Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Fluvial erosion and post-erosional processes on Titan

The surface of Titan has been revealed by Cassini observations in the infrared and radar wavelength ranges as well as locally by the Huygens lander instruments. Sand seas, recently discovered lakes, distinct landscapes and dendritic erosion patterns indicate dynamic surface processes. This study focus on erosional and depositional features that can be used to constrain the amount of liquids involved in the erosional process as well as on the compositional characteristics of depositional areas. Fluvial erosion channels on Titan as identified at the Huygens landing site and in RADAR and Visible and Infrared Mapping Spectrometer (VIMS) observations have been compared to analogous channel widths on Earth yielding average discharges of up to 1600 m³/s for short recurrence intervals that are sufficient to move centimeter-sized sediment and significantly higher discharges for long intervals. With respect to the associated drainage areas, this roughly translates to 1-150 cm/day runoff production rates with 10 years recurrence intervals and by assuming precipitation this implies 0.6-60 mm/h rainfall rates. Thus the observed surface erosion fits with the methane convective storm models as well as with the rates needed to transport sediment. During Cassini's T20 fly-by, the VIMS observed an extremely eroded area at 30° W, 7° S with resolutions of up to 500 m/pixel that extends over thousands of square kilometers. The spectral characteristics of this area change systematically, reflecting continuous compositional and/or particle size variations indicative of transported sediment settling out while flow capacities cease. To account for the estimated runoff production and widespread alluvial deposits of fine-grained material, release of area-dependent large fluid volumes are required. Only frequent storms with heavy rainfall or cryovolcanic induced melting can explain these erosional features.     

Community-level response of coastal microbial biofilms to ocean acidification in a natural carbon dioxide vent ecosystem

The impacts of ocean acidification on coastal biofilms are poorly understood. Carbon dioxide vent areas provide an opportunity to make predictions about the impacts of ocean acidification. We compared biofilms that colonised glass slides in areas exposed to ambient and elevated levels of pCO(2) along a coastal pH gradient, with biofilms grown at ambient and reduced light levels. Biofilm production was highest under ambient light levels, but under both light regimes biofilm production was enhanced in seawater with high pCO(2). Uronic acids are a component of biofilms and increased significantly with high pCO(2). Bacteria and Eukarya denaturing gradient gel electrophoresis profile analysis showed clear differences in the structures of ambient and reduced light biofilm communities, and biofilms grown at high pCO(2) compared with ambient conditions. This study characterises biofilm response to natural seabed CO(2) seeps and provides a baseline understanding of how coastal ecosystems may respond to increased pCO(2) levels.     

Modelling the tidal mixing fronts and seasonal stratification of the Northwest European Continental shelf

We investigate mixing processes under stratified conditions on the Northwest European Continental shelf using a numerical model (POLCOMS). Our results indicate that convection induced by vertical shearing of horizontal density gradients (‘shear-induced convection’) is a regularly occurring feature in the bottom and surface boundary layers in this open shelf-sea situation. Two types of turbulence models are investigated to study their capability for reproducing the observed location of tidal mixing fronts, and the physical processes occurring in seasonally stratified waters. The first model is a one-equation variant of the Mellor–Yamada model, whereas the second model combines a more recent second-momentum closure with a two-equation model. It is found that generally mean frontal positions (as estimated from ICES data) are predicted more accurately by the two-equation model. The one-equation model reproduces the mean frontal locations to 18.1 km (<3 grid spacings) and the two-equation model to 17.1 km; although in the Celtic Sea the accuracy is ∼33 and ∼12 km, respectively. Comparison with historical tide gauges, current metres, CTD stations, and thermistor chain data from the North Sea Project all show an improvement in accuracy when the two-equation model is used. This is particularly apparent in the model's ability to reproduce the spring–neap variability during stratification. We find that in the presence of shear-induced convection the routinely applied clipping of the turbulent length-scale, previously thought to be a minor ingredient in a turbulence model, has a dramatic effect on the results: if the length-scale clipping is not applied, substantial over-mixing is observed to occur. The causes and possible remedies of this effect are investigated. Overall our results demonstrate a sensitivity to the details of the turbulence model that is significantly greater than previously thought.     

The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate

A three-dimensional two-phase flow model is coupled to a non-linear reactive transport model to study the efficacy of potassium permanganate treatment on dense, non-aqueous phase liquid (DNAPL) source removal in porous media. A linear relationship between the soil permeability (k) and concentration of manganese dioxide precipitate ([MnO_2(s)]), k = k_o + S_rind [MnO_2(s)], is utilized to simulate nodal permeability reductions due to precipitate formation. Using published experimental column studies, an S_rind = −5.5 × 10⁻¹⁶ m² L/mg was determined for trichloroethylene (TCE) DNAPL. This S_rind was then applied to treatment simulations on three-dimensional TCE DNAPL source zones comprising either DNAPL at residual saturations, or DNAPL at pooled saturations.     

Climate of the past millennium inferred from varved proglacial lake sediments on northeast Baffin Island,Arctic Canada

This study uses ^239+240Pu-dated varved sediments from Big Round Lake, a proglacial lake on northeast Baffin Island, Arctic Canada to generate a 1000-year-long, annual-resolution record of past climate. Varve thickness is positively correlated with July–August–September temperature measured at Clyde River, 70 km to the north of the lake (r = 0.46, p < 0.001). We therefore interpret the variability and trends in varve thickness to partially represent summer temperature. The coolest Little Ice Age temperatures occurred in this record from 1575 to 1760 AD and were approximately 1.5°C cooler than today (average from 1995 to 2005 AD) and 0.2°C cooler than the last millennium (average from 1000 to 2000 AD). Pre-twentieth-century warmth occurred during two intervals, 970–1150 AD and 1375–1575 AD; temperatures were approximately 1.2°C cooler than today, but 0.1°C warmer than the last millennium. The Big Round Lake varve-thickness record contains features similar to that reconstructed elsewhere in the eastern Canadian Arctic. This high-resolution quantitative record expands our understanding of arctic climate during the past millennium.

Radiocarbon dating of small terrestrial gastropod shells in North America

Fossil shells of small terrestrial gastropods are commonly preserved in wetland, alluvial, loess, and glacial deposits, as well as in sediments at many archeological sites. These shells are composed largely of aragonite (CaCO₃) and potentially could be used for radiocarbon dating, but they must meet two criteria before their ¹⁴C ages can be considered to be reliable: (1) when gastropods are alive, the ¹⁴C activity of their shells must be in equilibrium with the ¹⁴C activity of the atmosphere, and (2) after burial, their shells must behave as closed systems with respect to carbon. To evaluate the first criterion, we conducted a comprehensive examination of the ¹⁴C content of the most common small terrestrial gastropods in North America, including 247 AMS measurements of modern shell material (3749 individual shells) from 46 different species. The modern gastropods that we analyzed were all collected from habitats on carbonate terrain and, therefore, the data presented here represent worst-case scenarios. In sum, ～78% of the shell aliquots that we analyzed did not contain dead carbon from limestone or other carbonate rocks even though it was readily available at all sites, 12% of the aliquots contained between 5 and 10% dead carbon, and a few (3% of the total) contained more than 10%. These results are significantly lower than the 20–30% dead carbon that has been reported previously for larger taxa living in carbonate terrain. For the second criterion, we report a case study from the American Midwest in which we analyzed fossil shells of small terrestrial gastropods (7 taxa; 18 AMS measurements; 173 individual shells) recovered from late-Pleistocene sediments. The fossil shells yielded ¹⁴C ages that were statistically indistinguishable from ¹⁴C ages of well-preserved plant macrofossils from the same stratum. Although just one site, these results suggest that small terrestrial gastropod shells may behave as closed systems with respect to carbon over geologic timescales. More work on this subject is needed, but if our case study site is representative of other sites, then fossil shells of some small terrestrial gastropods, including at least five common genera, Catinella, Columella, Discus, Gastrocopta, and Succinea, should yield reliable ¹⁴C ages, regardless of the local geologic substrate.     

Health, sexuality and place: the different geographies of HIV-positive gay men in Auckland, New Zealand

This paper employs interview narratives alongside participant-led photography and caption writing to examine the different daily geographies of 15 HIV-positive gay men in Auckland, New Zealand. Difference for these men is rooted in both their HIV status and their sexuality, and this difference has implications for their engagement with the world at a range of spatial and temporal scales. Giving voice to such experiences begins to answer calls for geographers to consider more deeply the connections between health, sexuality and place.