Morphological and speleothemic development in Brujas Cave (Southern Andean Range, Argentine): palaeoenvironmental significance

Brujas Cave, in the Southern Andean Range, is a well-known endokarstic site in Argentina. However, the origin and evolution of this cave system are poorly known. Based on morphological cave features as well as characteristics of cave deposits, we propose a meteogene drawdown cave genesis, including a change from phreatic to vadose conditions related to the high rate of fluvial downcutting in the area. During the vadose period, various cave-related deposits, including authogenic calcite and gypsum speleothems, allogenic volcanic ash and external tufas were deposited. Gypsum crusts are the oldest cave deposits identified (90.2–64.3 ky BP). Their origin, deduced from isotopic characteristics (∂³⁴S=9.6‰), is related to the oxidation of pyrite contained in the Jurassic limestone bedrock as well as the dissolution of overlying Jurassic–Triassic evaporite formations. Gypsum crust deposition is associated with evaporation of water flowing and seeping into the cave during arid environmental conditions. Calcite deposits precipitated from flowing water under equilibrium conditions represent the main speleothem growth period (67.6–34 ky BP in age). Their stable isotope values (∂¹³C=−3‰ to −5‰ and ∂¹⁸O=−9‰ to −11‰) may indicate slightly humid and warm conditions related to the regional Minchin lacustrine phase and global oxygen isotope stage 3. Following this stage, a seismic event is evidenced by accumulations of broken stalactites. Seepage calcite speleothems covering cave walls were deposited under disequilibrium conditions by evaporation, probably during Holocene time. Finally, another more recent gypsum deposition period represented by gypsum balls has been differentiated. Micromorphological as well as isotopic (∂³⁴S=5.6‰) data indicate that these gypsum forms are related to cyclic processes (solution–deposition) from water seeping into the cave under arid conditions. In addition, intense volcanic activity in the area during Holocene time is deduced from allogenic volcanic ash and lapilli located mainly at the entrance cave. At present, limited hydrological activity is observed in the cave and small tufa deposits at karstic discharge points are evidenced. We conclude that the geomorphological evolution of Brujas Cave was controlled by climatic changes (wet and dry stages) under semiarid environmental conditions in a very active tectonic and volcanic setting during Late Quaternary time.     

WA-PLS diatom-based pH, TP and DOC inference models from 42 lakes in the Abitibi clay belt area (Québec, Canada)

The relationship between surficial sediment diatom species and measured environmental variables was explored in lakes from the Abitibi region of western Quebec. Diatom assemblages in 42 lakes were identified and their relationship with measured environmental variables was examined using multivariate statistical methods. Canonical correspondence analysis with forward selection and Monte Carlo permutation tests revealed that the three environmental variables pH, TP and DOC each accounted for statistically significant fractions of the variation in diatom taxa. A training set with 164 modern diatom taxa was used to derive transfer functions for lake-water pH, TP and DOC using weighted-averaging-partial-least-squares (WA-PLS) techniques. The models were developed to infer lake water pH, TP and DOC within the ranges 4–8 for pH, 2.75–30.0 g l^–1 for TP, and 2.9–18.5 mg l^–1 for DOC. These quantitative inference models may now be used to help identify and estimate the effects of natural disturbances on the biogeochemistry of Abitibi lakes during their historical development.     

Thermo‐tectonic evolution of the south‐central Pyrenees from rifting to orogeny: insights from detrital zircon U/Pb and (U‐Th)/He thermochronometry

Constraining the thermal and denudational evolution of continental margins from extensional episodes to early orogenic stages is critical in the objective to better understand the sediment routing during the growth of orogenic topography. Here, we report 160 detrital zircon U/Pb ages and 73 (U‐Th)/He ages from Albian, Upper Cretaceous and Eocene sandstones from the south‐central Pyrenees. All samples show dominant zircon U/Pb age peaks at 310–320 Ma, indicating a primary contribution from Variscan granites of the central Pyrenean Axial Zone. A secondary population at 450–600 Ma documents zircon grains sourced from the eastern Pyrenees. Zircon (U‐Th)/He ages recovered from older samples document, a Triassic age peak at ca. 241 Ma, corresponding to denudation coeval with the initiation of Atlantic rifting. An Early Cretaceous cooling event at ca. 133 Ma appears consistent with rift‐related exhumation and thermal overprint on the Iberian margin. The (U‐Th)/He age peaks from ca. 80 Ma to ca. 68 Ma with decreasing depositional ages are interpreted to reflect the southward‐migrating thrust‐related exhumation on the pro‐wedge side of the Pyrenean orogen. The increase in lag times, from ca. 15 Ma in the Tremp Formation (ca. 65 Ma) to 28 Ma in the Escanilla Formation (ca. 40 Ma), suggests decreasing exhumation rates from 0.4 km Myr^–1 to 0.2 km Myr^–1. The apparent inconsistency with convergence rates is used to infer that rocks cooled at 68 Ma may have resided in the crust before final exhumation to the surface. Finally, the cooling event observed at 68 Ma provides support to the inferred acceleration of convergence, shortening and exhumation during Late Cretaceous times.     

Solubility of CO2 in a Ca-rich leucitite: effects of pressure,temperature, and oxygen fugacity

The solubility of carbon dioxide in a Ca-rich leucitite has been investigated as a function of pressure (0.1–2.0 GPa), temperature (1200–1600°C), and oxygen fugacity. The experiments were done in a rapid-quench internally-heated pressure vessel (0.1 GPa) and a piston cylinder (0.5–2.0 GPa). The leucitite glass, previously equilibrated at NNO, and silver oxalate were loaded in Fe-doped Pt capsules (oxidized conditions) and graphitelined Pt capsules (reduced conditions). Secondary Ion Mass Spectrometry and bulk carbon analyses were used to determine the amount of dissolved carbon. Speciation of carbon was characterized by Fourier transform microinfrared spectroscopy. At oxidized conditions, only CO₃ ^2- is observed as a dissolved species. The solubility is high with CO₂ contents in the melt attaining 6.2 wt% at 2.0 GPa and 1350°C. The solubility increases with pressure and shows a significant negative temperature dependence. An excellent correlation is obtained when the data are fit to a model, based on the simplified solubility reaction CO₂ ^(vapor)+O^2-(melt)CO₃ ^2-(melt), which describes the solubility of CO₂ as a function of pressure, temperature and fCO₂. At reduced conditions, the amount of carbon dissolved is significantly lower, and CO₃ ^2- is still the only species present in the melt. If the solubility model established at oxidized conditions is applied, the carbon dissolved appears to be essentially a function of fCO₂ alone although divergence increases in a consistent manner with pressure and temperature. This could suggest a low but significant solubility of CO with a positive temperature dependence or a departure of the calculated fluid compositions determined by the equation of state from the actual ones. The strong preferential solubility of carbon in its oxidized C⁴⁺ form, even at reduced conditions, implies that ascending melts with high CO₂ solubility can experience significant oxidation through degassing. This could reconcile the oxidized nature of some Ca-rich alkaline magmas with more reduced mantle source regions.     

Sources and chronology of fifteen elements in the sediments of lakes affected by metal deposition in a mining area

Sources and chronologies of metal contamination were studied in sediment cores of three lakes of the Rouyn-Noranda mining area (Québec, Canada) affected by atmospheric deposition of anthropogenic contaminants. One of the three lakes also received acid mine drainage. The sediments were dated using ²¹⁰Pb and ¹³⁷Cs and analysed for stable Pb isotope ratios and for total concentrations of 15 elements (Ag, Al, Au, Ca, Cu, Cd, Fe, Hg, Mn, Ni, P, Pb, S, Ti, Zn). Stable lead isotopic signatures helped to determine the quantitative contributions of different industrial Pb sources to our sampling sites. This source apportionment showed the dominant influence of the Rouyn-Noranda copper smelter in airborne Pb emissions for the decades following 1926, when industrialization began in the region. The smelter source had a low ratio of ²⁰⁶Pb/²⁰⁷Pb ranging between 0.90 and 1.05, as typical of the Abitibi Archean sulphides. The relationships between element (metal) sedimentary fluxes and anthropogenic Pb fluxes allowed us to infer the origin of the anthropogenic source. These relationships strongly suggest that the copper smelter was (and may still be) an atmospheric source of Cd, Cu, Pb, Zn, Ag and Hg to the surrounding lakes. Our study indicates that the efforts made by the Rouyn-Noranda copper smelter to reduce airborne emissions of metals have been translated in reduced atmospheric metal loadings to the surrounding lakes.     

Relationships among Gibbs energies of formation of sulfates,nitrates, carbonates,oxides and aqueous ions

A parameter _GO^2– is defined as the difference between the Gibbs free energy of formation from the elements of a given oxide and its corresponding aqueous cation. The Gibbs free energies of formation of compounds such as sulfates, nitrates or carbonates, from their constituent oxides, are shown to be linear functions of _GO^2– values of their constituent cations.     

An Engineering Approach to Seismic Risk Management in Hardrock Mines

The problem of mining-induced seismicity in hardrock mines has become significant as underground mines from around the world are pushing production to deeper levels. At many mines, the risk associated with large seismic events and rockburst damage must be managed to ensure the safety of mine workers and minimise production losses. In this paper, an engineering approach to seismic risk management is described. It relies on accepted risk management techniques, which principally include the identification and understanding of hazards from which risk mitigation measures can be developed. This is achieved using simple but effective analysis techniques of high resolution microseismic data.     

KArMars: A Breadboard Model for In Situ Absolute Geochronology Based on the K–Ar Method Using UV‐Laser‐Induced Breakdown Spectroscopy and Quadrupole Mass Spectrometry

We present a breadboard prototype to perform in situ dating applicable to planetary exploration. Based on the K–Ar dating method and using instruments inspired by flight‐proven analytical components, ‘KArMars’ ablated a geological sample under high vacuum with a quadrupled ultraviolet (UV at 266 nm) Nd:YAG laser. During ablation, the K content of the target material was given by laser‐induced breakdown spectroscopy and the released ⁴⁰Ar was measured with a quadrupole mass spectrometer. Because K was measured as a concentration and ⁴⁰Ar as a count of atoms, these values were converted using the ablated mass given by the product of the density and the ablated volume. The uncertainties of the age measurement were < 15%. The quality of the K–Ar measurements was enhanced by the advantages of UV laser ablation such as the minimisation of thermal effects on argon diffusion. This work demonstrates that a specialised instrument inspired by this set‐up could provide in situ absolute geochronology with sufficient precision for scientific investigations, particularly where the crater density counting provides higher uncertainties on Mars.     

Diatom taxonomic and morphological changes as indicators of metal pollution and recovery in Lac Dufault (Québec, Canada)

We studied diatom taxonomic composition and the presence of morphological alterations (size and deformations) along a sediment core collected in Lac Dufault, Abitibi, whose watershed has a long history of mining pollution presently undergoing mitigation. According to sediment dating with ²¹⁰Pb and metal profiles along the core, we could identify four periods in the contamination history of the lake, which were characterized by different diatoms. Tabellaria flocculosa was dominant in the pre-mining period but was drastically reduced at the onset of pollution when Fragilaria cf. tenera became important. This diatom, together with other Fragilaria species and cysts of Chaetoceros muelleri, typified the transition period in which Cu reached its maximum value and other metals started to increase. During the period of maximum contamination with Zn, Cd, and Fe accompanied by acid mine drainage, Achnanthes minutissima and Brachysira vitrea were dominant. These taxa started to wane in the most recent sediments representing a partial chemical recovery. Asterionella formosa, which almost vanished at mining onset, reappeared with high abundance in these superficial sections. Beside these taxonomical shifts, we observed during the contamination period significant reduction in valve length together with increased percentages of valve deformations. Because available data on water chemistry and a diatom-based pH reconstruction suggest that Lac Dufault escaped severe acidification, diatom patterns observed in the core can be mostly ascribed to metal contamination. Individual diatom abundance and valve length had strong statistical relationships with the different metals identified in the core. Diatom changes both taxonomic and morphological can be excellent specific indicator of metal contamination and early recovery.