Triple oxygen isotope analysis of nitrate using isotope exchange cavity ringdown laser spectroscopy.

RATIONALE: Triple oxygen isotopes (16 O/17 O/18 O) in nitrate are a valuable tool to ascertain the pathways of nitrate formation in the atmosphere and the fate of nitrate in ecosystems. Here we present a new method for determining Δ17 O values in nitrates, based on nitrate-water isotope equilibration (IE) and subsequent isotopic analysis of water using cavity ringdown laser spectroscopy (CRDS). METHODS: Nitrate oxygen (O-NO3 - ) is equilibrated with water oxygen (O-H2 O) at low pH and 80°C. Subsequently, the δ17 O and δ18 O values of equilibrated water are determined by CRDS, scaled to V-SMOW and V-SLAP and calibrated against nitrate standards (USGS-34, USGS-35 and IAEA-NO3). We provide isotopic measurements of synthetic and natural nitrates and a direct inter-lab comparison with the classic method of thermal-decomposition of nitrate followed by isotope ratio mass spectrometry of O2 (TD-IRMS). RESULTS: For synthetic NaNO3 , the precision (1SD) of the IE-CRDS method is 0.8‰ for δ17 O values, 1.7‰ for δ18 O values and 0.2‰ for Δ17 O values when using an O-NO3 - /O-H2 O ratio greater than 0.0114 ± 0.0001 (e.g. 12 µmol of NO3 - in 50 µL of acid solution). For natural samples, after purification of nitrates by column chemistry and reprecipitation as AgNO3 , the precision is better than 1.8‰ for δ17 O values, 3.2‰ for δ18 O values and 1‰ for Δ17 O values. IE-CRDS and TD-IRMS yield Δ17 O values within the analytical errors of the two methods. CONCLUSIONS: The IE-CRDS method for determining Δ17 O values in nitrates utilizes a user-friendly and relatively cheaper benchtop analytical instrument, representing an alternative to IRMS-based methods for certain applications.

Spatiotemporal distribution of δ(13)CCO2 in a shallow cave and its potential use as indicator of anthropic pressure.

This study deals with the spatiotemporal dynamics of CO2 and its isotopic composition (δ(13)CCO2) in the atmosphere of Altamira Cave (northern Spain) over two annual cycles. In general terms, the cavity shows two distinct ventilation modes, acting as a CO2 reservoir from October to May (recharge stage), while actively exchanging gases with the outside atmosphere between July and September (discharge stage). In recharge mode, the in-cave air shows higher and relatively homogeneous CO2 values (3332 ± 521 ppm) with lower δ(13)CCO2 (-23.2 ± 0.4‰). In contrast, during the discharge stage, the CO2 concentrations are lower and relatively more variable (1383 ± 435 ppm) and accompanied by higher δ(13)CCO2 (up to -12‰). This seasonal pattern is controlled by the distinct rates of exchange of air masses with the external atmosphere through the annual cycle, as well as by changes in the production of CO2 in the soil and natural fluctuations in the concentration of dissolved inorganic carbon transported by drip water into the cave. In contrast to the interpretations of previous studies in Altamira Cave, no local air intakes into the deepest cave sections were flagged by our δ(13)C measurements. This finding is also supported by analyses of CO2 and (222)Rn in air, density of airborne particles and air temperature. In addition, preliminary experiments examining the visitor-produced disturbances on δ(13)CCO2 were conducted during the various cave ventilation stages to explore the potential use of this parameter as an indicator of anthropic pressure in caves. Our data show that visits (overall stay of 60-85 min; i.e., 4 people for 20 min) significantly affected δ(13)CCO2 (up to Δδ(13)C âˆ¼ -2‰) in the Polychrome Hall of Altamira Cave under conditions of low natural CO2 (discharge stage), whereas it remained almost unaltered under circumstances of high CO2 concentration (recharge stage). This demonstrates that δ(13)CCO2 is sensitive to perturbations produced by visitors during certain periods.

Simultaneous analysis of (17) O/(16) O, (18) O/(16) O and (2) H/(1) H of gypsum hydration water by cavity ring-down laser spectroscopy.

RATIONALE: The recent development of cavity ring-down laser spectroscopy (CRDS) instruments capable of measuring (17) O-excess in water has created new opportunities for studying the hydrologic cycle. Here we apply this new method to studying the triple oxygen ((17) O/(16) O, (18) O/(16) O) and hydrogen ((2) H/(1) H) isotope ratios of gypsum hydration water (GHW), which can provide information about the conditions under which the mineral formed and subsequent post-depositional interaction with other fluids. METHODS: We developed a semi-automated procedure for extracting GHW by slowly heating the sample to 400°C in vacuo and cryogenically trapping the evolved water. The isotopic composition (δ(17) O, δ(18) O and δ(2) H values) of the GHW is subsequently measured by CRDS. The extraction apparatus allows the dehydration of five samples and one standard simultaneously, thereby increasing the long-term precision and sample throughput compared with previous methods. The apparatus is also useful for distilling brines prior to isotopic analysis. A direct comparison is made between results of (17) O-excess in GHW obtained by CRDS and fluorination followed by isotope ratio mass spectrometry (IRMS) of O2 . RESULTS: The long-term analytical precision of our method of extraction and isotopic analysis of GHW by CRDS is ±0.07‰ for δ(17) O values, ±0.13‰ for δ(18) O values and ±0.49‰ for δ(2) H values (all ±1SD), and ±1.1‰ and ±8 per meg for the deuterium-excess and (17) O-excess, respectively. Accurate measurement of the (17) O-excess values of GHW, of both synthetic and natural samples, requires the use of a micro-combustion module (MCM). This accessory removes contaminants (VOCs, H2 S, etc.) from the water vapour stream that interfere with the wavelengths used for spectroscopic measurement of water isotopologues. CRDS/MCM and IRMS methods yield similar isotopic results for the analysis of both synthetic and natural gypsum samples within analytical error of the two methods. CONCLUSIONS: We demonstrate that precise and simultaneous isotopic measurements of δ(17) O, δ(18) O and δ(2) H values, and the derived deuterium-excess and (17) O-excess, can be obtained from GHW and brines using a new extraction apparatus and subsequent measurement by CRDS. This method provides new opportunities for the application of water isotope tracers in hydrologic and paleoclimatologic research.

Organic geochemistry and mineralogy suggest anthropogenic impact in speleothem chemistry from volcanic show caves of the Galapagos.

The network of lava tubes is one of the most unexploited natural wonders of the Galapagos Islands. Here, we provide the first morphological, mineralogical, and biogeochemical assessment of speleothems from volcanic caves of the Galapagos to understand their structure, composition, and origin, as well as to identify organic molecules preserved in speleothems. Mineralogical analyses revealed that moonmilk and coralloid speleothems from Bellavista and Royal Palm Caves were composed of calcite, opal-A, and minor amounts of clay minerals. Extracellular polymeric substances, fossilized bacteria, silica microspheres, and cell imprints on siliceous minerals evidenced microbe-mineral interactions and biologically-mediated silica precipitation. Alternating depositional layers between siliceous and carbonate minerals and the detection of biomarkers of surface vegetation and anthropogenic stressors indicated environmental and anthropogenic changes (agriculture, human waste, and cave visits) on these unique underground resources. Stable isotope analysis and Py-GC/MS were key to robustly identify biomarkers, allowing for implementation of future protection policies.

Volcanic controls on the microbial habitability of Mars-analogue hydrothermal environments.

Due to their potential to support chemolithotrophic life, relic hydrothermal systems on Mars are a key target for astrobiological exploration. We analysed water and sediments at six geothermal pools from the rhyolitic Kerlingarfjöll and basaltic Kverkfjöll volcanoes in Iceland, to investigate the localised controls on the habitability of these systems in terms of microbial community function. Our results show that host lithology plays a minor role in pool geochemistry and authigenic mineralogy, with the system geochemistry primarily controlled by deep volcanic processes. We find that by dictating pool water pH and redox conditions, deep volcanic processes are the primary control on microbial community structure and function, with water input from the proximal glacier acting as a secondary control by regulating pool temperatures. Kerlingarfjöll pools have reduced, circum-neutral CO2 -rich waters with authigenic calcite-, pyrite- and kaolinite-bearing sediments. The dominant metabolisms inferred from community profiles obtained by 16S rRNA gene sequencing are methanogenesis, respiration of sulphate and sulphur (S0 ) oxidation. In contrast, Kverkfjöll pools have oxidised, acidic (pH < 3) waters with high concentrations of SO42- and high argillic alteration, resulting in Al-phyllosilicate-rich sediments. The prevailing metabolisms here are iron oxidation, sulphur oxidation and nitrification. Where analogous ice-fed hydrothermal systems existed on early Mars, similar volcanic processes would likely have controlled localised metabolic potential and thus habitability. Moreover, such systems offer several habitability advantages, including a localised source of metabolic redox pairs for chemolithotrophic microorganisms and accessible trace metals. Similar pools could have provided transient environments for life on Mars; when paired with surface or near-surface ice, these habitability niches could have persisted into the Amazonian. Additionally, they offer a confined site for biosignature formation and deposition that lends itself well to in situ robotic exploration.

The potential of gypsum speleothems for paleoclimatology: application to the Iberian Roman Human Period.

Carbonate cave deposits (speleothems) have been used widely for paleoclimate reconstructions; however, few studies have examined the utility of other speleothem-forming minerals for this purpose. Here we demonstrate for the first time that stable isotopes (δ17O, δ18O and δD) of structurally-bound gypsum (CaSO4·2H2O) hydration water (GHW) can be used to infer paleoclimate. Specifically, we used a 63 cm-long gypsum stalactite from Sima Blanca Cave to reconstruct the climate history of SE Spain from ~ 800 BCE to ~ 800 CE. The gypsum stalactite indicates wet conditions in the cave and humid climate from ~ 200 BCE to 100 CE, at the time of the Roman Empire apogee in Hispania. From ~ 100 CE to ~ 600 CE, evaporation in the cave increased in response to regional aridification that peaked at ~ 500-600 CE, roughly coinciding with the transition between the Iberian Roman Humid Period and the Migration Period. Our record agrees with most Mediterranean and Iberian paleoclimate archives, demonstrating that stable isotopes of GHW in subaerial gypsum speleothems are a useful tool for paleoclimate reconstructions.

Author Correction: The potential of gypsum speleothems for paleoclimatology: application to the Iberian Roman Humid Period.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Author Correction: Intensified summer monsoon and the urbanization of Indus Civilization in northwest India.

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Intensified summer monsoon and the urbanization of Indus Civilization in northwest India.

Today the desert margins of northwest India are dry and unable to support large populations, but were densely occupied by the populations of the Indus Civilization during the middle to late Holocene. The hydroclimatic conditions under which Indus urbanization took place, which was marked by a period of expanded settlement into the Thar Desert margins, remains poorly understood. We measured the isotopic values (δ18O and δD) of gypsum hydration water in paleolake Karsandi sediments in northern Rajasthan to infer past changes in lake hydrology, which is sensitive to changing amounts of precipitation and evaporation. Our record reveals that relatively wet conditions prevailed at the northern edge of Rajasthan from ~5.1 ± 0.2 ka BP, during the beginning of the agricultural-based Early Harappan phase of the Indus Civilization. Monsoon rainfall intensified further between 5.0 and 4.4 ka BP, during the period when Indus urban centres developed in the western Thar Desert margin and on the plains of Haryana to its north. Drier conditions set in sometime after 4.4 ka BP, and by ~3.9 ka BP an eastward shift of populations had occurred. Our findings provide evidence that climate change was associated with both the expansion and contraction of Indus urbanism along the desert margin in northwest India.

Linking groundwater pollution to the decay of 15th-century sculptures in Burgos Cathedral (northern Spain).

Precipitation of salts-mainly hydrated Mg-Na sulfates-in building materials is rated as one of the most severe threats to the preservation of our architectural and cultural heritage. Nevertheless, the origin of this pathology is still unknown in many cases. Proper identification of the cause of damage is crucial for correct planning of future restoration actions. The goal of this study is to identify the source of the degradation compounds that are affecting the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (northern Spain). To this end, detailed characterization of minerals by in situ (Raman spectroscopy) and laboratory techniques (XRD, Raman and FTIR) was followed by major elements (ICP and IC) and isotopic analysis (δ(34)S and δ(15)N) of both the mineral phases precipitated on the retro-choir and the dissolved salts in groundwater in the vicinity of the cathedral. The results reveal unequivocal connection between the damage observed and capillary rise of salts-bearing water from the subsoil. The multianalytical methodology used is widely applicable to identify the origin of common affections suffered by historical buildings and masterpieces.

Spectroscopic Raman study of sulphate precipitation sequence in Rio Tinto mining district (SW Spain).

Acidic waters and sulphate-rich precipitates are typical by-products of mining activity such as in Rio Tinto (Huelva, SW Spain). This river drains pyrite mines situated in the Iberian Pyrite Belt which have been in operation since the Bronze Age and probably constitutes the oldest continuously operating mining activity over the world. In the present work, we have used Raman spectroscopy to study a wide range of natural mineral samples collected at Rio Tinto which origin is related to evaporation and mineral transformation processes in a wet and extreme acidic environment. In addition, we simulated the phenomenon of mineral precipitation in controlled conditions by using a simulator developed at the laboratory evaporating natural water collected at Rio Tinto. Also, a series of experiments using the same waters as small droplets have been carried out using micro-Raman technique. The droplets were placed on substrates with different chemical composition and reactivity. The results reveal that the precipitation sequence occurred in Rio Tinto mainly comprises copiapite and coquimbite group minerals followed by several other low hydrated iron sulphates. The experiments carried out on droplets allow estimating with higher accuracy the precipitation sequence.