Application Of Proxies Research Articles

Deciphering the potential of Ba/Ca, Mo/Ca and Li/Ca profiles in the bivalve shell Pecten maximus as proxies for the reconstruction of phytoplankton dynamics

Shells of the fast-growing bivalve Pecten maximus serve as a geochemical archive for the reconstruction of past phytoplankton dynamics. Specifically, high-resolution, temporally accurately aligned molar barium-to-calcium (Ba/Cashell), molybdenum-to-calcium (Mo/Cashell) and lithium-to-calcium ratios (Li/Cashell) of the shell calcite revealed distinct peaks which are closely linked to phytoplankton dynamics. Yet, the development and applicability of these geochemical proxies is still at an early stage and needs further calibration. In this study, we examined the relationship between the timing and magnitude of Ba/Cashell, Mo/Cashell and Li/Cashell peaks of P. maximus and the occurrence of various phytoplankton species (diatoms and dinoflagellates) from a statistical perspective. Studied shell samples (three specimens per calendar year) as well as detailed phytoplankton observation data were derived from the well-studied costal ecosystem of the Bay of Brest (France) over three years (2011, 2012 and 2019). An algorithm-based pseudo-random sampling simulation technique was established that analyzed the complex phytoplankton datasets with respect to the profiles of Ba/Cashell, Mo/Cashell and Li/Cashell to identify potential patterns between phytoplankton and trace element time-series. The simulation results indicate that the timing and magnitude of Ba/Cashell, Mo/Cashell and Li/Cashell peaks agreed best with the occurrence of specific phytoplankton blooms that developed ca. one to two weeks earlier. The data suggest that the formation of transient Ba/Cashell peaks had a plurispecific origin, i.e., potentially linked to blooms of ingestible diatom, dinoflagellate and flagellate species enriched in Ba that occurred 8 to 12 days earlier. Observed peaks in Mo/Cashell profiles demonstrably followed the timing and intensity of blooms of the dominant dinoflagellate genus Gymnodinium spp. after a short time lag of around 8 days, potentially linked to an enhanced enzyme activity of nitrate reductase that requires the presence of Mo in the dinoflagellate cells. In addition, Mo/Cashell peaks agreed with periods of diatom aggregate formation which were hypothesized to induce the formation of Mo/Cashell peaks in scallop shells. Li/Cashell profiles revealed similar patterns as large blooms of the diatom Chaetoceros spp. as well as to neurotoxin producing diatoms of the genus Pseudo-nitzschia when considering a short time lag of 8 to 12 days. These findings highlight the great potential of using Ba/Cashell, Mo/Cashell and Li/Cashell chronologies in P. maximus shells as proxies of past phytoplankton dynamics.

North Atlantic Oscillation seesaw effect in leaf morphological records from dwarf birch shrubs in Greenland and Finland

The North Atlantic Oscillation (NAO) determines wind speed and direction, seasonal heat, moisture transport, storm tracks, cloudiness and sea-ice cover through atmospheric mass balance shifts between the Arctic and the subtropical Atlantic. The NAO is characterized by the typical, yet insufficiently understood, seesaw pattern of warmer winter and spring temperatures over Scandinavia and cooler temperatures over Greenland during the positive phase of the NAO, and vice versa during the negative phase. We tested the potential to reconstruct NAO variation beyond the meteorological record through the application of a microphenological proxy. We measured the Undulation Index (UI) in Betula nana epidermal cells from herbarium leaf samples and fossil peat fragments dating back to 1865—exceeding most meteorological records in the Arctic—to estimate imprints of spring thermal properties and NAO in Greenland and Finland. We found negative relations between Greenland UI and late winter, spring and early summer NAO, and mostly positive, but not significant, relations between Finland UI and NAO in years with pronounced NAO expression. The direction of the UI response in this common circumpolar species is, therefore, likely in line with the NAO seesaw effect, with leaf development response to NAO fluctuations in northern Europe opposing the response in Greenland and vice versa. Increased knowledge of the UI response to climate may contribute to understanding ecological properties of key Arctic species, whilst additionally providing a proxy for NAO dynamics.

Mineralogy and geochemistry of the sandstone facies of Campanian Lokoja formation in the Southern Bida basin, Nigeria: implications for provenance and weathering history

The upper Cretaceous Lokoja Formation is the earliest deposited stratigraphic unit in the intracratonic Bida Basin, Nigeria. It consists predominantly of sandstone and offers a potential hydrocarbon reservoir in the basin. In this study, we investigated the bulk elemental (major, trace and rare earth elements) and mineralogical compositions of the sandstones for the determination of their compositional maturity, tectonic setting, source and weathering history. The sandstone geochemical data indicates that the samples contain moderate amount of SiO2 and Al2O3 with average values of 78.3 % and 9.75 % respectively. Relatively high average values of K2O (1.59 %) and Na2O (1.52 %) and low Fe2O3 (2.56 %), MnO (0.05 %), TiO2 (0.31 %) and P2O5 (0.018 %) were obtained. Plots of relevant geochemical elements reveal that the sandstones are predominantly arkose and litharenite types with minor sub-litharenites. Application of some trace element geochemical proxies; La/Co (11.78), Th/Co (1.32), La/Th (7.04) and Eu/Eu∗ (0.82) to constrain the source history suggest protolith dominated by felsic rock. Relatively low average values of ΣREEs (12.81) and ΣHREEs (1.52) support the felsic provenance of the sandstones and the tectonic setting discriminant function plots indicate passive margin depositional basin. Paleo-weathering plot reveals a moderate humid climatic condition and the mean values of CIA (79.21), CIW (90.51), PIA (66.55) and A–CN–K diagram indicates low to moderate chemical weathering in the source area and compositional immaturity for the sediments. This study concludes that the sandstones of the Lokoja Formation are immature and were derived from the faulted blocks of granitic basement rocks at the margin of the basin and deposited proximally.

Incorporating lateral variability and extent of paleosols into proxy uncertainty

Paleosols (fossil soils) are valuable records of terrestrial climate and environments, and paleosol-based proxies are commonly used to reconstruct past climates and ecosystems. Results from relatively small outcrops or transects or from single vertical sections are frequently scaled up to represent basin-scale processes and conditions, and reconstructions are relied on for temporal changes in those basins. However, uncertainty arising from limited outcrop extent is not currently considered in the standard application of paleosol-based proxies. To explore uncertainty arising from lateral paleosol heterogeneity, we performed a random subsampling analysis on a newly-collected 2.9 km paleosol transect from SW Wyoming, along with two previously-published paleosols. We demonstrate the importance of sampling multiple paleosol profiles, considering lateral geochemical variability, and focusing on relative rather than absolute changes when outcrop-based uncertainty may require it. • Paleosol-based proxies provide unique records of terrestrial climate. • However, outcrop extent and lateral variability are not typically considered. • We statistically resample 3 paleosol transects (1, 1.5, and 3 km). • Sampling >3 profiles from a paleosol decreases proxy uncertainty. • Relative rather than absolute changes in proxy should be commonly used.

Holocene climate dynamics on the European scale: Insights from a coastal archaeological record from the temperate Bay of Biscay (SW France)

The main drivers of Europe's climate during the Holocene result from the coupling and interplay of external and internal radiative processes with the shifting patterns of many dynamic components (e.g. glaciers, ocean currents, wind fields, vegetation cover). Those driving forces were expressed across a range of geographical scales, from local to global, in a diverse set of records forming a patchwork of evidence as to the fundamental pacing effect of climate on past ecosystems. Various sedimentary deposits resulting from those complex forcing contexts bear climatic signatures that it is not always easy to disentangle especially with respect to local factors.The present paper focuses on a coastal archaeological site on the Medoc peninsula (the Lède du Gurp site in south-western France) that records Holocene palaeoenvironmental changes, decoded here century after century and integrated with ongoing events on a pan-North-Atlantic scale. Based on updated geoarchaeological approaches, thanks to new applications of proxies, especially X-ray fluorescence (XRF) core scanning methods for this article, continuous sedimentary records have been analysed in order to reconstruct a regional framework for past ecosystem events, including events potentially related to human activity. Our work identifies signals on various scales in the record under study, with both long- and short-term trends and local and global imprints, but all closely bound up with proximal North Atlantic Ocean dynamics. It highlights how western European environments (and so populations) were dependent upon the linearity of climate evolution at the key Northgrippian/Meghalayan transition.

Vegetation History in a Peat Succession Over the Past 8,000 years in the ISM-Controlled Kedarnath Region, Garhwal Himalaya: Reconstruction Using Molecular Fossils

The Holocene epoch has witnessed several natural climate variations and these are well encoded in various geological archives. The present biomarker investigation in conjunction with previously published multi-proxy records was applied to reconstruct organic matter (OM) sources forming the peat succession spanning the last 8000 cal yr BP and shift in hydrological conditions from the Kedarnath region, Garhwal Himalaya. Intensified monsoon prevailed from ∼7515 until ∼2300 cal yr BP but with reversal to transient arid period particularly between ∼5200 and ∼3600 cal yr BP as revealed by the variability in n-C23/n-C31, ACL (average chain length of n-alkanes) and Paq (P-aqueous) values. A prolonged arid phase is recognizable during the interval between ∼2200 and ∼370 cal yr BP suggested by the n-alkane proxies. Regional scale heterogeneity in the monsoonal pattern is known in the studied temporal range of mid to late Holocene across the Indian subcontinent that is probably a result of complex climate dynamics, sensitivity of proxies and impact of teleconnections. The biomarker signatures deduced from gas chromatography mass spectrometry (GCMS) analysis are suggestive of a mixed biotic input that includes prokaryotes, Sphagnum spp. and gymnosperm flora. The mid chain alkanes viz. n-C23 and n-C25 denote the presence of typical peat forming Sphagnum moss that preferentially grows in humid and waterlogged conditions. Diterpane marker such as ent-kaurane indicates contribution of gymnosperms, whereas the hopanes are signatures of microbial input. The preservation of organic matter is attributed to little microbial degradation in a largely suboxic depositional environment. Our study strengthens the applicability of organic geochemical proxies for the reconstruction of past climate history and indicates their suitability for use on longer timescales given the high preservation potential of the molecular remains.

Variation of Isoprenoid GDGTs in the Stratified Marine Water Column: Implications for GDGT-Based TEX86 Paleothermometry

Isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) derived from archaea are lipid biomarkers that exhibit high sensitivity to changes in water temperature, leading to the widespread application of the isoGDGT-based tetraether index of 86 carbon atoms (TEX86) in surface seawater temperature (SST) reconstruction. However, there remain some uncertainties regarding the robustness of TEX86 under changing water conditions (e.g., variations in water depth, oxygen and pH). Here, we analyzed isoGDGTs in suspended particles at different depths of the East China Sea (ECS) during summer 2020, aiming to constrain the applicability of the TEX86 proxy in coastal waters. Our data showed that the isoGDGTs were mainly derived from planktonic Thaumarchaeota, as revealed by the low ratio of GDGT-0/crenarchaeol (<0.5). The vertical distribution of isoGDGT concentration depicted a downward increase from the surface to the bottom. This observation was likely shaped by Thaumarchaeota, which regulate the extent of ammonia oxidation based on the availability of ammonium. The occurrence of maximal isoGDGT concentrations in the bottom layer suggests that the isoGDGTs in sediments are mainly controlled by bottom archaeal production rather than surface archaeal production. By reanalyzing the published isoGDGT data of surface sediments in the ECS inner shelf, we found that the sedimentary TEX86 relates much better to the annual mean bottom seawater temperature (BST) than to the annual mean SST, indicating that sedimentary TEX86 is more inclined to be a proxy for the BST in the shallow ECS. In addition, the positive bias of TEX86 driven by low dissolved oxygen and low pH was observed under the pycnocline, indicating that the application of TEX86 to reconstruct seawater temperature should be carefully appraised in coastal environments with strong water column stratification.

Plant wax biomarkers in human evolutionary studies.

Plant wax biomarkers are an innovative proxy for reconstructing vegetation composition and structure, rainfall intensity, temperature, and other climatic and environmental dynamics. Traditionally used in earth sciences and climate studies from "off-site" ocean and lake records, biomarker research is now incorporated in archeology and paleoanthropology to answer questions relating to past human-environment interactions and human evolution. Biomarker research is generating new and exciting information on the ecological context in which Homo and its closest relatives evolved, adapted, and invented stone tool technologies. In this review, we examine plant wax biomarkers and their use in reconstructing past plant landscapes and hydroclimates. We summarize the applications of plant wax molecular proxies in archeological research, assess challenges relating to taphonomy, consider the role of modern plant ecosystems in interpreting ancient habitats, and examine case studies conducted at key paleoanthropological locations in eastern and southern Africa and Europe.

Effects of Ozone Isotopologue Formation on the Clumped‐Isotope Composition of Atmospheric O2

AbstractTropospheric 18O18O is an emerging proxy for past tropospheric ozone and free‐tropospheric temperatures. The basis of these applications is the idea that isotope‐exchange reactions in the atmosphere drive 18O18O abundances toward isotopic equilibrium. However, previous work used an offline box‐model framework to explain the 18O18O budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the 18O18O proxy, we developed a scheme to simulate atmospheric 18O18O abundances (quantified as ∆36 values) online within the GEOS‐Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O2 isotopic equilibration scheme within GEOS‐Chem show quantitative agreement with measurements only in the middle stratosphere; modeled ∆36 values are too high elsewhere. Investigations using a comprehensive model of the O‐O2‐O3 isotopic photochemical system and proof‐of‐principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to ∆36 values: the anomalously efficient titration of 18O18O to form ozone. Incorporating these effects into the online ∆36 calculation scheme in GEOS‐Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of 18O18O in O2, the modeled change in the mean tropospheric ∆36 value since 1850 CE is only slightly altered; it is still quantitatively consistent with the ice‐core ∆36 record, implying that the tropospheric ozone burden increased less than 40% over the twentieth century.

Geochemistry of iron and sulfur in the Holocene marine sediments under contrasting depositional settings, with caveats for applications of paleoredox proxies

Cycling and fates of iron (Fe) and sulfur (S) in marine sediments are influenced by depositional settings to differential extents. The information is crucial for addressing the responses of their benthic diagenesis to changing climates and environments and also for reconstructing paleo-depositional conditions, but has not been well constrained. Detailed chemical speciation was utilized to characterize geochemistry of Fe and S, and then to reveal the impacts of depositional settings on their diagenesis at three locations, representing contrasting depositional environments: (i) highly dynamic Yangtze River estuary (YRE), (ii) the depocenter of South Yellow Sea (SYS), which is only remotely impacted by large river, and (iii) the middle Okinawa trough (OT), a back-arc deep basin along the outer edge of the East China Sea (ECS) slope. Results show that the YRE sediments favor accumulation of total highly reactive Fe (FeHR), while the SYS sediments are poor in FeHR due to low FeHR in their source material and/or preferential trapping of FeHR during sediment transport through the semi-enclosed Bohai Sea. Ferruginous sediment regimes in the highly dynamic YRE system facilitate Fe(III) reduction and burial of unsulfidized Fe(II), while the SYS and OT sediments favor sulfate reduction and pyritization of Fe(II). Pyrite is always the main sink of reduced S that escapes reoxidation in the entire continental margin, regardless of depositional environments. Abundant reactive Fe(III) but low total reduced inorganic sulfide (TRIS) contents in the three sites suggest that TRIS burial is largely controlled by the availability of degradable OC and/or dynamic regimes of sediments. The applicability of two widely used Fe- and S-based proxies to distinguish bottom-water conditions, that is, OC/TRIS ratio and FeHR to total Fe (FeHR/FeT) ratio, were examined in the three contrasting environments, and caveats were given for future applications of the two proxies.

Deep-water osmium-isotope record of the Permian–Triassic interval from Niushan, China reveals potential delayed volcanic signal post the mass extinction

The end Permian mass extinction event is one of the most severe biotic crisis of the Phanerozoic. The trigger of this event has been widely linked to massive volcanic activity associated with the Siberian Traps Large Igneous Province through the application of multiple geochronological (e.g., UPb and ArAr dating) and geochemical proxies (e.g., C, Hg, Zn, Os, etc.). Of these proxies, a few osmium (187Os/188Os) records are available for near-shore/shallow water depositional settings (e.g., Meishan, China; Opal Creek, Canada), which suggest multiple episodes of volcanism before, during and after the mass extinction event. Here, we present a new initial 187Os/188Os (Osi) stratigraphy across the deep-water Niushan Permian–Triassic boundary interval section of South China that reveals a single unradiogenic Os-isotope shift (from ~0.6 to 0.3) after the end Permian mass extinction event interval, which is interpreted to be related to volcanic activity. Above the unradiogenic excursion, a radiogenic shift to ~1.1 is detected across the Permian–Triassic boundary at Niushan that is correlative to the radiogenic Osi shift observed in the Meishan section. This increase in Os-isotope values is taken to reflect enhanced continental weathering. Both the unradiogenic and radiogenic excursions in the deep-water Niushan section are smaller in magnitude compared with the Os isotope profiles from more shallow-water sections of Meishan and Opal Creek. Our data suggest investigations of multiple sections across a variety of depositional environments may yield a more comprehensive understanding of the scale of the global perturbations related to volcanism and continental weathering intensity of the Permian–Triassic boundary interval.

Smart Proxy Modeling of a Fractured Reservoir Model for Production Optimization: Implementation of Metaheuristic Algorithm and Probabilistic Application

Numerical reservoir simulation has been recognized as one of the most frequently used aids in reservoir management. Despite having high calculability performance, it presents an acute shortcoming, namely the long computational time induced by the complexities of reservoir models. This situation applies aptly in the modeling of fractured reservoirs because these reservoirs are strongly heterogeneous. Therefore, the domains of artificial intelligence and machine learning (ML) were used to alleviate this computational challenge by creating a new class of reservoir modeling, namely smart proxy modeling (SPM). SPM is a ML approach that requires a spatio-temporal database extracted from the numerical simulation to be built. In this study, we demonstrate the procedures of SPM based on a synthetic fractured reservoir model, which is a representation of dual-porosity dual-permeability model. The applied ML technique for SPM is artificial neural network. We then present the application of the smart proxies in production optimization to illustrate its practicality. Apart from applying the backpropagation algorithms, we implemented particle swarm optimization (PSO), which is one of the metaheuristic algorithms, to build the SPM. We also propose an additional procedure in SPM by integrating the probabilistic application to examine the overall performance of the smart proxies. In this work, we inferred that the PSO had a higher chance to improve the reliability of smart proxies with excellent training results and predictive performance compared with the considered backpropagation approaches.

Geochemistry of Eocene Bawang Member turbidites of the Belaga Formation, Borneo: Implications for provenance, palaeoweathering, and tectonic setting

The Belaga Formation of the Rajang Group or Rajang Fold and Thrust Belt (Late Cretaceous to Late Eocene) is mostly exposed in Sibu Zone along with some exposures in the Miri Zone of Central Sarawak. This entire turbiditic sequence was believed to have been deposited in a deep marine environment in a basin having an overall passive margin setting, that is, the Rajang Sea. However, the Eocene age‐related stratigraphic record of this group (including Bawang Member) is much more complex, due to the complicated geological and tectonic settings which prevailed during their deposition. Here, we present field observations along with the application of various geochemical proxies and their constraints for the understanding of provenance, palaeo‐weathering, and tectonic evolution of the area during the deposition of Bawang turbidites. Based on field observation, it has been found that this member consists of four main lithofacies, including massive sandstone facies (MSF), thick‐bedded facies (TBF), heterolithic facies (HF), and mud facies (MF). Using geochemical data, chemical weathering indices (CIA and CIW) values and A‐CN‐K plot show that the source area for Bawang turbidites has undergone a moderate to an intense degree of chemical weathering and was influenced by the recycling effect. The slight depletion in sandstones and shales for Cr, Ni, and V values is consistent with the felsic dominated source region; however, La/Sc versus Co/Th and La/Th versus Hf plots show a mixed source (felsic and intermediate volcanic source) with some input of recycled sediments from the older sedimentary to metasedimentary rocks. Various geochemical ratios and discriminant diagrams verify that the Schwaner Mountains and its metamorphic group of rocks were the principal provenances for these sediments, along with some input from West Borneo. The results of the geochemical analysis also show that Bawang turbidite sediments were deposited in a basin associated with an initial active continental margin setting and the basin was shifting towards a passive setting (Late Eocene–Oligocene). The volcanic input in Bawang Member during the Late Eocene also suggests the involvement of some subsequent possible arc setting around the “Bawang subbasin”.

An Improved Cleaning Protocol for Foraminiferal Calcite from Unconsolidated Core Sediments: HyPerCal—A New Practice for Micropaleontological and Paleoclimatic Proxies

Paleoclimatic and paleoceanographic studies routinely rely on the usage of foraminiferal calcite through faunal, morphometric and physico-chemical proxies. The application of such proxies presupposes the extraction and cleaning of these biomineralized components from ocean sediments in the most efficient way, a process which is often labor intensive and time consuming. In this respect, in this study we performed a systematic experiment for planktonic foraminiferal specimen cleaning using different chemical treatments and evaluated the resulting data of a Late Quaternary gravity core sample from the Aegean Sea. All cleaning procedures adopted here were made on the basis of their minimum potential bias upon foraminiferal proxies, such as the faunal assemblages, degree of fragmentation, stable isotope composition (δ18O and δ13C) and/or Mg/Ca ratios that are frequently used as proxies for surface-ocean climate parameters (e.g., sea surface temperature, sea surface salinity). Six different protocols were tested, involving washing, sieving, and chemical treatment of the samples with hydrogen peroxide and/or sodium hexametaphosphate (Calgon®). Single species foraminifera shell weighing was combined with high-resolution scanning electron microscopy (SEM) and synchrotron X-ray microtomography (SμCT) of the material processed by each of the cleaning protocols, in order to assess the decontamination degree of specimen’s ultrastructure and interior. It appeared that a good compromise between time and cleaning efficiency is the simultaneous treatment of samples with a mixed hydrogen peroxide and Calgon solution, while the most effective way to almost completely decontaminate the calcareous components from undesirable sedimentary material is a two-step treatment—initially with hydrogen peroxide and subsequently with Calgon solutions.

What’s in a colluvial deposit? Perspectives from archaeopedology

Colluvial deposits are considered as sedimentary archives for the reconstruction of the sedimentation and climate history, past pedogenesis and phases of land use. However, the human contribution to the formation of colluvial deposits is mainly based on assumptions derived from the local chronostratigraphy and archaeology. For this reason, there is often a substantial gap in the identification of specific land use practices that promoted prehistoric soil erosion and sedimentation processes.We use an archaeopedological multi-proxy approach on a multi-layered colluvial deposit (six colluvial horizons) at the prehistoric site of Fürstenberg (Southwest Germany) to gain detailed insights into the sedimentation history, past pedogenesis and land use practices since the Neolithic. Soil and geochemical analyses such as X-ray fluorescence (XRF), X-ray diffraction (XRD), pedogenic oxides, pH-value and calcium carbonate content support the chronostratigraphy based on ages from optically stimulated luminescence (OSL) and AMS 14C dating. Further, biogeochemical analyses of phytoliths, charcoal spectra, black carbon (BC), soil organic matter (SOM) composition by using pyrolysis-field ionization mass spectroscopy (Py-FIMS), urease activity, steroid biomarker and heavy metals (HM) are used as land use proxies.The OSL and 14C ages and the local archaeological record indicate six phases of colluvial deposition that occurred through five phases of land use comprising the Early to Younger Neolithic, the Urnfield to Hallstatt period, the Iron to Roman Age, the High Middle Ages, and the pre-modern period. The soil and geochemical proxies correlate with a phase of geomorphodynamic stability between the Early to Younger Neolithic and the Urnfield to Hallstatt period. The high abundance of grass morphotypes since the Neolithic and the increase of Juniperus since the Urnfield to Hallstatt period indicate a persistent anthropogenic impact on the vegetation. Considerable amounts of burned OM (up to 676 g BC kg−1 SOC, also identified as thermally stabilized SOM compounds by Py-FIMS) in colluvial horizons provide information that fire clearing (e.g. slash-and-burn) was especially used to open and maintain the landscape until the Roman Age. The absence of phytolith species originating from cereals, the occurrence of Juniperus and the evidence from the analysis of urease activity and faecal biomarkers indicate that the slopes of the Fürstenberg were mainly used for livestock farming and wood procurement.Thus, the application of specific soil-biogeochemical proxies to colluvial deposits provide new information on the nature of past land use practices that caused the formation of colluvial deposits at that time. In general, archaeopedological multi-proxy analyses of colluvial deposits, integrating the local archaeological record, contributes to a refined understanding of how humans have shaped the landscape since the Neolithic.

Effects of redox conditions and temperature on the degradation of Sphagnumn-alkanes

Leaf wax n-alkanes in peat deposits are important proxies for paleoenvironmental reconstructions. The n-alkane compositions of Sphagnum species, which are important peat forming plants, are commonly dominated by the C23 and C25 homologs. However, questions remain about the stability of Sphagnum-derived n-alkanes to early diagenetic alterations. In this study, a 13-month litterbag decomposition study using Sphagnum palustre collected from the Dajiuhu peatland, central China, was conducted under controlled laboratory conditions to assess the influences of redox (aerobic vs anaerobic) conditions and environmental temperatures (15 °C vs 25 °C) on the chain-length distributions and carbon isotopic compositions of Sphagnum n-alkanes. Results clearly reveal the preferential degradation under aerobic conditions of mid-chain n-alkanes relative to their long-chain homologs (C29 and C31), resulting in the increase of the relative proportions of long-chain n-alkanes. The change in n-alkane distribution is accompanied by an increase in the δ13C values of the mid-chain n-alkanes, whereas those of the long-chain n-alkanes remain nearly constant. In contrast, neither chain-length distributions nor n-alkane δ13C values were much affected under anaerobic degradation conditions. Statistical analysis reveals that redox conditions play significant roles in the degradation of Sphagnum n-alkanes, whereas the influence of air temperature is not significant. These findings will improve applications of n-alkane paleoenvironmental proxies to reconstruct the types of plants and the depositional conditions that contributed to peat sequences, particularly under settings with fluctuating water levels that affect redox conditions.

Geochemical and sedimentological responses of arctic glacial Lake Ilirney, chukotka (far east Russia) to palaeoenvironmental change since ∼51.8 ka BP

Palaeoenvironmental reconstructions with temporal coverages extending beyond Marine Isotope Stage (MIS) three are scarce within the data sparse region of Chukotka, Far East Russia. The objective of this paper is to infer palaeoenvironmental variability from a 10.76 m long, OSL- and 14C- dated sediment core from Lake Ilirney, Chukotka (67°21′N, 168°19′E). We analysed high-resolution sediment-geochemistry (XRF), sedimentology (TC, TN, TOC, grain-size), mineralogy (XRD) and preliminary micropalaeontological data (diatoms and pollen) from the core as well as acoustic sub-bottom profiling data from the lake basin. Our results affirm the application of XRF-based sediment-geochemical proxies as effective tracers of palaeoenvironmental variability within arctic lake systems. Our study reveals that a lake formed during MIS3 from 51.8 (±4.1) ka BP, following extensive MIS4 glaciation. Catchment palaeoenvironmental conditions during this time remained harsh associated with the continued presence of a catchment glacier until 36.2 (±2.6) ka BP. Partial amelioration reflected by increased diatom, catchment vegetation and lake organic productivity and clastic sediment input from mixed sources from 36.2 (±2.6) ka BP resulted in a lake high-stand ∼15 m above present and is interpreted as evidence of a more productive palaeoenvironment coincident with the MIS3 interstadial optimum. A transitional period of deteriorating palaeoenvironmental conditions occurred ∼30–27.9 ka BP and was superseded by periglacial-glacial conditions from 27.9 (±0.8) ka BP, during the last glacial maximum. Deglaciation as marked by sediment-geochemical proxies commenced at 20.2 (±0.8) ka BP. Our findings are compared with lacustrine, Yedoma and river-bluff records from across Beringia and potentially yield limited support for a marked Younger Dryas cooling in the study area.

An isotope label method for empirical detection of carbonic anhydrase in the calcification pathway of the coccolithophore Emiliania huxleyi

Coccolithophores are a group of phytoplankton widely distributed in the ocean, which secrete extracellular calcite plates termed coccoliths. Coccoliths have been increasingly employed as an archive for geochemical, ecological and paleoclimate studies in recent years. A robust application of coccolith-based geochemical proxies relies on understanding the carbon acquisition strategies and the pathways of carbon supply for calcification. Carbonic anhydrase (CA) plays important roles in the carbon concentrating mechanism s of aquatic algae and potentially also in calcification. However, it is difficult to independently assess the role of CA in carbon supply for photosynthesis versus calcification. To fill this gap, we explored a new method to detect the CA activity inside coccolithophore. To achieve this, coccolithophores were cultured with oxygen and carbon isotope labeled dissolved inorganic carbon (DIC). By exploiting the different behavior of oxygen and carbon isotopes with (sea)water, this double label method can elucidate the significance of CA activity in the calcification pathway. Application of this method to Emiliania huxleyi shows that CA is present in the calcification pathway, and that there is no significant difference in the CA activity between a high and low CO2 treatment. However, under low CO2 treatment E. huxleyi enhanced the bicarbonate pumping rate on both cell and chloroplast membranes. This novel method could be performed on other species of coccolithophores in the future and have a potential to extend our knowledge on coccolith oxygen isotope vital effects.

Early diagenesis of foraminiferal calcite under anoxic conditions: A case study from the Landsort Deep, Baltic Sea (IODP Site M0063)

The chemical composition of foraminiferal calcite is widely used for studying past environmental conditions and biogeochemistry. However, high rates of microbial organic matter degradation and abundant dissolved metal sources in sediments and pore waters may impede the application of foraminifera-based proxies due to formation of secondary carbonates or other authigenic minerals on and/or inside of foraminiferal tests. Secondary carbonate precipitation severely alters the bulk foraminiferal geochemistry and can be difficult to eliminate through standard foraminiferal trace element cleaning procedures. We present results showing the mineral composition and formation sequence of diagenetic coatings on foraminiferal tests formed under extreme anoxic conditions in the Baltic Sea's deepest basin (the Landsort Deep, IODP Exp. 347, Site M0063). Our study focuses primarily on the diagenetic carbonates present on and in the tests of the low-oxygen tolerant benthic foraminiferal species Elphidium selseyensis and Elphidium clavatum. We applied various geochemical and imaging methods to ascertain the diagenesis processes and the authigenic mineral formation sequence on foraminifera. The authigenic carbonates were enriched in Mn, Mg, Fe and Ba, depending on the environmental redox conditions when the authigenic carbonates were precipitated. Concentrations of redox-sensitive elements such as Mn and Fe were particularly elevated in bottom waters and sedimentary pore waters under oxygen-depleted conditions in the Landsort Deep, resulting in formation of carbonates with highly elevated Mn and Fe contents. In addition to Mn- and Fe carbonates, several other types of authigenic minerals also formed on and in the foraminiferal chambers, including authigenic calcite, and non-carbonate accessory minerals. The formation sequence reveals the redox sensitivities of different elements and the preferential sequence of oxidants used by the microbes during organic matter oxidation and secondary redox reactions. This study provides a case study of extreme early diagenesis of foraminiferal calcite and may serve as a valuable guide when interpreting foraminiferal trace element records from low oxygen environments.

Uranium isotope compositions of biogenic carbonates – Implications for U uptake in shells and the application of the paleo-ocean oxygenation proxy

The application of U isotopes in carbonates as a paleo-ocean oxygenation proxy is based on the critical assumption that the calcareous shell-building organisms incorporate U into their shells without fractionation relative to the U isotopic composition of ambient seawater. Recent studies claim a small, but resolvable, isotopic offset during abiotic and biogenic aragonite precipitation, whereas no isotope fractionation has been recorded during calcite precipitation. Although aragonite is meta-stable and not preserved over geological timescales (>1 Myr) and U precipitates during diagenesis, the U isotope composition of biogenic aragonite is important because aragonite precipitation is an important U sink to carbonate sediments. In contrast, low-magnesium calcite (LMC) is preserved over geological timescales and may provide a reliable fingerprint of ancient ocean chemistry. Therefore, a more general study is needed that compares U isotope compositions of primary marine biogenic carbonate precipitates.We report the U isotope compositions of 32 modern samples from geographically distinct localities in the Atlantic Ocean including corals (Scleractinia, Octocorallia), brachiopods (Articulata), molluscs (Tellina Listeri, Codahia Obicularis) and barnacles as well as one fossil mollusc. These samples reflect variable primary minerals, water temperatures, water depths, pH-values of ambient water, and U concentrations. Several seawater samples have also been measured to compare our methods with those of previously published studies.The analyzed modern corals and brachiopods display U isotopic compositions that are indistinguishable from modern seawater. This suggests that these carbonates have the potential to faithfully record the U isotopic composition of the surrounding seawater in which they form. The analyzed brachiopods are of particular interest as they are composed of the calcium carbonate polymorph LMC that is stable over geological timescales. While this study shows for the first time that LMC phases are robust targets in ancient samples, their low U abundance presents analytical challenges for precise U isotope analyses. We also show that two barnacle shells collected with ambient seawater have U isotopic compositions that are both lighter and heavier than the ambient seawater. The mechanism to explain this offset is not determined, but it demonstrates that at least barnacle shells are not representative of the seawater in which they last lived. Two of three partially fossilized mollusc shells also show resolvable offsets from seawater, likely indicating secondary processes that are known to shift or fractionate U isotopes. Collectively, our new data indicate that: 1) aragonite delivers U with a seawater composition to carbonate sediments, and 2) LMC shells of brachiopods that are stable over geological timescales may be more suitable for reconstructing the U isotope composition of ancient oceans.