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7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Sulphur variations in annually layered stalagmites using benchtop micro-XRF

Variation of sulphur in annually laminated stalagmites can be used to infer the impact of past volcanic activities, anthropogenic pollution, and climate change due to increased bushfire activity. The synchrotron radiation micro-X-Ray fluorescence (SR-XRF) microprobe is a powerful tool to analyse and image sulphur recorded in stalagmites with micrometre resolution. However, access to SR-XRF beamlines can be limited, so researchers must select the most promising stalagmites for imaging. Benchtop micro-XRF is an effective tool for trace elemental analysis of speleothem samples and is a candidate for routine laboratory measurement of sulphur along stalagmite laminae and screening for SR-XRF. Here, this study describes a protocol using matrix-matched standards to measure annual variations of sulphur at trace to percent level along the laminae of two Western Australian stalagmites, one of which already having been analysed using SR-XRF. Parameters that affected quantitation include X-ray tube voltage and current, spot size of the X-ray beam and stalagmite surface roughness and porosity. The use of a 20 μm X-ray spot size provides sub-annual spatial resolution that can be completed in an overnight scan. The features in a 1000 point micro-XRF analysis of sulphur along a 20 mm transect show good consistency with SR-XRF microprobe data. Micro-XRF mapping was also performed to produce chemical images on the stalagmite and compared with Raman and X-ray diffraction (XRD) to confirm that the stalagmite is exclusively calcite, with no aragonite, and that the source of sulphur in the samples was gypsum and anhydrite. Regions of very high sulphur in the micro-XRF maps were found to be artefacts due to diffraction of the incident beam but these could be efficiently removed by using a multiple point statistics approach to produce a clean image suitable for analysis of the laminae. This work shows the potential of micro-XRF for routine analysis of sulphur in stalagmites, and to streamline sample characterisation before SR-XRF imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Shapes of ideal stalagmites

Stalagmites are isolated columns of calcium carbonate growing on a cave floor; their growth is driven by the constant dripping of supersaturated solutions from the roof of the cave. In this paper, we derive a closed-form expression for the shape of a steadily growing stalagmite. Our analysis gives rise to three distinct shapes, all of them observable in nature, with the shape characterized by a single dimensionless parameter. Transitions between different shapes occur at a specific value of this parameter, with additional selection rules determining the shape and size of stalagmites evolving under specific cave conditions. Our theory shows that the stalagmite shape influences the 13 C isotope shifts, which are an important source of paleoclimatic information.

invariant growth↗
DOE OSTI2022

Past fires and post-fire impacts reconstructed from a southwest Australian stalagmite

Speleothem records of past environmental change provide an important opportunity to explore fire frequency and intensity in the past, and the antecedent climatic conditions leading to fire events. Here, fire sensitive geochemical signals in a stalagmite from Yonderup Cave, a shallow cave in Western Australia, are compared to well-documented wildfire events that occurred in recent decades. The results are extended to identify wildfires during the growth interval of the speleothem (1760 CE–2005 CE). Principal component analysis of the stalagmite time-series revealed distinct peaks in a combination of phosphorus and metal (aluminium, zinc, copper and lead) concentrations in response to known fire events, which are interpreted to have come from ash. Varying responses in the geochemical signal in the pre- and post-European colonisation period are likely linked to changes in land management, fire frequency and fire intensities. Of note is what we infer to be a particularly intense fire event concluded to have occurred in 1897 ± 5 CE, which climate sensitive proxies (δ18O and bedrock-derived elements) indicate was preceded by a multi-decadal dry period that began in the late 1860s. The intensity of the deduced fire event is supported by a peak in P that is 6.3 times higher than elsewhere in the speleothem, accompanied by a peak in Zn. It was also inferred that changes to the surface-cave hydrology occurred as a result of this event, indicated by increased input of colloidal organic material onto the stalagmite that was interpreted to be caused by shallow karst bedrock fracturing from the heat-induced deformation that is observed after intense fires. These findings show the potential for speleothems to provide dated records of fire intensity and recurrence intervals. Further development could lead to a better understanding of the climate-fire relationship and the effects of land-management practices on wildfire frequency and intensity.

58 GEOSCIENCES↗
DOE OSTI2020

Semiquantitative Estimates of Rainfall Variability During the 8.2 kyr Event in California Using Speleothem Calcium Isotope Ratios

A multiproxy record from a fast-growing stalagmite reveals variable hydroclimate on the California coast across the 8.2 kyr event and a precursor event likely caused by initial drainage of proglacial Lake Agassiz. Using speleothem δ 44 Ca, we develop the first semiquantitative estimates of paleorainfall variability for California through calibration with measurements of the modern climate and cave environment. We find that the magnitude of rainfall variability during the 8.2 kyr event approached the multiyear variability observable in the recent past (1950–2019) and the magnitude of variability during the precursor event likely exceeded this range. Additionally, we observe other instances of multidecadal variability comparable in magnitude to the precursor event during the record. Finally, our work suggests that speleothem calcium isotope ratios are a powerful semiquantitative means to reconstruct paleorainfall, although numerous factors must be assessed in each cave system before applying this approach.

58 GEOSCIENCES↗
DOE OSTI2020

End of Green Sahara amplified mid- to late Holocene megadroughts in mainland Southeast Asia

Between 5 and 4 thousand years ago, crippling megadroughts led to the disruption of ancient civilizations across parts of Africa and Asia, yet the extent of these climate extremes in mainland Southeast Asia (MSEA) has never been defined. This is despite archeological evidence showing a shift in human settlement patterns across the region during this period. We report evidence from stalagmite climate records indicating a major decrease of monsoon rainfall in MSEA during the mid- to late Holocene, coincident with African monsoon failure during the end of the Green Sahara. Through a set of modeling experiments, we show that reduced vegetation and increased dust loads during the Green Sahara termination shifted the Walker circulation eastward and cooled the Indian Ocean, causing a reduction in monsoon rainfall in MSEA. Our results indicate that vegetation-dust climate feedbacks from Sahara drying may have been the catalyst for societal shifts in MSEA via ocean-atmospheric teleconnections.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Pathways for Nucleation and Growth in Confined Spaces and at Interfaces

Mineral crystallization is central to myriad natural processes from the formation of snowflakes to stalagmites, but the molecular-scale mechanisms are often far more complex than models reflect. Feedbacks between the hydro-, bio-, and geo-spheres drive complex crystallization processes that challenge our ability to observe and quantify them, motivating an expansion of crystallization theories. Here, in this article, we discuss how the driving forces and timescales of nucleation are influenced by factors ranging from simple geometric confinement to distinct interfacial solution structures involving solvent organization, electrical double layers, and surface charging effects. Taken together, these ubiquitous natural phenomena can preserve metastable intermediates, drive precipitation of undersaturated phases, and modulate crystallization in time and space.

biosphere↗
NASA NTRS2021

Hypogenic Karst of the Great Basin

Discoveries in the 1980s greatly expanded speleologists’ understanding of therole that hypogenic groundwater flow can play developingcaves at depth. Ascending groundwater charged with carbon dioxide and,especially,hydrogen sulfide,can readily dissolve carbonate bedrock just below and above the water table. Sulfuric acid speleogenesis, in which anoxic, rising, sulfidic groundwater mixes with oxygenated cave atmosphere to form aggressive sulfuric acid (H2SO4), formed spectacular caves in CarlsbadCaverns National Park. Cueva de Villa Luz in Mexico provides an aggressively active example of sulfuric acid speleogenesisprocesses, and the Frasassi Caves in Italy preserve the results of sulfuric acid speleogenesis in its upper levels while sulfidic groundwater currently enlarges cave passages in the lower levels. Manycaves in east-central Nevada and western Utah are products of hypogenic speleogenesis and formed before the current topography fully developed. Wet climate during the late Neogeneand Pleistocene brought extensive meteoric infiltration into the caves and calcite speleothems (e.g., stalactites, stalagmites, shields) coat the walls and floors of the caves, concealing evidence of the earlier hypogenic stage. However, by studying the speleogenetic features in well-established sulfuric acid speleogenesis caves, evidence ofhypogenic, probably sulfidic, speleogenesis inmany Great Basin caves can be teased out.Compelling evidence of hypogenicspeleogenesis in these cavesinclude folia, mammillaries, bubble trails, cupolas, and metatyuyamunite. Sulfuric acid speleogenesis signsinclude hollowcoralloidstalagmites,trays, gypsum crust, pseudoscallops, rills, and acid pool notches. Lehman Caves is particularly informative as a low-permeability capstone protected about half of the cave from significant meteoric infiltration, preserving early speleogeneticfeatures.

Louise D Hose↗