New-on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique

Mid- to late-Holocene archaeology, environment and climate in the northeast Kurdistan region of Iraq

This work presents new data from phytolith and speleothem analyses that cover the middle to late Holocene from northeastern Iraq in the Kurdistan region. Coupling these data with previous work, we demonstrate how the region’s environment and climate developed during a time when agriculture became not only established but settlements started to transform into larger urban areas. Results demonstrate a wetter phase during the middle Holocene relative to the present period; a highly seasonal climate with one rainy season is also suggested between 8025 ± 38 and 6977 ± 219 BP. Phytoliths not only suggest a relatively wet environment but they also indicate a diversity of plants used for settlement activity. Sedimentary results complement the indication of a relatively wetter middle Holocene. Archaeologically, terraced construction found in Gurga Chiya and the presence of drought tolerant crops suggest adaptation to stronger, seasonal rains and seasonal droughts in the middle Holocene. Sedimentary, phytolith, and speleothem results suggest relatively drier late-Holocene conditions, although the region continued to be conducive for rainfed agriculture

Moisture and Seasonality Shifts Recorded in Holocene and Pleistocene Speleothems From Southeastern Arabia

The source and seasonality of rainfall in southern Arabia during the early- to mid-Holocene and preceding humid periods are controversial because fossil lacustrine sediments provide solely indirect information on the amount of rainfall. Hydrogen and oxygen isotope measurements on fluid inclusion water trapped in Holocene and Pleistocene stalagmites from Hoti Cave in Northern Oman are direct indicators of the isotopic composition of paleoprecipitation. Isotope values of fluid inclusions formed during peak interglacial periods plot along monsoonal water lines and are indicative of a southern monsoonal moisture source. The last monsoon-dominated period lasting from ∼10,100 to 6,300 years before present was terminated within a few decades in southeastern Arabia. The subsequent reduction in rainfall amount and change from predominantly summer to predominantly winter rainfall had a profound impact on human communities living in this area and triggered migration from inland to coastal areas where resources were more abundant

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

Stalagmite water content as a proxy for drip water supply in tropical and subtropical areas

In this pilot study water was extracted from samples of two Holocene stalagmites from Socotra Island, Yemen, and one Eemian stalagmite from southern continental Yemen. The amount of water extracted per unit mass of stalagmite rock, termed "water yield" hereafter, serves as a measure of its total water content. Based on direct correlation plots of water yields and δ18Ocalcite and on regime shift analyses, we demonstrate that for the studied stalagmites the water yield records vary systematically with the corresponding oxygen isotopic compositions of the calcite (δ18Ocalcite). Within each stalagmite lower δ18Ocalcite values are accompanied by lower water yields and vice versa. The δ18Ocalcite records of the studied stalagmites have previously been interpreted to predominantly reflect the amount of rainfall in the area; thus, water yields can be linked to drip water supply. Higher, and therefore more continuous drip water supply caused by higher rainfall rates, supports homogeneous deposition of calcite with low porosity and therefore a small fraction of water-filled inclusions, resulting in low water yields of the respective samples. A reduction of drip water supply fosters irregular growth of calcite with higher porosity, leading to an increase of the fraction of water-filled inclusions and thus higher water yields. The results are consistent with the literature on stalagmite growth and supported by optical inspection of thin sections of our samples. We propose that for a stalagmite from a dry tropical or subtropical area, its water yield record represents a novel paleo-climate proxy recording changes in drip water supply, which can in turn be interpreted in terms of associated rainfall rates

Orbital and millenial-scale environmental changes between 64 and 25 ka BP recorded in Black Sea sediments

High-resolution pollen and dinoflagellate cyst records from sediment core M72/5-25-GC1 were used to reconstruct vegetation dynamics in northern Anatolia and surface conditions of the Black Sea between 64 and 20 ka BP. During this period, the dominance of Artemisia in the pollen record indicates a steppe landscape and arid climate conditions. However, the concomitant presence of temperate arboreal pollen suggests the existence of glacial refugia in northern Anatolia. Long-term glacial vegetation dynamics reveal two major arid phases ~64–55 and 40–32 ka BP, and two major humid phases ~54–45 and 28–20 ka BP, correlating with higher and lower summer insolation, respectively. Dansgaard–Oeschger (D–O) cycles are clearly indicated by the 25-GC1 pollen record. Greenland interstadials are characterized by a marked increase in temperate tree pollen, indicating a spread of forests due to warm/wet conditions in northern Anatolia, whereas Greenland stadials reveal cold and arid conditions as indicated by spread of xerophytic biomes. There is evidence for a phase lag of ~500 to 1500 yr between initial warming and forest expansion, possibly due to successive changes in atmospheric circulation in the North Atlantic sector. The dominance of Pyxidinopsis psilata and Spiniferites cruciformis in the dinocyst record indicates brackish Black Sea conditions during the entire glacial period. The decrease of marine indicators (marine dinocysts, acritarchs) at ~54 ka BP and increase of freshwater algae (Pediastrum, Botryococcus) from 32 to 25 ka BP reveals freshening of the Black Sea surface water. This freshening is possibly related to humid phases in the region, to connection between Caspian Sea and Black Sea, to seasonal freshening by floating ice, and/or to closer position of river mouths due to low sea level. In the southern Black Sea, Greenland interstadials are clearly indicated by high dinocyst concentrations and calcium carbonate content, as a result of an increase in primary productivity. Heinrich events show a similar impact on the environment in the northern Anatolia/Black Sea region as Greenland stadials

Noble gas based temperature reconstruction on a Swiss stalagmite from the last glacial–interglacial transition and its comparison with other climate records

Here we present the results of a first application of a “Combined Vacuum Crushing and Sieving (CVCS)” system to determine past (cave / soil) temperatures from dissolved noble gas concentrations in stalagmite samples grown under ‘cold’ climatic conditions (e.g. close to freezing point of water) during the last glacial-interglacial transition. To establish noble gas temperatures (NGTs) also for stalagmites grown in cold regions, we applied the CVCS system to samples from stalagmite M2 precipitated in the Milandre Cave, located in the Swiss Jura Mountains. The investigated stalagmite M2 covers the Allerød – Younger Dryas – Holocene transitions. Noble gas temperatures are determined by using a new algorithm based on noble gas and water abundances and not from concentrations. Noble gas results indicate annual mean temperatures in the Milandre Cave were 2.2 ± 1.8 °C during the late stages of the Allerød, then dropping to 〖0 〗_((-))^( +) 2.6 °C at the onset of the Younger Dryas. Such temperatures indicate conditions near to the freezing point of water during the first part of the Younger Dryas. During the last part of the Younger Dryas, the temperature increased to 6.3 ± 2.3 °C. No early Holocene temperature could be determined due the non-detectable water abundances in these samples, however one late Holocene sample indicates a cave temperature of 8.7 ± 2.7 °C which is close to the present day annual mean temperature. NGTs estimated for the Allerød – Younger Dryas – Holocene are in good agreement with paleo-temperature reconstructions from geochemical and biological proxies in lake sediments. The observed deviations between the different paleo-temperature reconstructions are minor if the according temperatures are rescaled to annual mean temperatures and are primarily attributed to the chronological tuning of the different records. As in other stalagmites, NGT reconstructions of the recently precipitated stalagmite (‘young’) samples again are biased, most likely due to diffusive gas loss during sample processing. We speculate that a reduced retentivity of noble gases during experimental sample processing is a general feature of recently precipitated stalagmite fabrics. Therefore, the recently precipitated stalagmite samples do not allow the reliable NGT determination given the currently available experimental methods. Nevertheless, this study makes the case that noble gas thermometry can be applied to stalagmites for physically based paleo-temperature reconstruction, also for stalagmites grown during cold climatic conditions

Sulfate and molybdate incorporation at the calcite–water interface: insights from ab initio molecular dynamics

Sulfur and molybdenum trace impurities in speleothems (stalagmites and stalactites) can provide long and continuous records of volcanic activity, which are important for past climatic and environmental reconstructions. However, the chemistry governing the incorporation of the trace element-bearing species into the calcium carbonate phases forming speleothems is not well understood. Our previous work has shown that substitution of tetrahedral oxyanions [XO4]2– (X = S and Mo) replacing [CO3]2– in CaCO3 bulk phases (except perhaps for vaterite) is thermodynamically unfavorable with respect to the formation of competing phases, due to the larger size and different shape of the [XO4]2– tetrahedral anions in comparison with the flat [CO3]2– anions, which implied that most of the incorporation would happen at the surface rather than at the bulk of the mineral. Here, we present an ab initio molecular dynamics study, exploring the incorporation of these impurities at the mineral–water interface. We show that the oxyanion substitution at the aqueous calcite (10.4) surface is clearly favored over bulk incorporation, due to the lower structural strain on the calcium carbonate solid. Incorporation at surface step sites is even more favorable for both oxyanions, thanks to the additional interface space afforded by the surface line defect to accommodate the tetrahedral anion. Differences between sulfate and molybdate substitutions can be mostly explained by the size of the anions. The molybdate oxyanion is more difficult to incorporate in the calcite bulk than the smaller sulfate oxyanion. However, when molybdate is substituted at the surface, the elastic cost is avoided because the oxyanion protrudes out of the surface and gains stability via the interaction with water at the interface, which in balance results in more favorable surface substitution for molybdate than for sulfate. The detailed molecular-level insights provided by our calculations will be useful to understand the chemical basis of S- and Mo-based speleothem records

Interpreting lake isotope records of Holocene environmental change in the Eastern Mediterranean

Oxygen isotope records from lake sediment archives are becoming an increasingly common tool for palaeoenvironmental reconstruction. We discuss their interpretation in the Eastern Mediterranean region with particular reference to three records, Zeribar, Van and Eski Acıgöl during the Holocene. The latter two records have been interpreted as controlled by changes in the precipitation to evaporation ratio, and the first due to changes in precipitation seasonality. In light of recent isotope work in the region and comparison with other proxy data from the same lakes, we show both of these initial interpretations to be oversimplified. Careful interpretations of complex lake isotope systems are therefore required in order that palaeoclimatic inferences are drawn correctly

Evidence for solar cycles in a late Holocene speleothem record from Dongge Cave, China

The association between solar activity and Asian monsoon (AM) remains unclear. Here we evaluate the possible connection between them based on a precisely-dated, high-resolution speleothem oxygen isotope record from Dongge Cave, southwest China during the past 4.2 thousand years (ka). Without being adjusted chronologically to the solar signal, our record shows a distinct peak-to-peak correlation with cosmogenic nuclide 14C, total solar irradiance (TSI) and sunspot number (SN) at multi-decadal to centennial timescales. Further cross-wavelet analyses between our calcite δ18O and atmospheric 14C show statistically strong coherence at three typical periodicities of ~80, 200 and 340 years, suggesting important roles of solar activities in modulating AM changes at those timescales. Our result has further indicated a better correlation between our calcite δ18O record and atmospheric 14C than between our record and TSI. This better correlation may imply that the Sun–monsoon connection is dominated most likely by cosmic rays and oceanic circulation (both associated to atmospheric 14C), instead of the direct solar heating (TSI)