New approaches for removing the Si-OH layer of biogenic silica before analysing oxygen isotopes - Helium Flow Dehydration (HFD) and Vacuum Bead Melting (VBM) technique

The analysis of oxygen isotopes from diatom silica (&#948;18OSi) in sediment cores has obtained importance for palaeoclimate reconstruction especially where carbonate proxies are either rare or not available. Compared to the widely accepted relation of oxygen isotopes of carbonate origin to climate-relevant parameters, challenges still occur using biogenic silica. These questions arise at sample preparation as well as and the analysis itself, but are especially related to the removal of loosely bound oxygen of the hydrous layer. It is the common view that diatoms consist of an isotopically homogenous inner Si-O-Si layer and a less dense, hydrous layer forming Si-OH bonds, which has to be removed from the sample prior to analysis. Three methods have been accepted so far to perform this step: Controlled Isotopic Exchange (CIE) followed by fluorination, Stepwise Fluorination (SWF) and inductive High-Temperature carbon reduction (iHTR). The former method of vacuum dehydration (VD) proved to be unable to remove all exchangeable oxygen.Here, a new, remotely-operated laser-fluorination based mass spectrometry unit is used for the analysis. The silica is reacted with a CO2 laser in a BrF5 atmosphere and oxygen is then transferred to and analysed in a mass spectrometer (PDZ Europa 20-20). As CIE is both time-consuming and work-intense and SWF is impractical for this setup mainly due to the high pressure increase during dehydration, a new, efficient and fast method should be developed to remove the hydrous layer using the laser-fluorinationprocess.Two approaches were tested to remove the Si-OH layer and the impact on &#948;18OSi was assessed by performing tests on internal standard materials of marine and lacustrine biogenic silica and of quartz. For VBM, a minimum of 1.5 mg of pure sample is melted to a bead with a defocused laser to eliminate the hydrous outer layer and to reduce the surface. After the bead has formed it is transferred into the reaction chamber completely reacted with a focused laser under BrF5 atmosphere and subsequently analysed on-line.The second method, HFD is an improvement of the outdated VD technique. The sample is heated to 1050°C in a He flow transporting away any removed exchangeable oxygen immediately and thus, not allowing it to re-react with the sample. Various tests have been performed considering pre-heating at 200°C, He flow adjustments and the time of the sample exposed to 1050°C.VBM has difficulties to fully remove the hydrous layer, which results in comparatively lower &#948;18O values. The final set-up was not found yet. The HFD generated similar data than SWF in other laboratories with a high reproducibility and accuracy (standard deviation <0.2 ). Best results could be achieved by pre-heating the sample at 200°C and later on expose it for 15 minutes under a Helium counter flow at 1050°C. Experience with both techniques will be discussed and the reliability of the data compared to other methods

Lacustrine oxygen isotope records from biogenic silica (δ18OBSi) – a global compilation and review

Isotope records are crucial for proxy-model comparison in paleoclimatology because of their advantage of being directly comparable with isotope-enabled paleoclimate model outputs. Oxygen isotopes (δ18O) are commonly measured on carbonates (i.e. ostracods, authigenic carbonates) and biogenic silica (mainly diatoms). Oxygen isotopes in lacustrine carbonates (δ18OCaCO3) have been studied extensively for several decades, yet they are subject to complex species-dependent fractionation processes and not available globally. Lacustrine oxygen isotope records from biogenic silica (δ18OBSi), on the other hand, likely do not display species-dependent fractionation effects (or only very minor) and offer insight even in data-sparse regions devoid of carbonates, such as the Arctic. To date, more than 70 lacustrine δ18OBSi records have been published. These case studies have been complemented with additional efforts addressing climatic and hydrological backgrounds, laboratory techniques and possible species-dependent fractionation as well as deposition and dissolution effects. Here, we present the first comprehensive review and global compilation of lacustrine δ18OBSi records, with explicit regard to their individual lake basin parameters. With this work, we aim at contributing to bridging the gap between modelling and isotope geochemistry approaches regarding terrestrial archives in paleoclimatology. Departing from hitherto prevalent case studies, we assess what we can learn from lacustrine δ18OBSi records globally, considering lake basin characteristics, spatial and temporal coverage as well as hydrological background information. This improves both the usability of δ18OBSi for proxy-model comparison and our understanding of the general constraints for interpreting lacustrine δ18OBSi records

Paleo-environmental gateways in the eastern Canadian arctic – Recent isotope hydrology and diatom oxygen isotopes from Nettilling Lake, Baffin Island, Canada

Nettilling Lake is located on Baffin Island, Nunavut, Canada between the areas of past warming (Canadian High Arctic to the North) and climatic stability (Northern Quebec and Labrador region to the South). Despite being the largest lake in the Nunavut region with a postglacial marine to lacustrine transition history only a few paleo-environmental investigations were completed in this area. The oxygen isotope composition of diatoms (d18O diatom) can provide valuable insights into paleo-environmental conditions. Here, the recent (isotope) hydrology and hydrochemical data from the lake are presented to facilitate the interpretation of a d18O diatom record from an 82 cm sediment core (Ni-2B). The well-mixed lake (d18O water = -17.4‰) is influenced by a heavier (less negative) isotope composition (-18.80‰) from Amadjuak River draining Amadjuak Lake to the South and water of lighter (more negative) isotopic composition (-16.4‰) from the Isurtuq River originating from Penny Ice Cap in the North-East. From the d18O water and d18O diatom of the topmost sample of core Ni-2B a D18O silica-water of 1000 ln alpha(silica-water) = 40.2‰ for sub-recent diatoms of Nettilling Lake was calculated matching the known water-silica fractionation for fossil sediments well and thereby showing the general applicability of this proxy for paleo-reconstructions in this region. Extremely large d18O diatom variations in the core of more than 13‰ are mainly induced by changes in the isotopic composition of the lake water due to a shift from glaciomarine (d18O diatom = +34.6‰) through brackish (+23.4 to +27.2‰) towards lacustrine (+21.5‰) conditions (transition zones glaciomarine to brackish at 69 cm/7300 yr cal. BP and brackish to lacustrine at 35 cm/6000 yr cal. BP) associated with a shift in the degree of salinity. Our study provides the first evidence that paleo-salinity can be reconstructed by d18O diatom. Additionally, for the lacustrine section it could be demonstrated that d18O diatom may serve as a proxy for past air temperature within the same core recording a late Holocene cooling of about 4°C being consistent with other published values for the greater Baffin region

Stable oxygen and carbon isotopes of carbonates in lake sediments as a paleoflood proxy

Lake sediments are increasingly explored as reliable paleoflood archives. In addition to established flood proxies including detrital layer thickness, chemical composition, and grain size, we explore stable oxygen and carbon isotope data as paleoflood proxies for lakes in catchments with carbonate bedrock geology. In a case study from Lake Mondsee (Austria), we integrate high-resolution sediment trapping at a proximal and a distal location and stable isotope analyses of varved lake sediments to investigate flood-triggered detrital sediment flux. First, we demonstrate a relation between runoff, detrital sediment flux, and isotope values in the sediment trap record covering the period 2011–2013 CE including 22 events with daily (hourly) peak runoff ranging from 10 (24) m3 s−1 to 79 (110) m3 s−1. The three- to ten-fold lower flood-triggered detrital sediment deposition in the distal trap is well reflected by attenuated peaks in the stable isotope values of trapped sediments. Next, we show that all nine flood-triggered detrital layers deposited in a sediment record from 1988 to 2013 have elevated isotope values compared with endogenic calcite. In addition, even two runoff events that did not cause the deposition of visible detrital layers are distinguished by higher isotope values. Empirical thresholds in the isotope data allow estimation of magnitudes of the majority of floods, although in some cases flood magnitudes are overestimated because local effects can result in too-high isotope values. Hence we present a proof of concept for stable isotopes as reliable tool for reconstructing flood frequency and, although with some limitations, even for flood magnitudes

Holocene hydrological variability of Lake Ladoga, northwest Russia, as inferred from diatom oxygen isotopes

This article presents a new comprehensive assessment of the Holocene hydrological variability of Lake Ladoga, northwest Russia. The reconstruction is based on oxygen isotopes of lacustrine diatom silica (δ18Odiatom) preserved in sediment core Co 1309, and is complemented by a diatom assemblage analysis and a survey of modern isotope hydrology. The data indicate that Lake Ladoga has existed as a freshwater reservoir since at least 10.8 cal. ka BP. The δ18Odiatom values range from +29.8 to +35.0‰, and relatively higher δ18Odiatom values around +34.7‰ between c. 7.1 and 5.7 cal. ka BP are considered to reflect the Holocene Thermal Maximum. A continuous depletion in δ18Odiatom since c. 6.1 cal. ka BP accelerates after c. 4 cal. ka BP, indicating Middle to Late Holocene cooling that culminates during the interval 0.8–0.2 cal. ka BP, corresponding to the Little Ice Age. Lake‐level rises result in lower δ18Odiatom values, whereas lower lake levels cause higher δ18Odiatom values. The diatom isotope record gives an indication for a rather early opening of the Neva River outflow at c. 4.4–4.0 cal. ka BP. Generally, overall high δ18Odiatom values around +33.5‰ characterize a persistent evaporative lake system throughout the Holocene. As the Lake Ladoga δ18Odiatom record is roughly in line with the 60°N summer insolation, a linkage to broader‐scale climate change is likely