A post-wildfire response in cave dripwater chemistry

Surface disturbances above a cave have the potential to impact cave dripwater discharge, isotopic composition and solute concentrations, which may subsequently be recorded in the stalagmites forming from these dripwaters. One such disturbance is wildfire; however, the effects of wildfire on cave chemistry and hydrology remains poorly understood. Using dripwater data monitored at two sites in a shallow cave, beneath a forest, in southwest Australia, we provide one of the first cave monitoring studies conducted in a post-fire regime, which seeks to identify the effects of wildfire and post-fire vegetation dynamics on dripwater δ18O composition and solute concentrations. We compare our post-wildfire δ18O data with predicted dripwater δ18O using a forward model based on measured hydro-climatic influences alone. This helps to delineate hydro-climatic and fire-related influences on δ18O. Further we also compare our data with both data from Golgotha Cave – which is in a similar environment but was not influenced by this particular fire – as well as regional groundwater chemistry, in an attempt to determine the extent to which wildfire affects dripwater chemistry. We find in our forested shallow cave that δ18O is higher after the fire relative to modelled δ18O. We attribute this to increased evaporation due to reduced albedo and canopy cover. The solute response post-fire varied between the two drip sites: at Site 1a, which had a large tree above it that was lost in the fire, we see a response reflecting both a reduction in tree water use and a removal of nutrients (Cl, Mg, Sr, and Ca) from the surface and subsurface. Solutes such as SO4 and K maintain high concentrations, due to the abundance of above-ground ash. At Site 2a, which was covered by lower–middle storey vegetation, we see a solute response reflecting evaporative concentration of all studied ions (Cl, Ca, Mg, Sr, SO4, and K) similar to the trend in δ18O for this drip site. We open a new avenue for speleothem science in fire-prone regions, focusing on the geochemical records of speleothems as potential palaeo-fire archives. © Author(s) 2016

Solar-forced diurnal regulation of cave drip rates via phreatophyte evapotranspiration

We present results of a detailed study of drip rate variations at 12 drip discharge sites in Glory Hole Cave, New South Wales, Australia. Our novel time series analysis, using the wavelet synchrosqueezed transform, reveals pronounced oscillations at daily and sub-daily frequencies occurring in 8 out of the 12 monitored sites. These oscillations were not spatially or temporally homogenous, with different drip sites exhibiting such behaviour at different times of year in different parts of the cave. We test several hypotheses for the cause of the oscillations, including variations in pressure gradients between karst and cave due to cave breathing effects or atmospheric and earth tides, variations in hydraulic conductivity due to changes in viscosity of water with daily temperature oscillations, and solar-driven daily cycles of vegetative (phreatophytic) transpiration. We conclude that the only hypothesis consistent with the data and hydrologic theory is that daily oscillations are caused by solar-driven pumping by phreatophytic trees which are abundant at the site. The daily oscillations are not continuous and occur sporadically in short bursts (2–14 days) throughout the year due to non-linear modification of the solar signal via complex karst architecture. This is the first indirect observation leading to the hypothesis of tree water use in cave drip water. It has important implications for karst hydrology in regards to developing a new protocol to determine the relative importance of trends in drip rate, such as diurnal oscillations, and how these trends change over timescales of weeks to years. This information can also be used to infer karst architecture. This study demonstrates the importance of vegetation on recharge dynamics, information that will inform both process-based karst models and empirical estimation approaches. Our findings support a growing body of research exploring the impact of trees on speleothem paleoclimate proxies

Sulphur: a proxy for wildfires in stalagmites

Bushfires are a global hazard that can have catastrophic impacts on communities and ecosystems. However, there is limited baseline data on how fire frequency and intensity have responded to climate change in the past. A speleothem-based bushfire record will allow us to determine long-term natural fire regimes and better understand the relationship between bushfires and climate. Recent research has demonstrated the potential of using sulphur as a speleothem paleofire proxy1 but a full characterisation of S in the karst environments of SW Western Australia is lacking. Here, we quantify the relative contributions of different sources of sulphur in a modern cave environment through the characterisation of rainfall, soil, bedrock, vegetation and cave drip water sulphate concentration and isotopic values (δ18O- SO4 and δ34S- SO4) to assess the role of sulphur cycling through the biomass in response to burn events at this site. This information will be used to interpret the SO4 isotope record, supported by other proxies in a 2-12 ka speleothem from SW Western Australia. This is the first speleothem SO4 isotope study in the southern hemisphere and the first in the world to use speleothem S isotopes in a paleofire context. © Author(s

What determines the calcium concentration of speleothem-forming drip waters?

Cave drip water calcium ion concentration is a primary determinant of speleothem deposition and growth rate. The factors that determine drip water calcium ion concentrations are the soil and vadose zone CO2 concentrations, and the hydrogeochemical evolution of the water from soil to cave. Here, we use a systematic literature review of cave drip water calcium concentrations, combined with PHREEQC equilibrium modelling, to investigate the global relationship between calcium concentration and surface climate. Our results are discussed in the context of understanding the climatic and environmental controls on drip water calcium concentration, speleothem growth rates and proxies of past climate and environmental change. We use an empirical, global soil CO2 concentration–temperature relationship to derive PHREEQC modelled cave drip water calcium concentrations. The global mean modelled drip water calcium concentration is close to that observed, but it over-predicts at high and low temperatures, and significantly under-predicts at temperate conditions. We hypothesise that closed system hydrochemical evolution due to water saturation is an important control on carbonate dissolution at colder temperatures. Under warmer conditions, for example temperate climates with a dry and hot or warm summer, seasonally-limited water availability can lead to: < 100% soil cover; water-limitations on microbial and root respiration; wildfire; and prior calcite precipitation, all of which limit drip water calcium concentrations. In temperate climates with no dry season, higher CO2 concentrations than modelled from soil values are necessary to explain the observed drip water calcium values, which we propose is from an additional source of CO2 from microbial activity and root respiration in the vadose zone during open system hydrochemical evolution

Dissolved organic matter in the unsaturated zone: the view from the cave

Soil organic matter content is typically a few percent of the total soil composition. Diffuse recharge can mobilise some of this soil-derived organic matter. While soil pore water dissolved organic matter (DOM) concentrations are up to 100 ppm, the resulting groundwater dissolved organic matter concentration is typically less than 2ppm. Dissolved organic matter transported from the soil can be both biodegraded and sorbed to minerals, and the relative importance of these two processes in the unsaturated zone is poorly understood.Caves in karstified limestone uniquely provide direct access to water percolating from the soil to the groundwater. Cave percolation waters can be analysed for their DOM concentration and character. This provides insights into the extent and type of biological and chemical processing of DOM during transport from the soil to the groundwater.We determine the concentration and characteristics of DOM in cave percolation waters using liquid chromatography (LC-OCD) and optical spectrophotometry (fluorescence and absorbance). We sample DOM from multiple caves in SE Australia (Cathedral Cave, Wellington; South Glory and Harrie Wood Caves, Yarrangobilly), permitting comparison of unsaturated zone DOM properties at different depths (up to 30m below land surface) and different climate zones (montane and temperate). We use caves with long-term hydrological monitoring programs so that DOM in waters of contrasting residence times can be compared. Additionally, we compare these cave percolation water DOM characteristics to those from local and regional groundwater, sampled from nearby wells. Our results will help improve our understanding of how DOM is processed from soil to groundwater, and is also relevant to speleothem scientists interested in using organic matter preserved in speleothems as a paleoclimate or paleoenvironmental proxy

A post-wildfire response in cave dripwater chemistry

Surface disturbances above a cave have the potential to impact cave dripwater discharge, isotopic composition and solute concentrations, which may subsequently be recorded in the stalagmites forming from these dripwaters. One such disturbance is wildfire; however, the effects of wildfire on cave chemistry and hydrology remains poorly understood. Using dripwater data monitored at two sites in a shallow cave, beneath a forest, in southwest Australia, we provide one of the first cave monitoring studies conducted in a post-fire regime, which seeks to identify the effects of wildfire and post-fire vegetation dynamics on dripwater <i>δ</i>¹⁸O composition and solute concentrations. We compare our post-wildfire <i>δ</i>¹⁸O data with predicted dripwater <i>δ</i>¹⁸O using a forward model based on measured hydro-climatic influences alone. This helps to delineate hydro-climatic and fire-related influences on <i>δ</i>¹⁸O. Further we also compare our data with both data from Golgotha Cave &ndash; which is in a similar environment but was not influenced by this particular fire &ndash; as well as regional groundwater chemistry, in an attempt to determine the extent to which wildfire affects dripwater chemistry. We find in our forested shallow cave that <i>δ</i>¹⁸O is higher after the fire relative to modelled <i>δ</i>¹⁸O. We attribute this to increased evaporation due to reduced albedo and canopy cover. The solute response post-fire varied between the two drip sites: at Site 1a, which had a large tree above it that was lost in the fire, we see a response reflecting both a reduction in tree water use and a removal of nutrients (Cl, Mg, Sr, and Ca) from the surface and subsurface. Solutes such as SO₄ and K maintain high concentrations, due to the abundance of above-ground ash. At Site 2a, which was covered by lower&ndash;middle storey vegetation, we see a solute response reflecting evaporative concentration of all studied ions (Cl, Ca, Mg, Sr, SO₄, and K) similar to the trend in <i>δ</i>¹⁸O for this drip site. We open a new avenue for speleothem science in fire-prone regions, focusing on the geochemical records of speleothems as potential palaeo-fire archives