Search

The isotope signature of cave waters provides an excellent opportunity to better understand the recharge in karst regions and the complexity of drainage systems in the vadose zone. We have developed a cave isotope hydrological model (ISODRIP) that requires entering basic hydrometeorological information and a precipitation δ 18 O record to simulate the discharge and δ 18 O signals of different drip sites. The model includes four different modules to simulate various flow route regimes: continuous and discontinuous drips under diffuse or preferential flows. We use precipitation and cave water δ 18 O records that were obtained in Eagle Cave (central Spain) during a 5-year period to test our model and to better understand the dynamics of karst aquifers. Eagle Cave waters do not record evaporation. The δ 18 O signals do not have seasonality, although they record intra-annual and inter-annual variability. Additionally, cave water δ 18 O signal falls within the range of the annual average weighted isotope composition of precipitation. Well-mixed cave waters, that characterize diffuse flows, record 1‰ δ 18 O variability, whereas partially-mixed waters, that flow along preferential drainage routes, have up to 3‰ δ 18 O variability. The results suggest that precipitation takes on average 15 months to reach the cave through the diffuse flow network, whereas under preferential flow the transit time is highly variable depending on the previous condition of the system. ISODRIP includes a soil layer above the vadose zone that controls large recharge events, together with direct recharge components that bypass the soil layer enabling at least some recharge all year round. Thus, the simulations reproduce the observed lack of seasonal bias in the cave water δ 18 O composition in relation to the average weighted isotope composition of precipitation. This research highlights the importance of understanding recharge dynamics and the configuration of particular drips sites to properly interpret speleothem δ 18 O records., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The controls that affect the structure and timing of terminations are still poorly understood. We studied a tufa deposit from the Iberian Peninsula that covers Termination II (T-II) and whose chronology was synchronized to speleothem records. We used the same chronology to synchronize ocean sediments from the North Atlantic to correlate major climate events in a common timescale. We identify two stages within T-II. The first stage started with the increase of boreal summer integrated solar insolation, and during this stage three millennial climate oscillations were recorded. These oscillations resulted from complex ocean-atmosphere interactions in the Nordic seas, caused by the progressive decay of Northern Hemisphere ice-sheets. The second stage commenced after a glacial outburst that caused the collapse of the Thermohaline Circulation, a massive Heinrich event, and the onset of the Bipolar Seesaw Mechanism (BSM) that eventually permitted the completion of T-II. The pace of the millennial oscillations during the first stage of T-II controlled the onset of the second stage, when the termination became a non-reversible and global phenomenon that accelerated the deglaciation. During the last the two terminations, the BSM was triggered by different detailed climate interactions, which suggests the occurrence of different modes of terminations.

The influence of wildfire on surface soil and hydrology has been widely investigated, while its impact on the karst vadose zone is still poorly understood. A moderate to severe experimental fire was conducted on a plot (10 m × 10 m) above the shallow Wildman's Cave at Wombeyan Caves, New South Wales, Australia in May 2016. Continuous sampling of water stable isotopes, inorganic geochemistry and drip rates were conducted from Dec 2014 to May 2017. After the fire, drip discharge patterns were significantly altered, which is interpreted as the result of increased preferential flows and decreased diffuse flows in the soil. Post-fire drip water δ 18 O decreased by 6.3‰ in the first month relative to the average pre-fire isotopic composition. Post-fire monitoring showed an increase in drip water δ 18 O in the following six months. Bedrock related solutes (calcium, magnesium, strontium) decreased rapidly after the fire due to reduced limestone dissolution time and potentially reduced soil CO 2 . Soil- and ash-derived solutes (boron, lead, potassium, sodium, silicon, iodine and iron) all decreased after the fire due to volatilisation at high temperatures, except for SO 4 2- . This is the first study to understand the hydrological impact from severe fires conducted on a karst system. It provides new insights on the cave recharge process, with a potential explanation for the decreased d18O in speleothem-based fire study, and also utilise the decreased bedrock solutes to assess the wildfire impacts both in short and long time scales., (Copyright © 2019. Published by Elsevier B.V.)

Fire dramatically modifies the surface environment by combusting vegetation and changing soil properties. Despite this well-documented impact on the surface environment, there has been limited research into the impact of fire events on karst, caves and speleothems. Here we report the first experiment designed to investigate the short-term impacts of a prescribed fire on speleothem-forming cave drip water geochemistry. Before and after the fire, water was collected on a bi-monthly basis from 18 drip sites in South Glory Cave, New South Wales, Australia. Two months post-fire, there was an increase in B, Si, Na, Fe and Pb concentrations at all drip sites. We conclude that this response is most likely due to the transport of soluble ash-derived elements from the surface to the cave drip water below. A significant deviation in stable water isotopic composition from the local meteoric water line was also observed at six of the sites. We hypothesise that this was due to partial evaporation of soil water resulting in isotopic enrichment of drip waters. Our results demonstrate that even low-severity prescribed fires can have an impact on speleothem-forming cave drip water geochemistry. These findings are significant because firstly, fires need to be considered when interpreting past climate from speleothem δ 18 O isotope and trace element records, particularly in fire prone regions such as Australia, North America, south west Europe, Russia and China. Secondly, it supports research that demonstrates speleothems could be potential proxy records for past fires., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Geological evidence indicates that grounded ice sheets reached sea level at all latitudes during two long-lived Cryogenian (58 and ≥5 My) glaciations. Combined uranium-lead and rhenium-osmium dating suggests that the older (Sturtian) glacial onset and both terminations were globally synchronous. Geochemical data imply that CO 2 was 10 2 PAL (present atmospheric level) at the younger termination, consistent with a global ice cover. Sturtian glaciation followed breakup of a tropical supercontinent, and its onset coincided with the equatorial emplacement of a large igneous province. Modeling shows that the small thermal inertia of a globally frozen surface reverses the annual mean tropical atmospheric circulation, producing an equatorial desert and net snow and frost accumulation elsewhere. Oceanic ice thickens, forming a sea glacier that flows gravitationally toward the equator, sustained by the hydrologic cycle and by basal freezing and melting. Tropical ice sheets flow faster as CO 2 rises but lose mass and become sensitive to orbital changes. Equatorial dust accumulation engenders supraglacial oligotrophic meltwater ecosystems, favorable for cyanobacteria and certain eukaryotes. Meltwater flushing through cracks enables organic burial and submarine deposition of airborne volcanic ash. The subglacial ocean is turbulent and well mixed, in response to geothermal heating and heat loss through the ice cover, increasing with latitude. Terminal carbonate deposits, unique to Cryogenian glaciations, are products of intense weathering and ocean stratification. Whole-ocean warming and collapsing peripheral bulges allow marine coastal flooding to continue long after ice-sheet disappearance. The evolutionary legacy of Snowball Earth is perceptible in fossils and living organisms.

The increasing carbon dioxide (CO2 ) concentration in the atmosphere in combination with climatic changes throughout the last century are likely to have had a profound effect on the physiology of trees: altering the carbon and water fluxes passing through the stomatal pores. However, the magnitude and spatial patterns of such changes in natural forests remain highly uncertain. Here, stable carbon isotope ratios from a network of 35 tree-ring sites located across Europe are investigated to determine the intrinsic water-use efficiency (iWUE), the ratio of photosynthesis to stomatal conductance from 1901 to 2000. The results were compared with simulations of a dynamic vegetation model (LPX-Bern 1.0) that integrates numerous ecosystem and land-atmosphere exchange processes in a theoretical framework. The spatial pattern of tree-ring derived iWUE of the investigated coniferous and deciduous species and the model results agreed significantly with a clear south-to-north gradient, as well as a general increase in iWUE over the 20th century. The magnitude of the iWUE increase was not spatially uniform, with the strongest increase observed and modelled for temperate forests in Central Europe, a region where summer soil-water availability decreased over the last century. We were able to demonstrate that the combined effects of increasing CO2 and climate change leading to soil drying have resulted in an accelerated increase in iWUE. These findings will help to reduce uncertainties in the land surface schemes of global climate models, where vegetation-climate feedbacks are currently still poorly constrained by observational data., (© 2014 John Wiley & Sons Ltd.)

Palaeorecords which depict changes in sulphur dynamics form an invaluable resource for recording atmospheric pollution. Tree rings constitute an archive that are ubiquitously available and can be absolutely dated, providing the potential to explore local- to regional-scale trends in sulphur availability. Rapid isotopic analysis by a novel "on-line" method using elemental analyser isotope ratio mass spectrometry (EA-IRMS) is developed, achieving sample precision of <0.4‰ using sample sizes of 40 mg wood powder. Tree cores from NE Italy show trends in pollution, evidenced through increasing concentrations of sulphur towards the youngest growth, and inverse trends in sulphur isotopes differentiating modern growth with light sulphur isotopes (+0.7‰) from pre-industrial growth (+7.5‰) influenced by bedrock composition. Comparison with speleothem records from the same location demonstrate replication, albeit offset in isotopic value due to groundwater storage. Using EA-IRMS, tree ring archives form a valuable resource for understanding local- to regional-scale sulphur pollution dynamics., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

For the first time the specific fluorescent characteristics of organic carbon (OC) in sequentially filtered cave dripwater samples have been studied and the proportions of organic carbon in each size fraction quantified. We examined the effects of pH, temperature and filtration on the fluorescent properties of OC sampled from four drip points in different seasons. Dripwaters were sampled from both normal (pH 7.5-8.5) and hyper-alkaline (pH 9-13) drip points in Poole's Cavern, Buxton, UK, which provides a model system for understanding the effects of pH on the chemical properties of OC. At high-pH values, charge stabilisation of OC is greatly enhanced, resulting in 10-20 times more coarse colloidal and particulate (>100 nm) organic carbon than in lower pH dripwaters; indicating that destabilisation (e.g. charge shielding) of colloidal OC is an important process control on the transmission of OC in cave dripwaters at near-neutral pH. OC fluorescence in high-pH dripwaters exhibited a high degree of pH sensitivity between pH 10 and 12, consistent with substantial changes in the coordination or neighbouring environment of fluorescent acidic functional groups. Inner-filter effects (IFE) associated with the coarse colloidal and particulate fraction of OM mask the true fluorescent signal, so that size fractionation is necessary to obtain a signal which is correlated with the concentration of organic carbon. Fluorescence intensities in the samples studied were best correlated with organic carbon with a dimension <100 nm. These results have important implications for the use of fluorescence as a tracer in hydrogeological studies., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The oxygen isotope composition of terrestrial sulfate is affected measurably by many Earth-surface processes. During the Neoproterozoic, severe "snowball" glaciations would have had an extreme impact on the biosphere and the atmosphere. Here, we report that sulfate extracted from carbonate lenses within a Neoproterozoic glacial diamictite suite from Svalbard, with an age of approximately 635 million years ago, falls well outside the currently known natural range of triple oxygen isotope compositions and indicates that the atmosphere had either an exceptionally high atmospheric carbon dioxide concentration or an utterly unfamiliar oxygen cycle during deposition of the diamictites.

Abrupt first-order shifts in strontium and phosphorus concentrations in stalagmite calcite deposited in western Ireland during the 8200-year event (the major cooling episode 8200 years before the present) are interpreted as responses to a drier climate lasting about 37 years. Both shifts are centered on 8330 +/- 80 years before the present, coinciding with a large oxygen isotope anomaly and a change in the calcite petrography. In this very high resolution (monthly) record, antipathetic second-order oscillations in phosphorus and strontium reveal decreased growth rates and increased rainfall seasonality. Growth rate variations within the event reveal a two-pronged structure consistent with recent model simulations.

Tidal flat and lagoonal dolostones of the Neoproterozoic Draken Formation, Spitsbergen, exhibit excellent preservation of carbonate fabrics, including heavily calcified microfossils. The crust-forming cyanobacterium Polybessurus is preserved locally by carbonate precipitated on and within sheaths in mildly evaporitic upper intertidal to supratidal environments. In contrast, calcified filaments in columnar stromatolites reflect subtidal precipitation. Filament molds in dolomicrites independently document extremely early lithification. The presence of heavily calcified cyanobacteria in Draken and other Proterozoic carbonates constrains potential explanations for the widespread appearance of calcified microorganisms near the Proterozoic-Cambrian boundary. We propose that the rarity of Proterozoic examples principally reflects the abundance and wide distribution of carbonate crystals precipitated on the sea floor or in the water column. Cyanobacterial sheaths would have competed effectively as sites for carbonate nucleation and growth only where calcitic and/or aragonitic nuclei were absent. In this view, the Proterozoic-Cambrian expansion of calcified microfossils primarily reflects the emergence of skeletons as principal agents of carbonate deposition.

The Draken Formation (120-250 m) of northeast Spitsbergen (Svalbard) forms part of a thick Upper Proterozoic carbonate platform succession. It consists predominantly of intraformational dolomitic conglomerates, with excellent textural preservation. Six main lithofacies were recognized in the field: quartz sandstones, stromatolitic mats, conglomerates with silicified intraclasts, dolostone conglomerates with desiccated mudrocks, oolitic/pisolitic grainstones and fenestral dolostones. A series of five main gradational biofacies were recognized from silicified (and rare calcified) microfossils. Biofacies 1 represents low-energy subtidal benthos (erect filaments) and plankton (acritarchs and vase-shaped microfossils) whereas biofacies 2 to 5 are microbial mat assemblages (with filamentous mat-builders, and associated dwellers and washed-in plankton) ranging from basal intertidal to high intertidal/supratidal. Colour values (a measure of the lightness of the colour shade) of sawn rock samples were quantified using a Munsell chart, and exhibit a pronounced variation (means of major groups varying from 4.0 to 5.95) across the spectrum of subtidal to supratidal sediments as inferred from other criteria. The lightening in progressively more exposed sediments is related to lowering of organic carbon contents, probably mainly by oxidation. Six types of early cement have been recognized. Calcite microspar (type 1) is common as a subtidal cement in many Proterozoic formations, whereas types 2 (subtidal isopachous fringes), 3 (subtidal hardground dolomicrite) and 4 (intertidal meniscus dolomicrite) are very similar to Phanerozoic examples except for their dolomitic mineralogy. Types 5 and 6 are complex and variable dolomite growths associated with expansion and replacive phenomena. They characterize the fenestral lithofacies and compare with modern supratidal cements. Consideration of diagenetic fabrics and truncation textures of intraclasts indicates that leaching, dolomitization, silicification were all significant syndepositional processes altering the original metastable carbonates. The data set provides evidence for a spectrum of peritidal environments including ooid shoals, protected subtidal, tidal sandflats and protected carbonate mudflats. Different sections show a preponderance of particular facies. The coastal lithofacies continuum was completely dolomitized, unlike offshore to ooid shoal facies of adjacent formations. Dolomitization thus bears a relationship to depositional bathymetry. Although hydrodynamics clearly have a role, the potential importance of whiting precipitation in raising Mg/Ca in marginal marine environments is also stressed.