Liquid-vapour homogenisation of fluid inclusions in stalagmites: Evaluation of a new thermometer for paleoclimate research

We present a new approach to determine palaeotemperatures (mean annual surface temperatures) based on measurements of the liquid–vapour homogenisation temperature of fluid inclusions in stalagmites. The aim of this study is to explore the potential and the limitations of this new palaeothermometer and to develop a reliable methodology for routine applications in palaeoclimate research. Therefore, we have investigated recent fluid inclusions from the top part of actively growing stalagmites that have formed at temperatures close to the present-day cave air temperature. A precondition for measuring homogenisation temperatures of originally monophase inclusions is the nucleation of a vapour bubble by means of single ultra-short laser pulses. Based on the observed homogenisation temperatures (Th(obs)) and measurements of the vapour bubble diameter at a known temperature, we calculated stalagmite formation temperatures (Tf) by applying a thermodynamic model that takes into account the effect of surface tension on liquid–vapour homogenisation. Results from recent stalagmite samples demonstrate that calculated stalagmite formation temperatures match the present-day cave air temperature within ± 0.2 °C. To avoid artificially induced changes of the fluid density we defined specific demands on the selection, handling and preparation of the stalagmite samples. Application of the method is restricted to stalagmites that formed at cave temperatures greater than ~ 9–11 °C.

The coupled δ13C-radiocarbon systematics of three Late Glacial/early Holocene speleothems: insights into soil and caveprocesses at climatic transitions

The coupled δ13C-radiocarbon systematics of threeEuropean stalagmites deposited during the Late Glacial and early Holocene were investigated to understand better how the carbon isotope systematics of speleothems respond to climate transitions. The emphasis is on understanding how speleothems may record climate-driven changes in the proportions of biogenic (soil carbon) and limestone bedrock derived carbon. At two of the three sites, the combined δ13C and 14C data argue against greater inputs of limestone carbon as the sole cause of the observed shift to higher δ13C during the cold Younger Dryas. In these stalagmites (GAR-01 from La Garma cave, N. Spain and So-1 from Sofular cave, Turkey), the combined changes in δ13C and initial 14C activities suggest enhanced decomposition of old stored, more recalcitrant, soil carbon at the onset of the warmer early Holocene. Alternative explanations involving gradual temporal changes between open- and closed-system behaviour during the Late Glacial are difficult to reconcile with observed changes in speleothem δ13C and the growth rates. In contrast, a stalagmite from Pindal cave (N. Spain) indicates an abrupt change in carbon inputs linked to local hydrological and disequilibrium isotope fractionation effects, rather than climate change. For the first time, it is shown that while the initial 14C activities of all three stalagmites broadly follow the contemporaneous atmospheric 14C trends (the Younger Dryas atmospheric 14C anomaly can be clearly discerned), subtle changes in speleothem initial 14C activities are linked to climate-driven changes in soil carbon turnover at a climate transition.

Pleistocene water intrusions from the Mediterranean and Caspian Seas into the Black Sea

The hydrological balance of the Black Sea is governed by riverine input and by the exchange with the Mediterranean Sea. A speleothem record from a cave in northern Turkey that tracks the isotopic signature of Black Sea surface water suggests an open connection to the Mediterranean Sea in at least twelve periods in the past 670,000 years.

Holocene and Pleistocene pluvial periods in Yemen, Southern Arabia

Arabia is an important potential pathway for the dispersal of Homo sapiens (“out of Africa”). Yet, because of its arid to hyper-arid climate humans could only migrate across southern Arabia during pluvial periods when environmental conditions were favorable. However, knowledge on the timing of Arabian pluvial periods prior to the Holocene is mainly based on a single and possibly incomplete speleothem record from Hoti Cave in Northern Oman. Additional terrestrial records from the Arabian Peninsula are needed to confirm the Hoti Cave record. Here we present a new speleothem record from Mukalla Cave in southern Yemen. The Mukalla Cave and Hoti Cave records clearly reveal that speleothems growth occurred solely during peak interglacial periods, corresponding to Marine Isotope Stages (MIS) 1 (early to mid-Holocene), 5.1, 5.3, 5.5 (Eemian), 7.1, 7.5 and 9. Of these humid periods, highest precipitation occurred during MIS 5.5 and lowest during early to middle Holocene.

Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

Choosing the most suitable analogue redesign method for forward-type digital power converters

This work proposes a method to objectively determine the most suitable analogue redesign method for forward type converters under digital voltage mode control. Particular emphasis is placed on determining the method which allows the highest phase margin at the particular switching and crossover frequencies chosen by the designer. It is shown that at high crossover frequencies with respect to switching frequency, controllers designed using backward integration have the largest phase margin; whereas at low crossover frequencies with respect to switching frequency, controllers designed using bilinear integration have the largest phase margins. An accurate model of the power stage is used for simulation, and experimental results from a Buck converter are collected. The performance of the digital controllers is compared to that of the equivalent analogue controller both in simulation and experiment. Excellent correlation between the simulation and experimental results is presented. This work will allow designers to confidently choose the analogue redesign method which yields the greater phase margin for their application.

New age estimates for the Palaeolithic assemblages and Pleistocene succession of Casablanca, Morocco

Marine and aeolian Quaternary sediments from Casablanca, Morocco were dated using the optically stimulated luminescence (OSL) signal of quartz grains. These sediments form part of an extensive succession spanning the Pleistocene, and contain a rich faunal and archaeological record, including an Acheulian lithic assemblage from before the Brunhes–Matayama boundary, and a Homo erectus jaw from younger cave deposits. Sediment samples from the sites of Reddad Ben Ali, Oulad J’mel, Sidi Abderhamane and Thomas Quarries have been dated, in order to assess the upper limits of OSL. The revision of previously measured mammalian tooth enamel electron spin resonance (ESR) dates from the Grotte des Rhinocéros, Oulad Hamida Quarry 1, incorporating updated environmental dose rate measurements and attenuation calculations, also provide chronological constraint for the archaeological material preserved at Thomas Quarries. Several OSL age estimates extend back to around 500,000 years, with a single sample providing an OSL age close to 1 Ma in magnetically reversed sediments. These luminescence dates are some of the oldest determined, and their reliability is assessed using both internal criteria based on stratigraphic consistency, and external lithostratigraphic, morphostratigraphic and independent chronological constraints. For most samples, good internal agreement is observed using single aliquot regenerative-dose OSL measurements, while multiple aliquot additive-dose measurements generally have poorer resolution and consistency. Novel slow-component and component-resolved OSL approaches applied to four samples provide significantly enhanced dating precision, and an examination of the degree of signal zeroing at deposition. A comparison of the OSL age estimates with the updated ESR dates and one U-series date demonstrate that this method has great potential for providing reliable age estimates for sediments of this antiquity. We consider the cause of some slight age inversion observed at Thomas Quarries, and provide recommendations for further luminescence dating within this succession.

Terahertz pulse investigation of paleolithic wall etchings

Results are presented of an examination of flow rock-covered Paleoloithic cave art using time-domain terahertz reflectometry.

Diet and lifestyle in Bronze Age Northwest Spain: the collective burial of Cova do Santo

A multidisciplinary investigation of the collective burial of Cova do Santo is presented as a novel approach to understand daily life during the Bronze Age in Northwest Iberia. The research is focused on three main aspects: i) taphonomy and patterns of disposal, ii) paleopathology and -demography as indicators of health status and lifestyle, and iii) stable isotope analysis to reconstruct paleodiet and to investigate the timing of the introduction of millet to the Iberian Peninsula. Osteological analyses were performed on 64 bones (61 human and 3 animal); additionally, bone collagen was extracted from 15 samples (13 human and 2 animal) and analyzed for its carbon and nitrogen stable isotopes composition. The radiocarbon age of the human remains is consistent with the Middle Bronze Age (c. 1890 to 1600 cal BC). The recovered remains belonged to a minimum number of 14 individuals with an estimated age at death of forty years or younger. This relatively young age is in contrast to a high prevalence of degenerative joint disease in the group. The isotopic results suggest a very homogeneous diet, which was almost exclusively based on C3 plants and terrestrial animal products. Overall, the data suggest that the studied population belonged to a period prior to the introduction of spring or summer-grown crops such as millets. The collective burial from the cave of Cova de Santo, Galicia, currently represents the largest assemblage of prehistoric human remains from Northwest Spain and the relatively good preservation of the bones offers a unique opportunity to investigate daily life in Northern Iberia during the Bronze Age.

Systematic selection of analogue redesign method for forward-type digital power converters

This article proposes a systematic approach to determine the most suitable analogue redesign method to be used for forward-type converters under digital voltage mode control. The focus of the method is to achieve the highest phase margin at the particular switching and crossover frequencies chosen by the designer. It is shown that at high crossover frequencies with respect to switching frequency, controllers designed using backward integration have the largest phase margin; whereas at low crossover frequencies with respect to switching frequency, controllers designed using bilinear integration with pre-warping have the largest phase margins. An algorithm has been developed to determine the frequency of the crossing point where the recommended discretisation method changes. An accurate model of the power stage is used for simulation and experimental results from a Buck converter are collected. The performance of the digital controllers is compared to that of the equivalent analogue controller both in simulation and experiment. Excellent closeness between the simulation and experimental results is presented. This work provides a concrete example to allow academics and engineers to systematically choose a discretisation method.

Speleothems as sensitive recorders of volcanic eruptions - the Bronze Age Minoan eruption recorded in a stalagmite from Turkey

Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621±251621±25 BC, whereas sulphur and molybdenum show peaks later at 1617±251617±25 and 1589±251589±25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey.

Technical note: how accurate can stalagmite formation temperatures be determined using vapour bubble radius measurements in fluid inclusions?

Stalagmites are natural archives containing detailed information on continental climate variability of the past. Microthermometric measurements of fluid inclusion homogenisation temperatures allow determination of stalagmite formation temperatures by measuring the radius of stable laser-induced vapour bubbles inside the inclusions. A reliable method for precisely measuring the radius of vapour bubbles is presented. The method is applied to stalagmite samples for which the formation temperature is known. An assessment of the bubble radius measurement accuracy and how this error influences the uncertainty in determining the formation temperature is provided. We demonstrate that the nominal homogenisation temperature of a single inclusion can be determined with an accuracy of ±0.25 °C, if the volume of the inclusion is larger than 105 μm3. With this method, we could measure in a proof-of-principle investigation that the formation temperature of 10–20 yr old inclusions in a stalagmite taken from the Milandre cave is 9.87 ± 0.80 °C, while the mean annual surface temperature, that in the case of the Milandre cave correlates well with the cave temperature, was 9.6 ± 0.15 °C, calculated from actual measurements at that time, showing a very good agreement. Formation temperatures of inclusions formed during the last 450 yr are found in a temperature range between 8.4 and 9.6 °C, which corresponds to the calculated average surface temperature. Paleotemperatures can thus be determined within ±1.0 °C.

Glacial-interglacial temperature change in the tropical West Pacific: a comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquid–vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O (‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glacial–interglacial cycles (Marine Isotope Stages (MIS) 12–9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquid–vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion δ18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion δ18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glacial–interglacial temperature change, indicating temperature shifts of 4–5 °C. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

A Lateglacial archaeological site in the far north-west of Europe at Rubha Port an t-Seilich, Isle of Islay, western Scotland: Ahrensburgian-style artefacts, absolute dating and geoarchaeology

The exact pattern, process and timing of the human re-colonization of northern Europe after the end of the last Ice Age remain controversial. Recent research has provided increasingly early dates for at least pioneer explorations of latitudes above 54°N in many regions, yet the far north-west of the European landmass, Scotland, has remained an unexplained exception to this pattern. Although the recently described Hamburgian artefacts from Howburn and an assemblage belonging to the arch-backed point complex from Kilmelfort Cave have established at least a sporadic human presence during earlier stages of the Lateglacial Interstadial, we currently lack evidence for Younger Dryas/Greenland Stadial 1 (GS-1) activity other than rare stray finds that have been claimed to be of Ahrensburgian affiliation but are difficult to interpret in isolation. We here report the discovery of chipped stone artefacts with technological and typological characteristics similar to those of the continental Ahrensburgian at a locality in western Scotland. A preliminary analysis of associated tephra, pollen and phytoliths, along with microstratigraphic analysis, suggest the artefacts represent one or more episodes of human activity that fall within the second half of GS-1 and the Preboreal period