Cave air and hydrological controls on prior calcite precipitation and stalagmite growth rates: Implications for palaeoclimate reconstructions using speleothems

Hourly resolved cave air P_CO2 and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air P_CO2 and drip water Ca²⁺ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air P_CO2 control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca²⁺ concentrations requires a P_CO2 shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air P_CO2 differential, and availability of low P_CO2 void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air P_CO2 appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca²⁺ concentrations (dilution) followed by much more gradual increases in drip water Ca²⁺ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.     

Electrical conductivity of orthopyroxene and plagioclase in the lower crust

The electrical conductivities of lower crustal orthopyroxene and plagioclase, as well as their dependence on water content, were measured at 6–12 kbar and 300–1,000°C on both natural and pre-annealed samples prepared from fresh mafic xenolith granulites. The complex impedance was determined in an end-loaded piston cylinder apparatus by a Solarton-1260 Impedance/Gain Phase analyzer in the frequency range of 0.1–10⁶ Hz. The spectra usually show an arc over the whole frequency range at low temperature and an arc plus a tail in the high and low frequency range, respectively, at high temperature. The arc is due to conduction in the sample interior, while the tails are probably due to electrode effects. Different conduction mechanisms have been identified under dry and hydrous conditions. For the dry orthopyroxene, the activation enthalpy is ~105 kJ/mol, and the conduction is likely due to small polarons, e.g., electrons hopping between Fe²⁺ and Fe³⁺. For the dry plagioclase, the activation enthalpy is ~161 kJ/mol, and the conduction may be related to the mobility of Na⁺. For the hydrous samples, the activation enthalpy is ~81 kJ/mol for orthopyroxene and ~77 kJ/mol for plagioclase, and the electrical conductivity is markedly enhanced, probably due to proton conduction. For each mineral, the conductivity increases with increasing water content, with an exponent of ~1, and the activation enthalpies are nearly independent of water content. Combining these data with our previous work on the conductivity of lower crustal clinopyroxene, the bulk conductivity of lower crustal granulites is modeled, which is usually >~10⁻⁴ S/m in the range of 600–1,000°C. We suggest that the high electrical conductivity in most regions of the lower crust, especially where it consists mostly of granulites, can be explained by the main constitutive minerals, particularly if they contain some water. Contributions from other highly conducting materials such as hydrous fluids, melts, or graphite films are not strictly necessary to explain the observed conductivities.     

Quantifying fracture geometry with X-ray tomography: Technique of Iterative Local Thresholding (TILT) for 3D image segmentation

This paper presents a new method—the Technique of Iterative Local Thresholding (TILT)—for processing 3D X-ray computed tomography (xCT) images for visualization and quantification of rock fractures. The TILT method includes the following advancements. First, custom masks are generated by a fracture-dilation procedure, which significantly amplifies the fracture signal on the intensity histogram used for local thresholding. Second, TILT is particularly well suited for fracture characterization in granular rocks because the multi-scale Hessian fracture (MHF) filter has been incorporated to distinguish fractures from pores in the rock matrix. Third, TILT wraps the thresholding and fracture isolation steps in an optimized iterative routine for binary segmentation, minimizing human intervention and enabling automated processing of large 3D datasets. As an illustrative example, we applied TILT to 3D xCT images of reacted and unreacted fractured limestone cores. Other segmentation methods were also applied to provide insights regarding variability in image processing. The results show that TILT significantly enhanced separability of grayscale intensities, outperformed the other methods in automation, and was successful in isolating fractures from the porous rock matrix. Because the other methods are more likely to misclassify fracture edges as void and/or have limited capacity in distinguishing fractures from pores, those methods estimated larger fracture volumes (up to 80 %), surface areas (up to 60 %), and roughness (up to a factor of 2). These differences in fracture geometry would lead to significant disparities in hydraulic permeability predictions, as determined by 2D flow simulations.     

Integration of optical and Synthetic Aperture Radar (SAR) imagery for delivering operational annual crop inventories

Agriculture plays a critical role within Canada’s economy and, as such, sustainability of this sector is of high importance. Targeting and monitoring programs designed to promote economic and environmental sustainability are a vital component within Canada’s agricultural policy. A hierarchy of land information, including up to date information on cropping practices, is needed to measure the impacts of programs on land use decision-making and to gauge the environmental and economic benefits of these investments. A multi-year, multi-site research activity was completed to develop a robust methodology to inventory crops across Canada’s large and diverse agricultural landscapes. To move towards operational implementation the methodology must deliver accurate crop inventories, with consistency and reliability. In order to meet these operational requirements and to mitigate risk associated with reliance on a single data source, the methodology integrated both optical and Synthetic Aperture Radar (SAR) imagery. The results clearly demonstrated that multi-temporal satellite data can successfully classify crops for a variety of cropping systems present across Canada. Overall accuracies of at least 85% were achieved, and most major crops were also classified to this level of accuracy. Although multi-temporal optical data would be the preferred data source for crop classification, a SAR-optical dataset (two Envisat ASAR images and one optical image) provided acceptable accuracies and will mitigate risk associated with operational implementation. The preferred dual-polarization mode would be VV–VH. Not only were these promising classification results repeated year after year, but the target accuracies were met consistently for multiple sites across Canada, all with varying cropping systems.     

Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO₂ real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (TPM/CO₂) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg C_{dry plant} and EF(Ct)=7.4±3.4 and 56±16 g C/kg C_{dry plant} for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.     

Biodegradation and environmental behavior of biodiesel mixtures in the sea: An initial study

Biodiesel, a mixture of fatty acid methyl esters (FAMEs) derived from animal fats or vegetable oils, is rapidly moving towards the mainstream as an alternative source of energy. However, the behavior of biodiesel, or blends of biodiesel with fossil diesel, in the marine environment have yet to be fully understood. Hence, we performed a series of initial laboratory experiments and simple calculations to evaluate the microbial and environmental fate of FAMEs. Aerobic seawater microcosms spiked with biodiesel or mixtures of biodiesel and fossil diesel revealed that the FAMEs were degraded at roughly the same rate as n-alkanes, and more rapidly than other hydrocarbon components. The residues extracted from these different microcosms became indistinguishable within weeks. Preliminary results from physical-chemical calculations suggest that FAMEs in biodiesel mixtures will not affect the evaporation rates of spilled petroleum hydrocarbons but may stabilize oil droplets in the water column and thereby facilitate transport.     

Fossil brines preserved in the St-Lawrence Lowlands, Québec, Canada as revealed by their chemistry and noble gas isotopes

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. ⁸⁷Sr/⁸⁶Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle ³He and large amounts of nucleogenic ²¹Ne^∗ and ³⁸Ar^∗ and radiogenic ⁴He and ⁴⁰Ar^∗. ⁴He/⁴⁰Ar^∗ and ²¹Ne^∗/⁴⁰Ar^∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of ⁴⁰Ar^∗ in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic ⁴⁰Ar^∗ into the brines. The last thermal event that could have facilitated the liberation of ⁴⁰Ar^∗ into fluids and contributed to mantle ³He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.     

The eruptive history of the Tequila volcanic field, western Mexico: ages, volumes, and relative proportions of lava types

The eruptive history of the Tequila volcanic field (1600 km²) in the western Trans-Mexican Volcanic Belt is based on ⁴⁰Ar/³⁹Ar chronology and volume estimates for eruptive units younger than 1 Ma. Ages are reported for 49 volcanic units, including Volcán Tequila (an andesitic stratovolcano) and peripheral domes, flows, and scoria cones. Volumes of volcanic units 1 Ma were obtained with the aid of field mapping, ortho aerial photographs, digital elevation models (DEMs), and ArcGIS software. Between 1120 and 200 kyrs ago, a bimodal distribution of rhyolite (~35 km³) and high-Ti basalt (~39 km³) dominated the volcanic field. Between 685 and 225 kyrs ago, less than 3 km³ of andesite and dacite erupted from more than 15 isolated vents; these lavas are crystal-poor and show little evidence of storage in an upper crustal chamber. Approximately 200 kyr ago, ~31 km³ of andesite erupted to form the stratocone of Volcán Tequila. The phenocryst assemblage of these lavas suggests storage within a chamber at ~2–3 km depth. After a hiatus of ~110 kyrs, ~15 km³ of andesite erupted along the W and SE flanks of Volcán Tequila at ~90 ka, most likely from a second, discrete magma chamber located at ~5–6 km depth. The youngest volcanic feature (~60 ka) is the small andesitic volcano Cerro Tomasillo (~2 km³). Over the last 1 Myr, a total of 128±22 km³ of lava erupted in the Tequila volcanic field, leading to an average eruption rate of ~0.13 km³/kyr. This volume erupted over ~1600 km², leading to an average lava accumulation rate of ~8 cm/kyr. The relative proportions of lava types are ~22–43% basalt, ~0.4–1% basaltic andesite, ~29–54% andesite, ~2–3% dacite, and ~18–40% rhyolite. On the basis of eruptive sequence, proportions of lava types, phenocryst assemblages, textures, and chemical composition, the lavas do not reflect the differentiation of a single (or only a few) parental liquids in a long-lived magma chamber. The rhyolites are geochemically diverse and were likely formed by episodic partial melting of upper crustal rocks in response to emplacement of basalts. There are no examples of mingled rhyolitic and basaltic magmas. Whatever mechanism is invoked to explain the generation of andesite at the Tequila volcanic field, it must be consistent with a dominantly bimodal distribution of high-Ti basalt and rhyolite for an 800 kyr interval beginning ~1 Ma, which abruptly switched to punctuated bursts of predominantly andesitic volcanism over the last 200 kyrs.Electronic Supplementary Material Supplementary material is available in the online version of this article at Editorial responsility: J. Donnelly-NolanThis revised version was published online in January 2005 with corrections to Tables 1 and 3.An erratum to this article can be found at     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.