High-resolution isotopic monitoring of cave air CO2.

RATIONALE: CO2 is the main driver of many chemical processes in cave environments. Understanding CO2 fluxes in a given cave system through monitoring campaigns has become a standard procedure in a wide variety of fields such as paleoclimatology or show cave management. However, conventional methods lack the resolution of isotopic data to capture many transient processes occurring in caves. METHODS: A novel approach using isotope ratio infrared spectrometry (IRIS) to monitor cave air pCO2 , δ13 C and δ18 O values in situ was tested and compared with conventional monitoring methods (handheld pCO2 meter and discrete cave air samples for conventional isotope ratio mass spectrometry). This also involved the development of a field-deployable experimental setup to operate the equipment in rough cave environments. RESULTS: Comparison between data obtained by means of a Thermo Fisher Scientific Delta Ray IRIS instrument shows overall good agreement with conventional monitoring methods in terms of pCO2 and δ13 C values. In addition, IRIS allows the δ18 O values of cave air CO2 to be measured. CONCLUSIONS: IRIS allows identification and tracking of processes at various timescales ranging from transient visitor impact on the cave atmosphere to seasonal trends in cave ventilation. However, the need for an uninterrupted power supply (110/220 V AC) and the relatively large dimensions of the equipment (698 × 1092 × 704 mm, 80 kg) limit the number of caves where deployment of the instrument is feasible. Copyright © 2017 John Wiley & Sons, Ltd.

Geothermometry of calcite spar at 10-50 °C.

Carbonate geothermometry is a fundamental tool for quantitative assessment of the geothermal and geochemical evolution of diagenetic and hydrothermal systems, but it remains difficult to obtain accurate and precise formation temperatures of low-temperature calcite samples (below ~ 40 to 60 °C). Here, we apply three geothermometry methods (∆47-thermometry, nucleation-assisted fluid inclusion microthermometry-hereafter NA-FIM-and oxygen isotope thermometry) to slow-growing subaqueous calcite spar samples to cross-validate these methods down to 10 °C. Temperatures derived by NA-FIM and Δ47-thermometry agree within the 95% confidence interval, except for one sample. Regression analyses suggest that the real uncertainty of ∆47-thermometry exceeds the 1 SE analytical uncertainty and is around ± 6.6 °C for calcite spar that formed at 10-50 °C. The application of δ18O thermometry was limited to a few samples that contained sufficient primary fluid inclusions. It yielded broadly consistent results for two samples with two other geothermometers, and showed higher temperature for the third spar. We also found that calcite with steep rhombohedral morphologies is characteristic of low temperatures (11-13 °C), whereas blunt rhombohedra prevail in the 10-29 °C domain, and the scalenohedral habit dominates > 30 °C. This suggests that the calcite crystal morphology can be used to qualitatively distinguish between low- and higher-temperature calcite.

A 350,000-year history of groundwater recharge in the southern Great Basin, USA.

Estimating groundwater recharge under various climate conditions is important for predicting future freshwater availability. This is especially true for the water-limited region of the southern Great Basin, USA. To investigate the response of groundwater recharge to different climate states, we calculate the paleo recharge to a groundwater basin in southern Nevada over the last 350,000 years. Our approach combines a groundwater model with paleo-water-table data from Devils Hole cave. The minimum water-table during peak interglacial conditions was more than 1.6 m below modern levels, representing a recharge decline of less than 17% from present-day conditions. During peak glacial conditions, the water-table elevation was at least 9.5 m above modern levels, representing a recharge increase of more than 233-244% compared to present-day conditions. The elevation of the Devils Hole water-table is 3-4 times more sensitive to groundwater recharge during dry interglacial periods, compared to wet glacial periods. This study can serve as a benchmark for understanding long-term effects of past and future climate change on groundwater resources.

Combined use of conventional and clumped carbonate stable isotopes to identify hydrothermal isotopic alteration in cave walls.

Alteration of conventional carbonate stable isotopes (δ18O, δ13C) in cave walls has been shown to be a useful tool to identify cave formation driven by deep-seated processes, i.e., hypogene karstification. If combined with a prior information on the paleowater stable isotope composition, further insights can be obtained on the temperature and the source of the paleowater. Clumped isotope composition (Δ47) of carbonates is an independent measurement of temperature, and if combined with the conventional stable isotopes, can provide information on the paleowater stable isotope composition. On the example of Provalata Cave (N. Macedonia), we apply for the first time, both conventional and clumped stable isotope analysis, and identify two different isotope alteration trends, reflecting two distinct hydrothermal events: an older, hotter one, where isotope alteration was likely related to isotope diffusion, lowering the δ18O values of the carbonate; and a younger one, related to the cave formation by low-temperature CO2-rich thermal waters, with dissolution-reprecipitation as the alteration mechanism, causing decrease in δ18O values, and unexpected increase in δ13C values. The findings are further corroborated by additional insight from optical petrography and cathodoluminescence microscopy, as well as fluid inclusion analysis of secondary calcite crystals related to the cave forming phase.

230Th dating of flowstone from Ignatievskaya Cave, Russia: Age constraints of rock art and paleoclimate inferences.

Paleolithic antiquity of parietal art in Ignatievskaya cave, Southern Ural, is supported by its subject (Late Pleistocene animals) as well as by paleontological and palynological data, and 14C dates from cultural layers associated with artistic activity (17.8-16.3 cal ka BP; association is established by finds of ochre in these layers). However, three 14C dates of charcoal motifs yielded younger, Holocene ages (7.4-6.0 cal ka BP). In this study, we constrain the age of parietal art in the cave by 230Th dating of flowstone that brackets the paintings. Flowstone did not form in the cave between c. 78 and 10 ka BP, due to widespread permafrost in northern Eurasia at that time. Our 230Th dates do not support the middle Holocene age of art in Ignatievskaya cave and are consistent with its Upper Paleolithic antiquity instead.

Hydrogen and oxygen isotopes of water from inclusions in minerals: design of a new crushing system and on-line continuous-flow isotope ratio mass spectrometric analysis.

An analytical line for stable isotope analyses of water recovered from fluid inclusions in minerals was built and successfully tested. The line is based on the principle of continuous-flow analysis of water via high-temperature reduction on glassy carbon. It includes a custom-designed set of high-efficiency crushers and a cryo-focusing cell. This paper provides details of the line design and discusses strategies for line conditioning and mitigation of memory effects. The line allows measurements of hydrogen and oxygen isotopes during a single acquisition. The precision of the analyses depends on the amount of water released from the inclusions. The best results are obtained for samples containing at least 0.1-0.2 microL (0.06-0.11 micromol) H(2)O. For such samples precision is better than 1.5 per thousand for deltaD and 0.5 per thousand for delta(18)O (1sigma). Smaller amounts of water can be measured but at lower precision. Analyses of modern calcite formed under stable conditions in a deep cave allowed assessment of the accuracy of the analyses. The deltaD values measured in fluid inclusions of this working standard match the deltaD value of the parent water, and the oxygen isotope values agree within ca. 0.5 per thousand. This indicates that fluid inclusions trapped in calcite at near-ambient temperatures (e.g. speleothems and low-temperatures phreatic calcite) faithfully preserve the original isotopic composition of the parent waters.

Groundwater of the Crimean peninsula: a first systematic study using stable isotopes.

Karst springs in the Main Range of the Crimean Mountains and the Crimean Piedmont show a restricted range of values (δ18O = -10.5 to -8.0 ‰, δ2H = -72 to -58 ‰), somewhat more negative than the weighted mean of meteoric precipitation. This suggests preferential recharge at higher elevations during winter months. Groundwater tapped by boreholes splits in three groups. A first group has isotopic properties similar to those of the springs. The second group shows significantly lower values (δ18O = -13.3 to -12.0 ‰, δ2H = -95 to -82 ‰), suggesting recharge during colder Pleistocene times. The third group has high isotope values (δ18O = -2.5 to +1.0 ‰, δ2H = -24 to -22 ‰); the data points are shifted to the right of the Local Meteoric Water Line, suggesting water-rock exchange processes in the aquifer. These boreholes are located in the Crimean Plains and discharge mineralized (ca. 25 g L-1) thermal (65°C) water from a depth of 1600-1800 m. Groundwater associated with mud volcanoes on the Kerch peninsula have distinct isotope characteristics (δ18O = -1.6 to +9.4 ‰, δ2H = -30 to -18 ‰). Restricted δ2H variability along with variable and high δ18O values suggest water-rock interactions at temperatures exceeding 95 °C.

Data on the 14C date obtained from the charcoal figure "Black fox" in Shulgan-Tash (Kapova) cave, Southern Ural, Russia.

Shulgan-Tash (Kapova) cave in southern Ural, Russia, is the easternmost European site hosting Late Paleolithic cave art. Most of the 195+ drawings catalogued in the cave are made with red natural pigment (ochre), and only a handful of drawings are made with charcoal, see "Catalogue of images" [4], "Höhlenmalerei im Ural: Kapova und Ignatievka; die altsteinzeitlichen Bilderhöhlen im sudlichen Ural," [5]. "Constraining the ages of the Late Palaeolithic cave paintings in the Shulgan-Tash cave, Southern Urals, Russia" [6]. None of the charcoal drawings were directly dated by 14C method so far. Black lines delineating a figure similar to the outline of a fox are known in the cave. Here we present data on the 14C AMS date of charcoal with which the lines were drawn. Calibration of the data was performed using the Bomb13NH1 dataset, see "Atmospheric radiocarbon for the period 1950-2010" [7] and the IntCal13 dataset, see "IntCal13 and Marine13 radiocarbon age calibration curves 0-50,000 years cal BP" [8]. The calibrated age distribution has maximum probability density (65.3%) between 1877 and 1918.

Moisture availability in the southwest United States over the last three glacial-interglacial cycles.

The projected long-term drying of the southwest (SW) United States in response to climate warming raises a sobering alarm for this already water-limited region, yet the climatic controls on moisture availability over longer time scales remain a topic of debate. Here, we present a 350,000-year record of past water table fluctuations in Devils Hole 2 cave that are driven by variations in recharge amount to the local groundwater flow system. Because of the unprecedented length and precision of our record, we can observe variations in regional moisture availability over the last three glacial-interglacial cycles at a millennial-scale resolution. The timing of past water table rises and falls (>9 m in amplitude) closely coincides with the expansion and reduction of Northern Hemisphere ice volume, which in turn influences the position and intensity of westerly winter storms on orbital time scales. Superimposed on this long-term trend are millennial-scale highstands recorded during the last glaciation that coincide with North Atlantic Heinrich events. Earlier millennial-scale highstands provide the first evidence of multiple short-lived wet periods in the SW United States linked to coeval cooling intervals in the North Atlantic during marine isotope stages 6 and 8. The Devils Hole 2 water table record is currently the longest independently dated paleomoisture record in the SW United States and thus provides a critical testbed to examine the controls on regional moisture availability over larger time scales.

Late Palaeolithic cave art and permafrost in the Southern Ural.

Shulgan-Tash (also known as Kapova) cave located on the western slope of the Ural Mountains (Russia) is the easternmost European cave art monument of late Palaeolithic age. Radiocarbon dates from cultural layers in the cave suggest an age of about 16.3 to 19.6 ka (cal BP), but dates directly on the paintings were not obtained. In order to constrain the age of this art using an independent method, we performed detailed 230Th-U dating of calcite flowstone underlying and overgrowing the paintings at 22 sites in three halls of the cave. The youngest age for the underlying calcite (i.e., the maximum age of the cave art) is 36.4 ± 0.1 ka, and the oldest overlying calcite (constraining the minimum age of the cave art) is 14.5 ± 0.04 ka. The ca. 21.9 ka-long hiatus in calcite deposition during which the paintings were made is attributed to regional permafrost conditions and sub-zero temperatures inside the cave during Marine Isotope Stage (MIS) 2. This is supported by samples of cryogenic cave calcite, which document seven episodes of freezing and thawing of permafrost associated with stadials and interstadials of MIS 3, respectively.

Response to Comments on "Reconciliation of the Devils Hole climate record with orbital forcing".

Winograd and Coplen question the thorium-230 distribution model proposed to explain the age bias observed with increasing depth during Termination II. We have evaluated both criticisms and find that all samples display virtually identical fabrics, argue that the modern setting is not analogous to the conditions during Termination II, and reiterate the robustness of our age models. Our conclusions remain unchanged.

Reconciliation of the Devils Hole climate record with orbital forcing.

The driving force behind Quaternary glacial-interglacial cycles and much associated climate change is widely considered to be orbital forcing. However, previous versions of the iconic Devils Hole (Nevada) subaqueous calcite record exhibit shifts to interglacial values ~10,000 years before orbitally forced ice age terminations, and interglacial durations ~10,000 years longer than other estimates. Our measurements from Devils Hole 2 replicate virtually all aspects of the past 204,000 years of earlier records, except for the timing during terminations, and they lower the age of the record near Termination II by ~8000 years, removing both ~10,000-year anomalies. The shift to interglacial values now broadly coincides with the rise in boreal summer insolation, the marine termination, and the rise in atmospheric CO2, which is consistent with mechanisms ultimately tied to orbital forcing.

Commentary: assessment of past infiltration fluxes through Yucca Mountain on the basis of the secondary mineral record-is it a viable methodology?

Two papers recently published in the Journal of Contaminant Hydrology by Marshall et al. [Marshall, B.D., Neymark, L.A., Peterman, Z.E., 2003. Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada. J. Contam. Hydrol. 62-63, 237-247] and Xu et al. [Xu, T., Sonnenthal, E., Bodvarsson, G., 2003. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock. J. Contam. Hydrol. 64, 113-127] attempt to assess past volumes of seepage and infiltration fluxes through the vadose zone of Yucca Mountain, Nevada, on the basis of the modeling of the spatial distribution of secondary calcite. In this commentary, we argue that the employed methodology is not viable. In addition, the thermal boundary conditions used in simulations do not correspond to the temperatures of the mineral forming fluids established on the basis of the fluid inclusion studies.

Analysis of the treatment, by the U.S. Department of Energy, of the FEP hydrothermal activity in the Yucca Mountain Performance Assessment.

The U.S. Code of Federal Regulations, 10 CFR Part 63, stipulates that the expected performance of the geological high-level nuclear waste repository must be demonstrated through a total system performance assessment (TSPA). The TSPA represents an analysis that identifies all features, events, and processes (FEPs) that might affect the disposal system and examines the effects of the identified FEPs upon the performance of the system. Secondary minerals from the thick unsaturated zone of Yucca Mountain were deposited from waters with temperatures up to 70-90 degrees C. U-Pb dating constrained the ages of the elevated temperatures to the period between 10 and 5-6 million years ago. Relatively youthful circulation of thermal waters (hydrothermal activity) would be of concern for the safety of the disposal facility. A phenomenological model was advanced by the U.S. Department of Energy (DOE), which proposed that the minerals were deposited by infiltrating meteoric waters that were heated upon contact with the bedrock; it was hypothesized that the latter was conductively heated by a shallow silicic magma body. The model rendered processes responsible for elevated water temperatures inconsequential for the safety of the proposed nuclear waste facility. However, attempts by DOE at validating the model by means of numeric thermal simulations and analogue system observations were unsuccessful. Regulations specify two criteria for exclusion of a FEP from consideration in the TSPA: low probability and low consequence. The lack of a plausible phenomenological model makes it impossible to apply either of these two criteria to the FEP Hydrothermal Activity. Despite the lack of a valid criterion for exclusion, it was excluded from the TSPA. Both the development of DOE's thermal model and the formal FEP analysis were associated with deviations from DOE's quality assurance regulations.