Winter Wonderland Cave, Utah, USA: A Natural Laboratory for the Study of Cryogenic Cave Carbonate and Thawing Permafrost

doi:10.21203/rs.3.rs-114446/v1

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Winter Wonderland Cave, Utah, USA: A Natural Laboratory for the Study of Cryogenic Cave Carbonate and Thawing Permafrost

https://doi.org/10.21203/rs.3.rs-114446/v1

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published 19 Mar, 2021

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Winter Wonderland Cave contains perennial ice associated with two types of cryogenic cave carbonate (CCC) formed during the freezing of water. CCC_fine is characterized by relatively enriched δ¹³C values, whereas CCC_coarse exhibits notably depleted δ¹⁸O values indicating precipitation under (semi)closed-system conditions in a pool of residual water beneath an ice lid. Previous work has concluded that CCC_coarse forms during permafrost thaw, making the presence of this precipitate a valuable indicator of past cryospheric change. Available geochronologic evidence indicates that CCC formation in this cave is a Late Holocene or contemporary process, and field observations suggest that the cave thermal regime recently changed in a manner that permits the ingress of liquid water. This is the first documented occurence of CCC_coarse in the Western Hemisphere and one of only a few locations where these minerals have been found in association with ice. Winter Wonderland Cave is a natural laboratory for studying CCC genesis.

Geology

Atmospheric Sciences

CCC

cryogenic

Holocene

The cryosphere is responding rapidly to climate warming, and paleoclimate records are critical for understanding the novelty of these responses^1,2. A persistent challenge is that many paleoclimate archives are biased toward extremes, for instance the most extensive glacial advances³, most widespread periglacial conditions⁴, or sea level high- and low-stands⁵. Yet records of past climatic transition are crucial for placing contemporary global change into a longer-term context⁶. This is especially true in Arctic and high mountain environments where temperatures are warming rapidly^7,8, leading to dramatic diminishment of ice extent^9,10 and degradation of permafrost^11,12. Thus there is an urgent need for better records of how the cryosphere changed in the past, to clarify when and how rapidly changes occurred, and in what pattern these changes unfolded across the landscape.

A unique proxy demonstrated to provide information about past episodes of permafrost thaw, a transition that is often particularly disruptive to landscapes, ecosystems and infrastructure, is cryogenic cave carbonate (CCC). These minerals form when liquid water enters a cave containing subzero temperature conditions¹³. As this water freezes, solutes are concentrated in the remaining liquid until saturation is reached and precipitation of CCC is induced^14,15. Although seasonal subzero conditions can be created inside a cave entrance by winter cold, more significant permanently subzero conditions are maintained in so-called “ice caves” by ventilation regimes that preferentially allow the ingress of winter air while excluding summer warmth^16,17. For instance, caves with a single downward sloping entrance can trap cold air through density settling in winter; air that is not replaced by warmer, less dense air in the summer. Alternatively, caves with multiple entrances at different elevations are susceptible to chimney effects that support freezing conditions where large amounts of cold air are pulled into the cave in winter. Either way, CCC is precipitated when water containing sufficient dissolved solutes encounters the subzero conditions.

Two types of CCC have been identified. One group, referred to as CCC_fine, forms when a film of water freezes on the surface of pre-existing ice¹⁸. The large surface area of this thin layer facilitates degassing of CO₂, preferentially removing ¹²C, and leaving the remaining water enriched in ¹³C through kinetic effects^19,20. Simultaneously, the preferential incorporation of ¹⁸O in the ice is counterbalanced by evaporation of lighter H₂¹⁶O from the water surface, yielding a characteristically enriched δ¹³C and relatively unaltered δ¹⁸O signature¹⁸. The ice involved in the formation of CCC_fine does not need to be perennial, however the presence of CCC_fine in a currently ice-free cave is nonetheless clear evidence for colder conditions in the past.

In contrast, CCC_coarse is a more specific proxy because it forms when a descending permafrost table driven by permafrost thaw intersects the upper part of a cave, allowing dripwater to enter and form pools on the ice surface^21,22. Because the temperature in the main part of the cave (below the permafrost table) is still subzero, these pools freeze over, creating (semi)closed-system conditions in which degassing of CO₂ and evaporation of water are greatly reduced²¹. Slow freezing of these isolated volumes of water precipitates CCC_coarse distinguished by less enriched δ¹³C and notably depleted values of δ¹⁸O compared with CCC_fine^13,15,23. As is apparent throughout Arctic and high mountain environments today, elevation of ground temperature above 0°C, thawing of permafrost, and melting of ground ice are step-changes with dramatic repercussions for landscape and environmental evolution²⁴. CCC_coarse, therefore, is a critical proxy because it records past episodes of permafrost thaw.

Here we report the first discovery of CCC_coarse in North America from an unusual setting where apparently young CCC is present in association with modern perennial ice. Our work provides an important point of comparison for CCC from well-studied caves in Europe, and documents a setting in which theories for CCC genesis could be evaluated.

Location

The CCC studied in this project was collected from Winter Wonderland Cave (WWC) in the Uinta Mountains of northeastern Utah, USA (Fig. 1). This solution cave has developed in the Carboniferous-age Madison Limestone, a regionally extensive rock unit that in this area consists of fine to coarse-grained dolomite and limestone, with locally abundant nodules of chert²⁵. The entrance to WWC is at an elevation of 3140 m asl in a north-facing cliff at the edge of the karstified Blind Stream Plateau (40.53°N, 110.73°W), a sparsely forested subalpine landscape. The mean annual air temperature (1985-2020) at the Brown Duck snowpack telemetry (SNOTEL) station at a similar elevation (3223 m) 12 km to the east of WWC is 0.3°C (https://wcc.sc.egov.usda.gov/nwcc/site?sitenum=368). Elsewhere in the Uinta Mountains, the Chepeta remote automated weather station (RAWS) at an elevation of 3694 m recorded a mean temperature of -2.0°C between 2000 and 2019 (https://wrcc.dri.edu/cgi-bin/rawMAIN.pl?utCHEP). Inside WWC temperatures were consistently subzero from 2016-2018 because of a ventilation regime that brings cold winter air in through the main entrance, and inhibits the entry of warm air in the summer. As a result, about half of the cave, which has a mapped length of 245 m, is floored by perennial ice up to 3 m thick. CCC is present as a lag on the ice surface, drapes rocks emerging from the sublimating ice, and occurs as discrete layers within the ice body (Fig. 2a). Additional details about the cave and its climatology are presented in Munroe (2020).

Representative CCC samples, numbered YS-1 through YS-6 (Table S1) were collected from the ice surface along with three samples that were submerged in small (~10-30 cm deep) pools (Fig. 2b) of water filling depressions in the ice (CP, YP, and TF). Additional samples of Madison Limestone bedrock and water from pools were also collected for analysis.

CCC Morphology.

An array of morphologies is present in the CCC samples from WWC. The smallest size fractions are spherulitic, with large aggregates reaching diameters of 50 µm, and individual spherules from 10 to 20 µm in diameter (Fig. 2c). This observation is corroborated by results from laser scattering, which reveal mean grain sizes from 24 to 42 µm in the <75-µm fraction. Rounded grains are typically clumped in botryoidal aggregates with smooth surfaces, and dumbbell structures are common. Occasionally more sharp-edged morphologies are present, with needle-like points that rarely exceed 5 μm in length. Larger size fractions (250-75 μm) contain rafts of aggregated grains in excess of 200 μm long. The TF samples, which were collected from the water surface, are characterized by arrow-shaped blades 10 to 20 µm long, grouped into thin rafts (Fig. 2d). All of these observations match CCC morphologies reported in the literature. For instance, previous work has established that CCC often occurs as raft-like aggregates of crystals, and spherical forms^21,22,26. Rafts are generally flat and composed of interlocking crystals in a manner similar to floating carbonate minerals reported from non-cryogenic cave environments²⁷. Crystal splitting has been invoked as a mechanism for the growth of spherical forms²⁸, which are sometimes superimposed on a branching, sheaf-life skeleton²⁹. Finally, spherules are reported to display smooth surfaces, and often connect during growth to form dumbbell shapes²¹ or chains²².

On the other hand, the CCC in WWC is considerably finer than precipitates with similarly depleted δ¹⁸O values reported from European caves. Although there is a wide range in sizes, CCC is typically described as having crystals from <1 mm to ~40 mm^21,22,26 compared with the 10 to 20-µm diameter spherules common in WWC. The significance of this difference is unclear; it may simply indicate that CCC in WWC formed from smaller-volume pools, or from water with a lower total dissolved load.

Types of CCC Present in WWC. Although, as their names suggest, early studies differentiated CCC_fineand CCC_coarse by grain size, δ¹³C and δ¹⁸O data reflecting different C and O isotope fractionation mechanisms are now recognized as the only valid criteria for distinguishing between the two groups¹⁸. With this in mind, values of δ¹³C and δ¹⁸O indicate that both types of CCC are present in WWC (Fig. 3a). Samples YS-3 and YS-4 have δ¹³C averaging 6‰ and an average δ¹⁸O of -7.3‰ (Table S2), suggesting that both are CCC_fine. In contrast, samples YS-1, YS-2, YS-5, YS-6, CP, and YP have lower values of δ¹³C, averaging 3.5‰, and notably more depleted δ¹⁸O, averaging -16‰. These values identify these samples as CCC_coarse(Table S2). Sample TF also plots in the CCC_coarse field (Fig. 3a), although it was collected from a pool that had just begun to freeze, which may explain why its δ¹⁸O value is less depleted than the other CCC_coarse samples. For comparison, samples of the Madison Limestone collected in WWC have an average δ¹³C of 2.2‰ and δ¹⁸O of -5.9‰ (Fig. 3a). Consistency of stable isotope values within individual size fractions (250-165 µm, 165-75 µm, and <75 µm) emphasizes that YS-5, YS-6, CP, and YP are pure CCC_coarse (Fig. 3b). In YS-1 and YS-2, CCC_coarse is concentrated in the <75-µm fraction. In contrast, YS-4 is consistently CCC_fine in all size fractions.

The results of additional analyses permit further interpretation of these samples. XRD reveals that YS-3 and YS-4 (CCC_fine) are a mixture of calcite and quartz (Fig. S1), and rounded quartz grains were visible in the <250-µm size fraction. The presence of quartz is confirmed in the XRF results, where sample YS-4 contains 52% SiO₂ (Table S3)_. YS-3 and YS-4 also have much higher chondrite-normalized REE values (Table S4, Fig. S2). These observations, along with the isotope data for size fractions presented above, are evidence for a detrital component in these CCC_fine samples, which were collected from bedrock shelves above the current ice surface (Fig. 1). In contrast, XRD analysis indicates that the CCC_coarse samples are composed solely of calcite, as are the bedrock samples (Fig. S1). Major element analysis (Table S3) reinforces the abundance of calcite in YS-6 (70% as CaO), and Mg is considerably more abundant in YS-6 (12.2% as MgO) than in YS-4 (1.8%). Collectively the mineralogical and geochemical analyses support the conclusion from the isotope results that both CCC_coarse and CCC_fine are present in WWC.

CCC Ages. Previous studies have successfully applied ²³⁰Th/²³⁴U disequilibrium dating²⁶ to CCC¹⁵. Accordingly, an attempt was made to date CCC_coarse from WWC (Table S5). The resulting ages are imprecise due to low ²³⁰Th/²³²Th ratios, a situation that has complicated other work^22,26, meaning that the correction for detrital ²³⁰Th, and the uncertainty on that correction, are large. On the other hand, one of the samples analyzed (TF) is clearly modern because it was collected in 2018 from a pool of water that was not present in 2016. The initial ²³⁰Th/²³²Th for this sample was, therefore, applied to the others (with a 25% 2-σ uncertainty) to refine the age calculations. Results indicate that the CCC in WWC likely formed during the Holocene, and nearly all of the ages have error estimates that overlap with modern (Table S5, Fig. S3). Thus these ages, imprecise as they are, are consistent with CCC formation as a recent or current process in WWC. This result is significant because the majority of published CCC ages are from the Late Pleistocene^{e.g. 21,30}, with only a few reports of Holocene ages^22,26,31.

Two additional lines of evidence support the interpretation that the CCC in WWC is young. First, rafts of calcite from sample YS-6 yielded a radiocarbon result of f_Modern 1.111 ± 0.005, consistent with formation in the late 20^th Century when calibrated with the NH1 bomb curve in Oxcal 4.4³² (Fig. S4). Second, samples of rodent fecal pellets from the ice beneath the surface lag of CCC yielded radiocarbon ages that calibrate to between AD 1600 and 1850³³ using the IntCal20 calibration curve³⁴. Together this evidence strongly supports the conclusion that CCC formation in WWC occurred in the late Holocene, and is still occurring today.

Winter Wonderland Cave as a Unique Natural Laboratory for the study of CCC.

Because of its utility as a paleoclimate proxy, numerous studies have investigated CCC^{e.g. 21,30,35,36}. However, there are only a few reports of CCC from locations outside Eurasia^19,37, and all of these are categorized isotopically as CCC_fine. Winter Wonderland Cave is, therefore, the first location in the Western Hemisphere where the unique paleoclimate indicator CCC_coarse has been identified.

Furthermore, nearly all previous observations of CCC describe these minerals from locations where they are present as loose concentrations of mineral grains on an ice-free cave floor^21,26. Only twice has CCC_coarse been reported in association with modern, perennial ice^31,36, and a recent comprehensive review noted that “Despite increasing evidence for Holocene CCC_coarse, actively forming sites have not yet been observed”¹³. In WWC, CCC_coarse with late Holocene to modern ages is present in association with perennial ice, making this cave an exceptional natural laboratory in which to study these precipitates and their genesis.

Furthermore, firsthand observations indicate that the situation within WWC is consistent with the model for the formation of CCC_coarse. During summer visits in 2014, 2015, and 2016, the cave was dry and the ice surface exhibited a complex pattern of elongated ridges and troughs with local relief on the order of 30 cm (Fig. 4) formed as a result of sublimation³⁸. Short-term studies in an ice cave in Alberta, Canada suggest ice sublimation rates on the order of 3 mm per year³⁹, although rates up to 10× higher have also been reported¹³. Either way, extrapolation from these benchmarks suggests that the relief observed on the ice surface in 2016 reflects 10¹ to 10² years of sublimation without the addition of new water. In contrast, in summer 2018, and again in 2019, liquid water entered the cave, filling many of the furrows, and freezing to create a new ice surface (Fig. 4). Deeper pools of water had lids of ice from 1 to 5 cm thick (Fig. 2b), precisely the mechanism proposed for the formation of CCC_coarse^15,21,23. This water ranged from clear to a deep yellow color, and CCC was observed on the floor of each pool (Table S1). From the available data we cannot determine if this CCC precipitated from the water, or whether it was present as a lag on the ice surface before the pools formed. However, the concentration of solutes in this pool water was very high, with the highest values (K, Mg, and Ca >200 mg/L) corresponding to the yellow color (Fig. S5), consistent with conditions necessary for mineral precipitation through freezing-induced saturation¹⁴.

The change from 2016 to 2018 suggests that the thermal state of the epikarst has recently shifted, at least locally, to allow liquid water to penetrate to the level of the cave (~100 m below the ground surface), or to produce meltwater from ice farther back in inaccessible parts of the cave system. Under extensive permafrost conditions, caves are unlikely to contain ice sourced from dripwater because the permafrost inhibits the downward movement of liquid water⁴⁰. Only when permafrost is degrading is it possible for liquid water to reach a cave where temperatures remain consistently subzero. The available evidence supports the interpretation that WWC and its surrounding host rock comprise a sporadic permafrost body that is currently undergoing this transition. Numerical modeling suggests that the time window between thawing and ultimate loss of permafrost is relatively short⁴¹, and studies have noted that cave ice is rapidly ablating in various locations around the world⁴². Future investigations in WWC should take advantage of this singular opportunity to observe the formation of different types of CCC in (near) real time, with the goal of improving our ability to use the presence of these features in currently ice-free caves as a dateable indicator of past permafrost thaw²¹.

Winter Wonderland Cave in the Uinta Mountains of Utah contains cryogenic cave carbonate (CCC) associated with perennial ice. Two types of CCC with different genesis are present and can be distinguished on the basis of O and C isotope values. CCC_fine is produced through open system freezing as a thin film of water flows over the ice surface. In contrast, CCC_coarse is produced by (semi) closed-system freezing in deeper pools of water beneath thickening lids of ice. These conditions arise during permafrost thaw, thus CCC_coarse records past episodes of permafrost degradation. Available age control suggests that CCC formation occurred in this cave during the late Holocene and may be a contemporary process. This cave is the first location in the world where such young CCC_coarse has been found, and is the first location in the Western Hemisphere where CCC_coarse has been identified. Records of past cryosphere transitions are critical context for assessing contemporary changes in Arctic and alpine environments. Winter Wonderland Cave provides a singular opportunity to test and improve theories of CCC genesis that will ultimately allow better insight into how permafrost responded to past climatic transitions.

The methods employed in sample analysis are briefly described here; full details are presented in the supporting information. At Middlebury College, CCC samples were wet sieved into >250, 250-75, and <75 µm size fractions. The morphology of all fractions was examined with a Tescan Vega 3 LMU scanning electron microscope (SEM). Energy dispersive x-ray spectroscopy (EDS) was used to evaluate whether contrasting grain morphologies observed in samples YS-3, YS-6, TS-2, CP, YP, and TF correspond to different elemental compositions.

The grain size distribution of the <75-µm fraction of each sample was investigated with laser scattering in a Horiba LA-950 particle size analyzer. Samples were dispersed in distilled water, and sonified before analysis.

CCC mineralogy, along with representative samples of the Madison Limestone collected from the cave, was investigated with a Bruker D8 Advance x-ray diffractometer. The mineralogy of several samples was compared across different size fractions (<75 µm and 250-75 µm) to detect any compositional differences. Because none were apparent, the <75-µm and 250-75-µm fractions were used interchangeably for subsequent analyses depending on the amount of sample remaining.

The abundance of major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P) in the samples was investigated with x-ray fluorescence on a Thermo Scientific ARL QuantX energy dispersive XRF. Trace elements were measured in the <75-µm fraction of samples YS-3, YS-4, YS-5, YS-6, TS-1, TS-2, in a representative bedrock sample, and in the 250-75-µm fraction of sample YS-4 with inductively coupled plasma mass spectrometry on a Thermo Scientific iCAP Q ICP-MS after dissolution in HNO₃. The ICP-MS was also used to investigate the hydrochemistry of the water samples.

Values of δ¹⁸O and δ¹³C were measured in all <75-µm size fractions except CP and YP 250-75 µm at Union College using a GasBench II connected to a Thermo Delta Advantage isotope ratio mass spectrometer in continuous flow mode. Analytical uncertainties were better than 0.1 ‰ (1σ) for δ¹⁸O and 0.05 ‰ (1σ) for δ¹³C. Eleven samples of bedrock, along with separate size fractions of samples YS-1 through YS-6, CP, and YP were analyzed at the University of Innsbruck on a Thermo Scientific Delta V Plus isotope ratio mass spectrometer (IRMS) connected to a GasBench II⁴³. This system produces a typical precision (1σ) of ±0.06 ‰ for δ¹³C and ±0.08 ‰ for δ¹⁸O⁴⁴. All isotope results were calibrated against international standards and reported in permil (‰) relative to VPDB.

The age of 5 samples (YS-5, YS-6, CP, YP, and TF) was assessed using U-Th techniques at the Massachusetts Institute of Technology. U and Th were analyzed on separate aliquots using a Nu Plasma II-ES multi-collector ICP-MS equipped with a CETAC Aridus II desolvating nebulizer⁴⁵. U-Th ages were first calculated using standard decay constants for ²³⁰Th, ²³⁴U, and ²³⁸U^46–48, then recalculated given the observation that the TF sample is modern. Reported errors for ²³⁸U and ²³²Th concentrations are estimated to be ±1% due to uncertainties in spike concentration, whereas analytical errors are smaller. Variability of initial ²³⁰Th/²³²Th throughout the cave was assumed to be ±25% at 2σ.

Data Availability: The dataset generated in this study has been deposited in the Hydroshare repository and will have the doi https://doi.org/10.4211/hs.b5f0000096174af9af94fe62bd2065d6 after publication.

Acknowledgments

C.W. was crucial to the success of this challenging fieldwork. P.R. and J.S. assisted with the ICP-MS analysis. Thanks to D.G. at Union College for help with the initial isotope measurements. Financial support was provided by the Middlebury College URO.

Author Contributions:

JM designed the study, wrote the manuscript, and prepared the figures. KK participated in fieldwork, conducted the geochemical and preliminary isotope analyses, and prepared samples for U/Th dating. CS oversaw isotope analyses at the University of Innsbruck. DM and GSM oversaw the U/Th dating at MIT. DH ensured safe passage to and from the cave, and provided the mapping upon which Figure 1 was based. All authors reviewed the manuscript before submission.

Competing Interests: The authors declare no conflict of interest.

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published 19 Mar, 2021

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Winter Wonderland Cave, Utah, USA: A Natural Laboratory for the Study of Cryogenic Cave Carbonate and Thawing Permafrost

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