagoonal conditions when closed Quercus–Pinus‐Tsuga canadensis regional woodland existed. Comparison with plant records from The Netherlands indicates that these deposits are most likely attributable to either the Early Pleistocene Bavel Interglacial (marine oxygen isotope stage (MIS) 31), or an interglacial of the Waalian (MIS 37–49) or Tiglian (MIS 63–79). In addition, clays assigned to the Argiles du Gurp sensu stricto, were similarly deposited in either an estuary or lagoon, which subsequently was cut off from the sea. A freshwater lake with vegetation dominated by Azolla filiculoides then developed. This was succeeded by reedswamp and an organic mud (termed Lignite in the corresponding French stratigraphical records) formed. Regional Quercus–Abies woodland was replaced by one with Pinus dominant and Pterocarya a minor component. Comparison with plant records from France and other parts of Europe suggest that the clays and organic mud might be correlated with the Holsteinian (Praclaux) Interglacial (MIS 11c). Copyright © 2003 John Wiley & Sons, Ltd.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Geology and mammalian fauna of the Middle Pleistocene site, Medzhybozh, Ukraine

Qualitative and quantitative faunal associations of molluscs, mammals and other vertebrates (Pisces, Amphibia, Reptilia, Aves) have been determined at a new important site at Medzhybozh, in western Ukraine. Geological and taphonomic conditions of the remains’ preservation are described. The transient (Mindelian–Rissian) fauna is identified and correlated with the Middle Pleistocene Holsteinian (Likhvin) Stage. This sequence represents a warm period of the Holsteinian, followed by with a short cooling in the middle of the period. The human cultural material (of Acheulian and Upper Palaeolithic age) has also been studied at this site. It indicates the oldest migration of humans into the region.     

Driftwood in the Eemian interglacial lacustrine unit from the Faroe Islands and its possible source areas: palaeobotanical and ichnological analysis

The coastal cliffs in Klaksvík (Borðoyar Bay) are the only known locality with Eemian sediments in the Faroe Islands. Previous studies carried out there focused on the sedimentology, tephra chemistry, paleoecology including aquatic environment, or the age of the deposits. In the lacustrine, clayey to silty gyttja we collected scattered wood fragments, identified as Larix sp., Pinus sp., Taxus sp. and Betulaceae? In addition, these wood remains contain numerous trace fossils, made by marine wood‐boring bivalves (Teredolites longissimus), which together with a discussion about the areal extent of the identified tree species leads us to conclude that they are non‐native, i.e. driftwood. Northern Siberia is usually regarded as the most likely source area for driftwood in the eastern North Atlantic region. We combined the approximate transport distance from the areal extent of the wood with the main directions of marine currents in the relevant section of the North Atlantic. Adding the known average marine current velocities during the penultimate interglacial resulted in 130–200 days for transport from North America and 350–1100 days from Siberia. Comparing this with the maximal buoyancy period for the identified tree species, we conclude that the Faroese driftwood may originate not only from Siberia, but also from the eastern coast of North America, especially from the region around the Great Lakes, as well as from western Europe.     

Calculated phase equilibria for low- and medium-pressure metapelites in the KFMASH and KMnFMASH systems

Petrogenetic grids in the KFMASH and KMnFMASH model systems calculated with the software thermocalc 3.1 are presented for the P–T range 0.5–12 kbar and 450–900 °C, for assemblages involving garnet, muscovite, chloritoid, biotite, chlorite, staurolite, cordierite, spinel, orthopyroxene, K‐feldspar, Al₂SiO₅ phases, quartz, water and melt. Based on calculated compatibility diagrams and P–T and T–M_Mn [Mn/(Mg + Fe + Mn)] pseudosections for different metapelitic bulk compositions, the principal conclusions are that the addition of Mn to the KFMASH system: (i) enhances the stability of garnet, and, to a lesser extent, aluminosilicates; (ii) reduces the stability of staurolite, cordierite and, to a lesser extent, chlorite; and (iii) extends the medium pressure stability of muscovite and the low‐P stability field of K‐feldspar. The influence of Mn on individual mineral stabilities is strongly related to rock composition, in particular, to the relative contents of Al₂O₃ and K₂O. For metapelites of a range of compositions and M_Mn values, P–T pseudosections in the KFMASH system, in most cases, do not adequately predict the mineral assemblages observed in natural assemblages under medium and low‐pressure conditions. In contrast, the P–T pseudosections in the KMnFMASH system generally provide more satisfactory results, suggesting that MnO is one of the non‐KFMASH components that should not be neglected in documenting the phase equilibria of medium‐ and low‐P metapelites.     

A new Middle Pleistocene interglacial record from Denmark: Chronostratigraphic correlation,palaeovegetation and fire dynamics

Previously only three terrestrial interglacial periods were known from southern Scandinavia, all of which could be relatively easily correlated within the central European stratigraphical framework. Here, we present a new interglacial–interstadial pollen, plant macrofossil and charcoal record from Trelde Klint, Denmark, and analyse its biostratigraphy, correlation with other European records, vegetation development, fire dynamics and absolute dating. Except for a slight truncation of the early part of the record, the pollen stratigraphy exhibits a full interglacial succession, including temperate trees (Quercus, Ulmus and Tilia) during its mesocratic stage. Macrofossil analysis allowed identification to species level for Quercus robur, Picea abies and two mosses. Conifers (Pinus and Picea) dominate the pollen record of the interglacial sequence, and the occurrence of Larix pollen in the top part of the interglacial record as well as in the interstadial sediments is especially indicative of this interglacial. The overall diversity of tree genera is rather low. These biostratigraphical features suggest that Trelde Klint is unique among Danish records, but it is similar to records from northern Germany. Numerical analyses (REVEALS and DCA) indicate that forests during the temperate stage were dense and that vegetation openness increased only towards the end of the interglacial, accompanied by increased fire occurrence. A short interstadial sequence with a dominance of Pinus and Betula and the presence of Larix is present above the interglacial deposit. We argue that lack of attention to differences in fire regimes may hamper understanding of between‐site correlations of interglacial pollen records. OSL dating, using a novel feldspar technique, yields an average age of 350±20 ka for the sandy sediments above the interglacial layers at Trelde Klint, suggesting that the whole interglacial–interstadial succession belongs to Marine Isotope Stage 11.     

Distribution of metals in soils and plants around mineralized zones at Cartagena-La Unión mining district (SE,Spain)

A geochemical and mineralogical characterization of three zones (namely oxides zones, hydrothermal alteration zone and mining wastes zone) from a mineralized zone in the upper part of the Cartagena-La Unión range was carried out by analysing rocks, soils and three plant species (Piptatherum miliaceum, Ditrichia viscosa and Hirsfeldia incana). The transference and bioavailability of some metals (especially Pb, Zn, As and Fe) from soils to plants was also checked. Results show that rocks have a large content of Fe and Pb which are transferred to surrounding soils also highly enriched in these elements (Fe ranges from 9 to 35% and Pb 1 to 2.9%). Regarding soil to plant transfer, it was shown a differential behaviour for both the three plant species and the soil zones, with a higher level of metal accumulation rates for Piptatherum miliaceum in the hydrothermal alteration zone. Values of accumulation rates obtained for Pb in Piptatherum miliaceum allow considering it a good choice for phytoremediation purposes.     

The significance of Mn‐rich ilmenite and the determination of P–T paths from zoned garnet in metasedimentary rocks from the western Cape Breton Highlands,Nova Scotia

The Jumping Brook Metamorphic Suite in the western Cape Breton Highlands of Nova Scotia is part of an inverted Barrovian sequence that formed during a Late Silurian–Early Devonian promontory–promontory collision in the Canadian Appalachians. In this study, systematic discrepancies between geochemical observations and thermodynamic model predictions led to the discovery of a systematic relationship linking the style of garnet core isopleth intersection (GCII) to the pyrophanite (MnTiO₃) component of co‐existing ilmenite. Samples that yielded tight GCIIs at or near the garnet‐in curve were found to contain ilmenite with negligible pyrophanite components, whereas samples yielding GCIIs far removed (up to 105°C) from the garnet‐in curve were found to contain ilmenite with significant pyrophanite and/or ecandrewsite (ZnTiO₃) components. Based on petrographic and geochemical observations, Mn(±Zn)‐rich ilmenite are interpreted to have sequestered Mn throughout prograde metamorphism due to sluggish intracrystalline diffusion. The amount of reactive Mn input into the thermodynamic models from whole‐rock analyses were, in some cases, overestimated, resulting in garnet‐in curve topologies that extend to erroneously low P–T conditions. Modifications to the whole‐rock chemistry that account for Mn sequestration into ilmenite, however, yielded robust model results. Our results show that, in addition to uncertainties in thermodynamic data sets and phenomenon related to reaction kinetics, Mn‐rich ilmenite may superimpose additional complexities related to the interpretation of predicted equilibria involving garnet. Numerical simulations of garnet crystallization were used to infer P–T paths of metamorphism for one sample from the garnet zone (Mn corrected) and two samples from the staurolite zone (Mn uncorrected) of the inverted sequence. Model results are remarkably similar among the three samples and indicate that garnet crystallization occurred along relatively steep (31–37°C/km) clockwise P–T paths. The peak conditions of garnet crystallization and metamorphism (560–590°C, 7.4–8.0 kbar) are interpreted to have been attained approximately simultaneously, such that the paths are characterized by tight prograde‐to‐retrograde transitions. The hairpin nature of the P–T paths is interpreted to represent the onset of thrust‐related exhumation and isograd inversion along ductile shear zones, consistent with available field and geochronological constraints.     

The contrasting biogeochemistry of iron and manganese in the Pacific Ocean

Vertical and horizontal distributions of dissolved and suspended particulate Fe and Mn, and vertical fluxes of these metals (obtained with sediment traps) were determined throughout the Pacific Ocean. In general, dissolved Fe is low in surface and deep waters (0.1 to 0.7 nmol/kg), with maxima associated with the intermediate depth oxygen minimum zone (2.0 to 6.6 nmol/kg). Vertical distributions of dissolved Mn are similar to previous reports, exhibiting a surface maximum, a subsurface minimum, a Mn maximum layer coincident with the oxygen minimum zone, and lowest values in deep waters.Near-shore removal processes are more intense for dissolved Fe than for dissolved Mn. Dissolved Mn in the surface mixed layer remains elevated much farther offshore than dissolved Fe. Elevated near-surface dissolved Mn concentrations occur in the North Pacific Equatorial Current, suggesting transport from the eastern boundary. Near-surface mixed-layer dissolved Mn concentrations are higher in the North Pacific gyre reflecting enhanced northern hemisphere aeolian sources.Residence time estimates for the settling of refractory paniculate Fe and Mn from the upper water column are 62–220 days (Fe), and 105–235 days (Mn). In contrast, residence times for the scavenging of dissolved Fe and Mn are 2–13 years (Fe) and 3–74 years (Mn). Scavenging residence times for dissolved Mn based on horizontal mixing in the surface mixed layer of the northeast Pacific are 0.4 years (nearshore) to 19 years (1000 km offshore).There is no evidence for in situ Fe redox dissolution within sub-oxic waters in the eastern tropical North Pacific. Dissolved Fe appeared to be controlled by dissolution from sub-oxic sediments, with oxidative scavenging in the water column or upper sediment layers. However, in situ Mn dissolution within the oxygen minimum zone was evident.     

Assessing modern arboreal phytolith sensitivity to vegetation variations in temperate forest regions

To assess the reliability of arboreal phytoliths for differentiating vegetation types in temperate forest regions, we systematically analysed arboreal leaf phytoliths from 72 arboreal plants and 49 modern soils from three forest types in northeast China. The arboreal leaf phytolith production and morphotypes were highly variable between species. The arboreal leaf phytolith assemblages could clearly distinguish between broadleaf and coniferous species, but they were much less successful in differentiating broadleaved trees into subtaxa. Coniferous leaf morphotypes were successfully used to differentiate coniferous trees into families and subtaxa, especially in the Pinaceae. Two diagnostic broadleaved and six coniferous phytolith morphotypes were recognized within the modern soil beneath forest ecosystems. These arboreal phytoliths comprised up to 10–15% of the total soil phytoliths, and were dominated by coniferous types. Arboreal phytolith concentrations and phytolith assemblages in the soils fluctuated substantially amongst the three forest types. Soil arboreal phytolith assemblages were successfully used to differentiate samples from Larix mixed forest, broadleaf forest and Pinus koraiensis mixed forest. In addition, the arboreal index quantitatively distinguished the three forest types, with B/BE values <0.4 for Larix mixed forest samples, values from 0.4 to 0.6 for broadleaf forest samples, and values from 0.6 to 0.9 for P. koraiensis mixed forest. Thus, our surface soil arboreal phytolith assemblages and arboreal index are a useful reference for differentiating forest ecotypes, and they also provide reliable analogues for arboreal phytoliths from palaeoecological contexts in temperate forest regions.